Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2O 3 nanocrystalline films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.

Here, an approach is presented to design refractory-metal incorporated Ga 2O 3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga 2O 3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga 2O 3), higher Mo-content results in amorphization. Chemically-induced band gap variability (E g ~ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality andmore » performance of Ga-Mo-O films is possible by tuning the Mo-content.« less

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2O 3 nanocrystalline films

DOE PAGES

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.; ...

2017-07-01

Here, an approach is presented to design refractory-metal incorporated Ga 2O 3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga 2O 3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga 2O 3), higher Mo-content results in amorphization. Chemically-induced band gap variability (E g ~ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality andmore » performance of Ga-Mo-O films is possible by tuning the Mo-content.« less

Cadmium sulfide thin films growth by chemical bath deposition

NASA Astrophysics Data System (ADS)

Hariech, S.; Aida, M. S.; Bougdira, J.; Belmahi, M.; Medjahdi, G.; Genève, D.; Attaf, N.; Rinnert, H.

2018-03-01

Cadmium sulfide (CdS) thin films have been prepared by a simple technique such as chemical bath deposition (CBD). A set of samples CdS were deposited on glass substrates by varying the bath temperature from 55 to 75 °C at fixed deposition time (25 min) in order to investigate the effect of deposition temperature on CdS films physical properties. The determination of growth activation energy suggests that at low temperature CdS film growth is governed by the release of Cd2+ ions in the solution. The structural characterization indicated that the CdS films structure is cubic or hexagonal with preferential orientation along the direction (111) or (002), respectively. The optical characterization indicated that the films have a fairly high transparency, which varies between 55% and 80% in the visible range of the optical spectrum, the refractive index varies from 1.85 to 2.5 and the optical gap value of which can reach 2.2 eV. It can be suggested that these properties make these films perfectly suitable for their use as window film in thin films based solar cells.

Hard and soft acids and bases: structure and process.

PubMed

Reed, James L

2012-07-05

Under investigation is the structure and process that gives rise to hard-soft behavior in simple anionic atomic bases. That for simple atomic bases the chemical hardness is expected to be the only extrinsic component of acid-base strength, has been substantiated in the current study. A thermochemically based operational scale of chemical hardness was used to identify the structure within anionic atomic bases that is responsible for chemical hardness. The base's responding electrons have been identified as the structure, and the relaxation that occurs during charge transfer has been identified as the process giving rise to hard-soft behavior. This is in contrast the commonly accepted explanations that attribute hard-soft behavior to varying degrees of electrostatic and covalent contributions to the acid-base interaction. The ability of the atomic ion's responding electrons to cause hard-soft behavior has been assessed by examining the correlation of the estimated relaxation energies of the responding electrons with the operational chemical hardness. It has been demonstrated that the responding electrons are able to give rise to hard-soft behavior in simple anionic bases.

Elastohydrodynamic Traction Properties of Seed Oils

USDA-ARS?s Scientific Manuscript database

The elastohydrodynamic traction coefficient (tc) properties of nine seed oils of varying chemical structures, PAO and hexadecane, were investigated using a ball-on disk traction apparatus. The seed oils were: castor oil, a triglyceride with hydroxyl functional group; jojoba, a monoglyceride; and s...

Ambiguity of non-systematic chemical identifiers within and between small-molecule databases.

PubMed

Akhondi, Saber A; Muresan, Sorel; Williams, Antony J; Kors, Jan A

2015-01-01

A wide range of chemical compound databases are currently available for pharmaceutical research. To retrieve compound information, including structures, researchers can query these chemical databases using non-systematic identifiers. These are source-dependent identifiers (e.g., brand names, generic names), which are usually assigned to the compound at the point of registration. The correctness of non-systematic identifiers (i.e., whether an identifier matches the associated structure) can only be assessed manually, which is cumbersome, but it is possible to automatically check their ambiguity (i.e., whether an identifier matches more than one structure). In this study we have quantified the ambiguity of non-systematic identifiers within and between eight widely used chemical databases. We also studied the effect of chemical structure standardization on reducing the ambiguity of non-systematic identifiers. The ambiguity of non-systematic identifiers within databases varied from 0.1 to 15.2 % (median 2.5 %). Standardization reduced the ambiguity only to a small extent for most databases. A wide range of ambiguity existed for non-systematic identifiers that are shared between databases (17.7-60.2 %, median of 40.3 %). Removing stereochemistry information provided the largest reduction in ambiguity across databases (median reduction 13.7 percentage points). Ambiguity of non-systematic identifiers within chemical databases is generally low, but ambiguity of non-systematic identifiers that are shared between databases, is high. Chemical structure standardization reduces the ambiguity to a limited extent. Our findings can help to improve database integration, curation, and maintenance.

OPERA models for predicting physicochemical properties and environmental fate endpoints.

PubMed

Mansouri, Kamel; Grulke, Chris M; Judson, Richard S; Williams, Antony J

2018-03-08

The collection of chemical structure information and associated experimental data for quantitative structure-activity/property relationship (QSAR/QSPR) modeling is facilitated by an increasing number of public databases containing large amounts of useful data. However, the performance of QSAR models highly depends on the quality of the data and modeling methodology used. This study aims to develop robust QSAR/QSPR models for chemical properties of environmental interest that can be used for regulatory purposes. This study primarily uses data from the publicly available PHYSPROP database consisting of a set of 13 common physicochemical and environmental fate properties. These datasets have undergone extensive curation using an automated workflow to select only high-quality data, and the chemical structures were standardized prior to calculation of the molecular descriptors. The modeling procedure was developed based on the five Organization for Economic Cooperation and Development (OECD) principles for QSAR models. A weighted k-nearest neighbor approach was adopted using a minimum number of required descriptors calculated using PaDEL, an open-source software. The genetic algorithms selected only the most pertinent and mechanistically interpretable descriptors (2-15, with an average of 11 descriptors). The sizes of the modeled datasets varied from 150 chemicals for biodegradability half-life to 14,050 chemicals for logP, with an average of 3222 chemicals across all endpoints. The optimal models were built on randomly selected training sets (75%) and validated using fivefold cross-validation (CV) and test sets (25%). The CV Q 2 of the models varied from 0.72 to 0.95, with an average of 0.86 and an R 2 test value from 0.71 to 0.96, with an average of 0.82. Modeling and performance details are described in QSAR model reporting format and were validated by the European Commission's Joint Research Center to be OECD compliant. All models are freely available as an open-source, command-line application called OPEn structure-activity/property Relationship App (OPERA). OPERA models were applied to more than 750,000 chemicals to produce freely available predicted data on the U.S. Environmental Protection Agency's CompTox Chemistry Dashboard.

Distributed structure-searchable toxicity (DSSTox) public database network: a proposal.

PubMed

Richard, Ann M; Williams, ClarLynda R

2002-01-29

The ability to assess the potential genotoxicity, carcinogenicity, or other toxicity of pharmaceutical or industrial chemicals based on chemical structure information is a highly coveted and shared goal of varied academic, commercial, and government regulatory groups. These diverse interests often employ different approaches and have different criteria and use for toxicity assessments, but they share a need for unrestricted access to existing public toxicity data linked with chemical structure information. Currently, there exists no central repository of toxicity information, commercial or public, that adequately meets the data requirements for flexible analogue searching, Structure-Activity Relationship (SAR) model development, or building of chemical relational databases (CRD). The distributed structure-searchable toxicity (DSSTox) public database network is being proposed as a community-supported, web-based effort to address these shared needs of the SAR and toxicology communities. The DSSTox project has the following major elements: (1) to adopt and encourage the use of a common standard file format (structure data file (SDF)) for public toxicity databases that includes chemical structure, text and property information, and that can easily be imported into available CRD applications; (2) to implement a distributed source approach, managed by a DSSTox Central Website, that will enable decentralized, free public access to structure-toxicity data files, and that will effectively link knowledgeable toxicity data sources with potential users of these data from other disciplines (such as chemistry, modeling, and computer science); and (3) to engage public/commercial/academic/industry groups in contributing to and expanding this community-wide, public data sharing and distribution effort. The DSSTox project's overall aims are to effect the closer association of chemical structure information with existing toxicity data, and to promote and facilitate structure-based exploration of these data within a common chemistry-based framework that spans toxicological disciplines.

Elastohydrodynamic (EHD) traction properties of seed oils

USDA-ARS?s Scientific Manuscript database

The elastohydrodynamic traction coefficient (tc) properties of nine seed oils of varying chemical structures, PAO and hexadecane, were investigated using a ball-on disk traction apparatus. The seed oils were: castor oil, a triglyceride with hydroxyl functional group; jojoba, a monoglyceride; and sev...

Tribological properties of limonene bisphosphonates

USDA-ARS?s Scientific Manuscript database

Limonene was chemically modified by reacting it with dialkyl phosphites of varying alkyl structures under inert atmosphere in the presence of free radical initiators. The reaction gave a mixture of mono- and di-adduct products, and was optimized to produce only the diadduct product limonene bisphosp...

CURRENT PRACTICES IN QSAR DEVELOPMENT AND APPLICATIONS

EPA Science Inventory

Current Practices in QSAR Development and Applications

Although it is commonly assumed that the structure and properties of a single chemical determines its activity in a particular biological system, it is only through study of how biological activity varies with changes...

Structural changes in gluten protein structure after addition of emulsifier. A Raman spectroscopy study

NASA Astrophysics Data System (ADS)

Ferrer, Evelina G.; Gómez, Analía V.; Añón, María C.; Puppo, María C.

2011-06-01

Food protein product, gluten protein, was chemically modified by varying levels of sodium stearoyl lactylate (SSL); and the extent of modifications (secondary and tertiary structures) of this protein was analyzed by using Raman spectroscopy. Analysis of the Amide I band showed an increase in its intensity mainly after the addition of the 0.25% of SSL to wheat flour to produced modified gluten protein, pointing the formation of a more ordered structure. Side chain vibrations also confirmed the observed changes.

Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge

DOE PAGES

Romero-Mangado, Jaione; Nordlund, Dennis; Soberon, Felipe; ...

2016-02-12

This paper presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure(NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure.more » The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD.« less

Structure elucidation of a novel oligosaccharide (Medalose) from camel milk

NASA Astrophysics Data System (ADS)

Gangwar, Lata; Singh, Rinku; Deepak, Desh

2018-02-01

Free oligosaccharides are the third most abundant solid component in milk after lactose and lipids. The study of milk oligosaccharides indicate that nutrients are not only benefits the infant's gut but also perform a number of other functions which include stimulation of growth, receptor analogues to inhibit binding of pathogens and substances that promote postnatal brain development. Surveys reveal that camel milk oligosaccharides possess varied biological activities that help in the treatment of diabetes, asthma, anaemia, piles and also a food supplement to milking mothers. In this research, camel milk was selected for its oligosaccharide contents, which was then processed by Kobata and Ginsburg method followed by the HPLC and CC techniques. Structure elucidation of isolated compound was done by the chemical degradation, chemical transformation and comparison of chemical shift of NMR data of natural and acetylated oligosaccharide structure reporter group theory, the 1H, 13C NMR, 2D-NMR (COSY, TOCSY and HSQC) techniques, and mass spectrometry. The structure was elucidated as under: MEDALOSE

Effect of gamma radiation on low density polyethylene (LDPE) films: optical, dielectric and FTIR studies.

PubMed

Moez, A Abdel; Aly, S S; Elshaer, Y H

2012-07-01

The low density polyethylene (LDPE) films were irradiated with gamma radiation in the dose range varied from 20 to 400 kGy. The induced changes in the chemical structure and dielectric properties for the irradiated films were investigated. The structure modifications: crystallinity as well as possible molecular changes of the polymer were recognized using Fourier Transform Infrared Spectroscopy (FTIR). The optical results were determined from transmission, reflection and absorption spectra for these films. The dielectric properties of these films were calculated using optical methods. Result indicates small variation in crystallinity which could be increased or decreased depending on the relative importance of the structural and chemical changes. Copyright © 2012 Elsevier B.V. All rights reserved.

Dynamic transition in the structure of an energetic crystal during chemical reactions at shock front prior to detonation.

PubMed

Nomura, Ken-Ichi; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya; van Duin, Adri C T; Goddard, William A

2007-10-05

Mechanical stimuli in energetic materials initiate chemical reactions at shock fronts prior to detonation. Shock sensitivity measurements provide widely varying results, and quantum-mechanical calculations are unable to handle systems large enough to describe shock structure. Recent developments in reactive force-field molecular dynamics (ReaxFF-MD) combined with advances in parallel computing have paved the way to accurately simulate reaction pathways along with the structure of shock fronts. Our multimillion-atom ReaxFF-MD simulations of l,3,5-trinitro-l,3,5-triazine (RDX) reveal that detonation is preceded by a transition from a diffuse shock front with well-ordered molecular dipoles behind it to a disordered dipole distribution behind a sharp front.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1986-01-01

Describes two demonstrations designed to help chemistry students visualize certain chemical properties. One experiment uses balloons to illustrate the behavior of gases under varying temperatures and pressures. The other uses a makeshift pea shooter and a commercial model to demonstrate atomic structure and the behavior of high-speed particles.…

Method of varying a characteristic of an optical vertical cavity structure formed by metalorganic vapor phase epitaxy

DOEpatents

Hou, Hong Q.; Coltrin, Michael E.; Choquette, Kent D.

2001-01-01

A process for forming an array of vertical cavity optical resonant structures wherein the structures in the array have different detection or emission wavelengths. The process uses selective area growth (SAG) in conjunction with annular masks of differing dimensions to control the thickness and chemical composition of the materials in the optical cavities in conjunction with a metalorganic vapor phase epitaxy (MOVPE) process to build these arrays.

Leaching behavior and chemical stability of copper butyl xanthate complex under acidic conditions.

PubMed

Chang, Yi Kuo; Chang, Juu En; Chiang, Li Choung

2003-08-01

Although xanthate addition can be used for treating copper-containing wastewater, a better understanding of the leaching toxicity and the stability characteristics of the copper xanthate complexes formed is essential. This work was undertaken to evaluate the leaching behavior of copper xanthate complex precipitates by means of toxicity characteristics leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) using 1 N acetic acid solution as the leachant. Also, the chemical stability of the copper xanthate complex during extraction has been examined with the studying of variation of chemical structure using UV-vis, Fourier transform infrared and X-ray photoelectron spectroscopies (XPS). Both TCLP and SDLT results showed that a negligible amount of copper ion was leached out from the copper xanthate complex precipitate, indicating that the complex exhibited a high degree of copper leaching stability under acidic conditions. Nevertheless, chemical structure of the copper xanthate complex precipitate varied during the leaching tests. XPS data suggested that the copper xanthate complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acid extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the copper xanthate complex.

Current Status and Future Prospects of Marine Natural Products (MNPs) as Antimicrobials.

PubMed

Choudhary, Alka; Naughton, Lynn M; Montánchez, Itxaso; Dobson, Alan D W; Rai, Dilip K

2017-08-28

The marine environment is a rich source of chemically diverse, biologically active natural products, and serves as an invaluable resource in the ongoing search for novel antimicrobial compounds. Recent advances in extraction and isolation techniques, and in state-of-the-art technologies involved in organic synthesis and chemical structure elucidation, have accelerated the numbers of antimicrobial molecules originating from the ocean moving into clinical trials. The chemical diversity associated with these marine-derived molecules is immense, varying from simple linear peptides and fatty acids to complex alkaloids, terpenes and polyketides, etc. Such an array of structurally distinct molecules performs functionally diverse biological activities against many pathogenic bacteria and fungi, making marine-derived natural products valuable commodities, particularly in the current age of antimicrobial resistance. In this review, we have highlighted several marine-derived natural products (and their synthetic derivatives), which have gained recognition as effective antimicrobial agents over the past five years (2012-2017). These natural products have been categorized based on their chemical structures and the structure-activity mediated relationships of some of these bioactive molecules have been discussed. Finally, we have provided an insight into how genome mining efforts are likely to expedite the discovery of novel antimicrobial compounds.

ToxCast Chemical Landscape: Paving the Road to 21st Century Toxicology.

PubMed

Richard, Ann M; Judson, Richard S; Houck, Keith A; Grulke, Christopher M; Volarath, Patra; Thillainadarajah, Inthirany; Yang, Chihae; Rathman, James; Martin, Matthew T; Wambaugh, John F; Knudsen, Thomas B; Kancherla, Jayaram; Mansouri, Kamel; Patlewicz, Grace; Williams, Antony J; Little, Stephen B; Crofton, Kevin M; Thomas, Russell S

2016-08-15

The U.S. Environmental Protection Agency's (EPA) ToxCast program is testing a large library of Agency-relevant chemicals using in vitro high-throughput screening (HTS) approaches to support the development of improved toxicity prediction models. Launched in 2007, Phase I of the program screened 310 chemicals, mostly pesticides, across hundreds of ToxCast assay end points. In Phase II, the ToxCast library was expanded to 1878 chemicals, culminating in the public release of screening data at the end of 2013. Subsequent expansion in Phase III has resulted in more than 3800 chemicals actively undergoing ToxCast screening, 96% of which are also being screened in the multi-Agency Tox21 project. The chemical library unpinning these efforts plays a central role in defining the scope and potential application of ToxCast HTS results. The history of the phased construction of EPA's ToxCast library is reviewed, followed by a survey of the library contents from several different vantage points. CAS Registry Numbers are used to assess ToxCast library coverage of important toxicity, regulatory, and exposure inventories. Structure-based representations of ToxCast chemicals are then used to compute physicochemical properties, substructural features, and structural alerts for toxicity and biotransformation. Cheminformatics approaches using these varied representations are applied to defining the boundaries of HTS testability, evaluating chemical diversity, and comparing the ToxCast library to potential target application inventories, such as used in EPA's Endocrine Disruption Screening Program (EDSP). Through several examples, the ToxCast chemical library is demonstrated to provide comprehensive coverage of the knowledge domains and target inventories of potential interest to EPA. Furthermore, the varied representations and approaches presented here define local chemistry domains potentially worthy of further investigation (e.g., not currently covered in the testing library or defined by toxicity "alerts") to strategically support data mining and predictive toxicology modeling moving forward.

Advances in Chemical and Structural Characterization of Concretion with Implications for Modeling Marine Corrosion

NASA Astrophysics Data System (ADS)

Johnson, Donald L.; DeAngelis, Robert J.; Medlin, Dana J.; Carr, James D.; Conlin, David L.

2014-05-01

The Weins number model and concretion equivalent corrosion rate methodology were developed as potential minimum-impact, cost-effective techniques to determine corrosion damage on submerged steel structures. To apply the full potential of these technologies, a detailed chemical and structural characterization of the concretion (hard biofouling) that transforms into iron bearing minerals is required. The fractions of existing compounds and the quantitative chemistries are difficult to determine from x-ray diffraction. Environmental scanning electron microscopy was used to present chemical compositions by means of energy-dispersive spectroscopy (EDS). EDS demonstrates the chemical data in mapping format or in point or selected area chemistries. Selected-area EDS data collection at precise locations is presented in terms of atomic percent. The mechanism of formation and distribution of the iron-bearing mineral species at specific locations will be presented. Based on water retention measurements, porosity in terms of void volume varies from 15 v/o to 30 v/o (vol.%). The void path displayed by scanning electron microscopy imaging illustrates the tortuous path by which oxygen migrates in the water phase within the concretion from seaside to metalside.

Pseudomonas aeruginosa biofilm formation and UV/irradiation exposure change surface and chemical structures of Pre-Production Resin Pellets

NASA Astrophysics Data System (ADS)

Stam, C. N.; Neal, A.; Park, S.; Mielke, R.; Tsapin, A. I.; Bhartia, R.; Salas, E.; Hug, W.; Behar, A. E.; Nadeau, J. L.

2011-12-01

Microbial interactions with synthetic polymers in open ocean is poorly understood. Plastics are a major and persistent contaminant of ocean waters. Many of these plastics are contaminated with toxic and synthetic chemicals that persist in the environment with minimal degradation. The purpose of this study is to look at the effects that microbial biofilm communities have on both surface and chemical structures of pre-production resin pellets (PRPs). Pseudomonas aeruignosa was grown with PRPs under multiple growth and nutrient conditions. These conditions were combined with varying lengths of UV exposures common to ocean environments. Material degradation of the PRPs and the changing surface and chemical structures of these synthetic polymers was evaluated using a combination of Fourier transform infrared spectroscopy, environmental scanning electron microscopy, scanning transmission electron microscopy, X-ray microtomography, and ArcGIS mapping. This study correlates with previous studies conducted on environmental PRP's , collected on the 2009 Project Kaisei expedition in the Subtropical Convergence Zone of the North Pacific Gyre. Further studies are needed to develop a full understanding of degradation rates of synthetic polymers in oceanic environments.

Recent Developments in Toxico-Cheminformatics: A New ...

EPA Pesticide Factsheets

Efforts to improve public access to chemical toxicity information resources, coupled with new high-throughput screening (HTS) data and efforts to systematize legacy toxicity studies, have the potential to significantly improve predictive capabilities in toxicology. Important recent developments include: 1) large and growing public resources that link chemical structures to biological activity and toxicity data in searchable format, and that offer more nuanced and varied representations of activity; 2) standardized relational data models that capture relevant details of chemical treatment and effects of published in vivo experiments; and 3) the generation of large amounts of new data from public efforts that are employing HTS technologies to probe a wide range of bioactivity and cellular processes across large swaths of chemical space. Most recently, EPA’s DSSTox project has published several new EPA chemical data inventories (IRIS, HPV, ToxCast) and added an on-line capability for structure (substructure or similarity)-searching through all or parts of the published DSSTox data files. These efforts are, for the first time in many cases, opening up a structure-paved two-way highway between previously inaccessible or isolated public chemical data repositories and large public resources, such as PubChem. In addition, public initiatives (such as ToxML) are developing systematized data models of toxicity study areas, and introducing standardized templates, contr

Structure of complex cell wall polysaccharides isolated from Trichoderma and Hypocrea species.

PubMed

Prieto, A; Leal, J A; Poveda, A; Jiménez-Barbero, J; Gómez-Miranda, B; Domenech, J; Ahrazem, O; Bernabé, M

1997-11-28

The structure of fungal polysaccharides isolated from the cell wall of Trichoderma reesei, T. koningii, and Hypocrea psychrophila, have been investigated by means of chemical analyses and 1D and 2D NMR spectroscopy. The polysaccharides have an irregular structure, idealized as follows: [formula: see text] The proportions of the different side chains vary from a species to another, being n above some three times larger in H. psychrophila than in T. reesei or T. koningii.

Programmable assembly of pressure sensors using pattern-forming bacteria.

PubMed

Cao, Yangxiaolu; Feng, Yaying; Ryser, Marc D; Zhu, Kui; Herschlag, Gregory; Cao, Changyong; Marusak, Katherine; Zauscher, Stefan; You, Lingchong

2017-11-01

Biological systems can generate microstructured materials that combine organic and inorganic components and possess diverse physical and chemical properties. However, these natural processes in materials fabrication are not readily programmable. Here, we use a synthetic-biology approach to assemble patterned materials. We demonstrate programmable fabrication of three-dimensional (3D) materials by printing engineered self-patterning bacteria on permeable membranes that serve as a structural scaffold. Application of gold nanoparticles to the colonies creates hybrid organic-inorganic dome structures. The dynamics of the dome structures' response to pressure is determined by their geometry (colony size, dome height, and pattern), which is easily modified by varying the properties of the membrane (e.g., pore size and hydrophobicity). We generate resettable pressure sensors that process signals in response to varying pressure intensity and duration.

Asymmetric Membranes from Two Chemically Distinct Triblock Terpolymers Blended during Standard Membrane Fabrication.

PubMed

Li, Yuk Mun; Srinivasan, Divya; Vaidya, Parth; Gu, Yibei; Wiesner, Ulrich

2016-10-01

Deviating from the traditional formation of block copolymer derived isoporous membranes from one block copolymer chemistry, here asymmetric membranes with isoporous surface structure are derived from two chemically distinct block copolymers blended during standard membrane fabrication. As a first proof of principle, the fabrication of asymmetric membranes is reported, which are blended from two chemically distinct triblock terpolymers, poly(isoprene-b-styrene-b-(4-vinyl)pyridine) (ISV) and poly(isoprene-b-styrene-b-(dimethylamino)ethyl methacrylate) (ISA), differing in the pH-responsive hydrophilic segment. Using block copolymer self-assembly and nonsolvent induced phase separation process, pure and blended membranes are prepared by varying weight ratios of ISV to ISA. Pure and blended membranes exhibit a thin, selective layer of pores above a macroporous substructure. Observed permeabilities at varying pH values of blended membranes depend on relative triblock terpolymer composition. These results open a new direction for membrane fabrication through the use of mixtures of chemically distinct block copolymers enabling the tailoring of membrane surface chemistries and functionalities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The cuticle modulates ultraviolet reflectance of avian eggshells

PubMed Central

Fecheyr-Lippens, Daphne C.; Igic, Branislav; D'Alba, Liliana; Hanley, Daniel; Verdes, Aida; Holford, Mande; Waterhouse, Geoffrey I. N.; Grim, Tomas; Hauber, Mark E.; Shawkey, Matthew D.

2015-01-01

ABSTRACT Avian eggshells are variedly coloured, yet only two pigments, biliverdin and protoporphyrin IX, are known to contribute to the dramatic diversity of their colours. By contrast, the contributions of structural or other chemical components of the eggshell are poorly understood. For example, unpigmented eggshells, which appear white to the human eye, vary in their ultraviolet (UV) reflectance, which may be detectable by birds. We investigated the proximate mechanisms for the variation in UV-reflectance of unpigmented bird eggshells using spectrophotometry, electron microscopy, chemical analyses, and experimental manipulations. We specifically tested how UV-reflectance is affected by the eggshell cuticle, the outermost layer of most avian eggshells. The chemical dissolution of the outer eggshell layers, including the cuticle, increased UV-reflectance for only eggshells that contained a cuticle. Our findings demonstrate that the outer eggshell layers, including the cuticle, absorb UV-light, probably because they contain higher levels of organic components and other chemicals, such as calcium phosphates, compared to the predominantly calcite-based eggshell matrix. These data highlight the need to examine factors other than the known pigments in studies of avian eggshell colour. PMID:25964661

Reduced graphs and their applications in chemoinformatics.

PubMed

Birchall, Kristian; Gillet, Valerie J

2011-01-01

Reduced graphs provide summary representations of chemical structures by collapsing groups of connected atoms into single nodes while preserving the topology of the original structures. This chapter reviews the extensive work that has been carried out on reduced graphs at The University of Sheffield and includes discussion of their application to the representation and search of Markush structures in patents, the varied approaches that have been implemented for similarity searching, their use in cluster representation, the different ways in which they have been applied to extract structure-activity relationships and their use in encoding bioisosteres.

Carbon Isotope Chemistry in Molecular Clouds

NASA Technical Reports Server (NTRS)

Robertson, Amy N.; Willacy, Karen

2012-01-01

Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

IMPORTANCE OF ACTIVATED CARBON'S OXYGEN SURFACE FUNCTIONAL GROUPS ON ELEMENTAL MERCURY ADSORPTION

EPA Science Inventory

The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury [Hg(0)] was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N2), air oxidat...

Digitally tunable physicochemical coding of material composition and topography in continuous microfibres.

PubMed

Kang, Edward; Jeong, Gi Seok; Choi, Yoon Young; Lee, Kwang Ho; Khademhosseini, Ali; Lee, Sang-Hoon

2011-09-04

Heterotypic functional materials with compositional and topographical properties that vary spatiotemporally on the micro- or nanoscale are common in nature. However, fabricating such complex materials in the laboratory remains challenging. Here we describe a method to continuously create microfibres with tunable morphological, structural and chemical features using a microfluidic system consisting of a digital, programmable flow control that mimics the silk-spinning process of spiders. With this method we fabricated hydrogel microfibres coded with varying chemical composition and topography along the fibre, including gas micro-bubbles as well as nanoporous spindle-knots and joints that enabled directional water collection. We also explored the potential use of the coded microfibres for tissue engineering applications by creating multifunctional microfibres with a spatially controlled co-culture of encapsulated cells.

High within-canopy variation in isoprene emission potentials in temperate trees: Implications for predicting canopy-scale isoprene fluxes

NASA Astrophysics Data System (ADS)

Niinemets, ÜLo; Copolovici, Lucian; Hüve, Katja

2010-12-01

Isoprene emission potential (ES) varies in tree canopies, and such variations have potentially major implications for predicting canopy level emissions. So far, quantitative relationships of ES with irradiance are missing, and interspecific variation in ES plasticity and potential effects on canopy level emissions have not been characterized. ES, foliage structural, chemical, and photosynthetic characteristics were studied relative to integrated within-canopy daily quantum flux density (Qint) in temperate deciduous tree species Quercus robur, Populus tremula, Salix alba, and Salix caprea, and canopy isoprene emissions were calculated considering observed variation in ES and under different simplifying assumptions. Strong positive curvilinear relationships between nitrogen and dry mass per unit area, photosynthetic potentials and ES per area with Qint were observed. Structural, chemical, and photosynthetic traits varied 1.5-fold to 4-fold and ES per area 3-fold to 27-fold within the canopy. ES variation reflected accumulation of mesophyll cell layers and greater emission capacity of average cells. Species with largest structural and photosynthetic plasticity had greatest plasticity in ES. Relative to the simulation considering within-canopy variation in ES, the bias from assuming a constant ES varied between -8% and +68%, and it scaled positively with ES plasticity. The bias of big-leaf simulations varied between -22% and -35%, and it scaled negatively with ES plasticity. A generalized canopy response function of ES developed for all species resulted in the lowest bias between -11% and 6% and can be recommended for practical applications. The results highlight huge within-canopy and interspecific variation in ES and demonstrate that ignoring these variations strongly biases canopy emission predictions.

Chitin and Chitosan Preparation from Marine Sources. Structure, Properties and Applications

PubMed Central

Younes, Islem; Rinaudo, Marguerite

2015-01-01

This review describes the most common methods for recovery of chitin from marine organisms. In depth, both enzymatic and chemical treatments for the step of deproteinization are compared, as well as different conditions for demineralization. The conditions of chitosan preparation are also discussed, since they significantly impact the synthesis of chitosan with varying degree of acetylation (DA) and molecular weight (MW). In addition, the main characterization techniques applied for chitin and chitosan are recalled, pointing out the role of their solubility in relation with the chemical structure (mainly the acetyl group distribution along the backbone). Biological activities are also presented, such as: antibacterial, antifungal, antitumor and antioxidant. Interestingly, the relationship between chemical structure and biological activity is demonstrated for chitosan molecules with different DA and MW and homogeneous distribution of acetyl groups for the first time. In the end, several selected pharmaceutical and biomedical applications are presented, in which chitin and chitosan are recognized as new biomaterials taking advantage of their biocompatibility and biodegradability. PMID:25738328

Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses.

PubMed

Kansal, Ishu; Reddy, AlluAmarnath; Muñoz, Francisco; Choi, Seong-Jun; Kim, Hae-Won; Tulyaganov, Dilshat U; Ferreira, José M F

2014-11-01

We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO-MgO-SiO2-P2O5-CaF2 system. The (29)Si and (31)P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na2O/MgO ratios exhibit a silicate glass network with the dominance of Q(2)(Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1h and 7 days while their chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Increasing Na(+)/Mg(2+) ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium. Copyright © 2014 Elsevier B.V. All rights reserved.

Numerical simulation of two-dimensional flow over a heated carbon surface with coupled heterogeneous and homogeneous reactions

NASA Astrophysics Data System (ADS)

Johnson, Ryan Federick; Chelliah, Harsha Kumar

2017-01-01

For a range of flow and chemical timescales, numerical simulations of two-dimensional laminar flow over a reacting carbon surface were performed to understand further the complex coupling between heterogeneous and homogeneous reactions. An open-source computational package (OpenFOAM®) was used with previously developed lumped heterogeneous reaction models for carbon surfaces and a detailed homogeneous reaction model for CO oxidation. The influence of finite-rate chemical kinetics was explored by varying the surface temperatures from 1800 to 2600 K, while flow residence time effects were explored by varying the free-stream velocity up to 50 m/s. The reacting boundary layer structure dependence on the residence time was analysed by extracting the ratio of chemical source and species diffusion terms. The important contributions of radical species reactions on overall carbon removal rate, which is often neglected in multi-dimensional simulations, are highlighted. The results provide a framework for future development and validation of lumped heterogeneous reaction models based on multi-dimensional reacting flow configurations.

Correlations Between Structural and Magnetic Properties of Co2 FeSi Heusler-Alloy Thin Films

NASA Astrophysics Data System (ADS)

Zhu, Weihua; Wu, Di; Zhao, Bingcheng; Zhu, Zhendong; Yang, Xiaodi; Zhang, Zongzhi; Jin, Q. Y.

2017-09-01

The structural and magnetic properties are the most important parameters for practical applications of Co-based Heusler alloys. The correlations between the crystallization degree, chemical order, magnetic coercivity, saturation magnetization (MS ), and in-plane magnetic anisotropies are systematically investigated for Co2FeSi (CFS) films fabricated at different temperatures (TS ). XRD shows that the CFS layer changes progressively from a disordered crystal structure into a chemically disordered A 2 structure and further into a chemically ordered B 2 and even L 21 structures when increasing TS up to 480 °C . Meanwhile, the static angular remanence magnetization curves show a clear transition of magnetic anisotropy from twofold to fourfold symmetry, due to the competition effect between the uniaxial anisotropy field HU and biaxial anisotropy field HB . The HU value is found to be weakly dependent on TS , while HB shows a continuous enhancement at TS>300 °C , implying that the enhancement of the L 21 ordering degree would not weaken the biaxial anisotropy. The varying trend of HB is similar to MS , which can be respectively attributed to the improved crystal structure and chemical order. The anisotropic fields and their variation behaviors determined by a vibrating sample magnetometer are highly consistent with the results by a time-resolved magneto-optical Kerr effect study. Our findings provide a better understanding of the structural ordering and magnetic anisotropy, which will be helpful for designing advanced spintronic devices.

Programmable assembly of pressure sensors using pattern-forming bacteria

PubMed Central

Cao, Yangxiaolu; Feng, Yaying; Ryser, Marc D.; Zhu, Kui; Herschlag, Gregory; Cao, Changyong; Marusak, Katherine; Zauscher, Stefan; You, Lingchong

2017-01-01

Biological systems can generate microstructured materials that combine organic and inorganic components and possess diverse physical and chemical properties. However, these natural processes in materials fabrication are not readily programmable. Here, we use a synthetic-biology approach to mimic such natural processes to assemble patterned materials.. We demonstrate programmable fabrication of three-dimensional (3D) materials by printing engineered self-patterning bacteria on permeable membranes that serve as a structural scaffold. Application of gold nanoparticles to the colonies creates hybrid organic-inorganic dome structures. The dynamics of the dome structures' response to pressure is determined by their geometry (colony size, dome height and pattern), which is easily modified by varying the properties of the membrane (e.g., pore size and hydrophobicity). We generate resettable pressure sensors that process signals in response to varying pressure intensity and duration. PMID:28991268

Current Status and Future Prospects of Marine Natural Products (MNPs) as Antimicrobials

PubMed Central

Choudhary, Alka; Naughton, Lynn M.; Montánchez, Itxaso

2017-01-01

The marine environment is a rich source of chemically diverse, biologically active natural products, and serves as an invaluable resource in the ongoing search for novel antimicrobial compounds. Recent advances in extraction and isolation techniques, and in state-of-the-art technologies involved in organic synthesis and chemical structure elucidation, have accelerated the numbers of antimicrobial molecules originating from the ocean moving into clinical trials. The chemical diversity associated with these marine-derived molecules is immense, varying from simple linear peptides and fatty acids to complex alkaloids, terpenes and polyketides, etc. Such an array of structurally distinct molecules performs functionally diverse biological activities against many pathogenic bacteria and fungi, making marine-derived natural products valuable commodities, particularly in the current age of antimicrobial resistance. In this review, we have highlighted several marine-derived natural products (and their synthetic derivatives), which have gained recognition as effective antimicrobial agents over the past five years (2012–2017). These natural products have been categorized based on their chemical structures and the structure-activity mediated relationships of some of these bioactive molecules have been discussed. Finally, we have provided an insight into how genome mining efforts are likely to expedite the discovery of novel antimicrobial compounds. PMID:28846659

Toxico-Cheminformatics: New and Expanding Public ...

EPA Pesticide Factsheets

High-throughput screening (HTS) technologies, along with efforts to improve public access to chemical toxicity information resources and to systematize older toxicity studies, have the potential to significantly improve information gathering efforts for chemical assessments and predictive capabilities in toxicology. Important developments include: 1) large and growing public resources that link chemical structures to biological activity and toxicity data in searchable format, and that offer more nuanced and varied representations of activity; 2) standardized relational data models that capture relevant details of chemical treatment and effects of published in vivo experiments; and 3) the generation of large amounts of new data from public efforts that are employing HTS technologies to probe a wide range of bioactivity and cellular processes across large swaths of chemical space. By annotating toxicity data with associated chemical structure information, these efforts link data across diverse study domains (e.g., ‘omics’, HTS, traditional toxicity studies), toxicity domains (carcinogenicity, developmental toxicity, neurotoxicity, immunotoxicity, etc) and database sources (EPA, FDA, NCI, DSSTox, PubChem, GEO, ArrayExpress, etc.). Public initiatives are developing systematized data models of toxicity study areas and introducing standardized templates, controlled vocabularies, hierarchical organization, and powerful relational searching capability across capt

Insight into Amyloid Structure Using Chemical Probes

PubMed Central

Reinke, Ashley A.; Gestwicki, Jason E.

2011-01-01

Alzheimer’s disease (AD) is a common neurodegenerative disorder characterized by the deposition of amyloids in the brain. One prominent form of amyloid is composed of repeating units of the amyloid-β (Aβ) peptide. Over the past decade, it has become clear that these Aβ amyloids are not homogeneous; rather, they are composed of a series of structures varying in their overall size and shape and the number of Aβ peptides they contain. Recent theories suggest that these different amyloid conformations may play distinct roles in disease, although their relative contributions are still being discovered. Here, we review how chemical probes, such as congo red, thioflavin T and their derivatives, have been powerful tools for better understanding amyloid structure and function. Moreover, we discuss how design and deployment of conformationally selective probes might be used to test emerging models of AD. PMID:21457473

CONTRIBUTIONS OF CHEMICAL EXCHANGE TO T1ρ DISPERSION IN A TISSUE MODEL

PubMed Central

Cobb, Jared G.; Xie, Jingping; Gore, John C.

2015-01-01

Variations in T1ρ with locking-field strength (T1ρ dispersion) may be used to estimate proton exchange rates. We developed a novel approach utilizing the second derivative of the dispersion curve to measure exchange in a model system of cross-linked polyacrylamide gels. These gels were varied in relative composition of co-monomers, increasing stiffness, and in pH, modifying exchange rates. MR images were recorded with a spin-locking sequence as described by Sepponen et al. These measurements were fit to a mono-exponential decay function yielding values for T1ρ at each locking-field measured. These values were then fit to a model by Chopra et al. for estimating exchange rates. For low stiffness gels, the calculated exchange values increased by a factor of 4 as pH increased, consistent with chemical exchange being the dominant contributor to T1ρ dispersion. Interestingly, calculated chemical exchange rates also increased with stiffness, likely due to modified side-chain exchange kinetics as the composition varied. This paper demonstrates a new method to assess the structural and chemical effects on T1ρ relaxation dispersion with a suitable model. These phenomena may be exploited in an imaging context to emphasize the presence of nuclei of specific exchange rates, rather than chemical shifts. PMID:21590720

Spherical silicon-shell photonic band gap structures fabricated by laser-assisted chemical vapor deposition

NASA Astrophysics Data System (ADS)

Wang, H.; Yang, Z. Y.; Lu, Y. F.

2007-02-01

Laser-assisted chemical vapor deposition was applied in fabricating three-dimensional (3D) spherical-shell photonic band gap (PBG) structures by depositing silicon shells covering silica particles, which had been self-assembled into 3D colloidal crystals. The colloidal crystals of self-assembled silica particles were formed on silicon substrates using the isothermal heating evaporation approach. A continuous wave Nd:YAG laser (1064nm wavelength) was used to deposit silicon shells by thermally decomposing disilane gas. Periodic silicon-shell/silica-particle PBG structures were obtained. By removing the silica particles enclosed in the silicon shells using hydrofluoric acid, hollow spherical silicon-shell arrays were produced. This technique is capable of fabricating structures with complete photonic band gaps, which is predicted by simulations with the plane wave method. The techniques developed in this study have the potential to flexibly engineer the positions of the PBGs by varying both the silica particle size and the silicon-shell thickness. Ellipsometry was used to investigate the specific photonic band gaps for both structures.

Protein Structural Analysis via Mass Spectrometry-Based Proteomics

PubMed Central

Artigues, Antonio; Nadeau, Owen W.; Rimmer, Mary Ashley; Villar, Maria T.; Du, Xiuxia; Fenton, Aron W.; Carlson, Gerald M.

2017-01-01

Modern mass spectrometry (MS) technologies have provided a versatile platform that can be combined with a large number of techniques to analyze protein structure and dynamics. These techniques include the three detailed in this chapter: 1) hydrogen/deuterium exchange (HDX), 2) limited proteolysis, and 3) chemical crosslinking (CX). HDX relies on the change in mass of a protein upon its dilution into deuterated buffer, which results in varied deuterium content within its backbone amides. Structural information on surface exposed, flexible or disordered linker regions of proteins can be achieved through limited proteolysis, using a variety of proteases and only small extents of digestion. CX refers to the covalent coupling of distinct chemical species and has been used to analyze the structure, function and interactions of proteins by identifying crosslinking sites that are formed by small multi-functional reagents, termed crosslinkers. Each of these MS applications is capable of revealing structural information for proteins when used either with or without other typical high resolution techniques, including NMR and X-ray crystallography. PMID:27975228

Tortuous path chemical preconcentrator

DOEpatents

Manginell, Ronald P.; Lewis, Patrick R.; Adkins, Douglas R.; Wheeler, David R.; Simonson, Robert J.

2010-09-21

A non-planar, tortuous path chemical preconcentrator has a high internal surface area having a heatable sorptive coating that can be used to selectively collect and concentrate one or more chemical species of interest from a fluid stream that can be rapidly released as a concentrated plug into an analytical or microanalytical chain for separation and detection. The non-planar chemical preconcentrator comprises a sorptive support structure having a tortuous flow path. The tortuosity provides repeated twists, turns, and bends to the flow, thereby increasing the interfacial contact between sample fluid stream and the sorptive material. The tortuous path also provides more opportunities for desorption and readsorption of volatile species. Further, the thermal efficiency of the tortuous path chemical preconcentrator is comparable or superior to the prior non-planar chemical preconcentrator. Finally, the tortuosity can be varied in different directions to optimize flow rates during the adsorption and desorption phases of operation of the preconcentrator.

Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations.

PubMed

Wang, Tuo; Yang, Hui; Kubicki, James D; Hong, Mei

2016-06-13

The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D (13)C-(13)C correlation spectra of uniformly (13)C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose (13)C chemical shifts differ significantly from the (13)C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing, and hydrogen bonding from celluloses of other organisms. 2D (13)C-(13)C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Celluloses f and g are well mixed chains on the microfibril surface, celluloses a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of bacterial, algal, and animal cellulose, interacts with hemicellulose, is poorly hydrated, and is targeted by the protein expansin during wall loosening. To obtain information about the C6 hydroxymethyl conformation of these plant celluloses, we carried out DFT calculations of (13)C chemical shifts, using the Iα and Iβ crystal structures as templates and varying the C5-C6 torsion angle. Comparison with the experimental chemical shifts suggests that all interior cellulose favor the tg conformation, but cellulose d also has a similar propensity to adopt the gt conformation. These results indicate that cellulose in plant primary cell walls, due to their interactions with matrix polysaccharides, and has polymorphic structures that are not a simple superposition of the Iα and Iβ allomorphs, thus distinguishing them from bacterial and animal celluloses.

Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations

PubMed Central

Wang, Tuo; Yang, Hui; Kubicki, James D.; Hong, Mei

2017-01-01

The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D 13C-13C correlation spectra of uniformly 13C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose 13C chemical shifts differ significantly from the 13C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing and hydrogen bonding from celluloses of other organisms. 2D 13C-13C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Cellulose f and g are well mixed chains on the microfibril surface, cellulose a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of bacterial, algal and animal cellulose, interacts with hemicellulose, is poorly hydrated, and is targeted by the protein expansin during wall loosening. To obtain information about the C6 hydroxymethyl conformation of these plant celluloses, we carried out DFT calculations of 13C chemical shifts, using the Iα and Iβ crystal structures as templates and varying the C5-C6 torsion angle. Comparison with the experimental chemical shifts suggests that all interior cellulose favor the tg conformation, but cellulose d also has a similar propensity to adopt the gt conformation. These results indicate that cellulose in plant primary cell walls, due to their interactions with matrix polysaccharides, has polymorphic structures that are not a simple superposition of the Iα and Iβ allomorphs, thus distinguishing them from bacterial and animal celluloses. PMID:27192562

Structure and chemical composition of layers adsorbed at interfaces with champagne.

PubMed

Aguié-Béghin, V; Adriaensen, Y; Péron, N; Valade, M; Rouxhet, P; Douillard, R

2009-11-11

The structure and the chemical composition of the layer adsorbed at interfaces involving champagne have been investigated using native champagne, as well as ultrafiltrate (UFch) and ultraconcentrate (UCch) obtained by ultrafiltration with a 10(4) nominal molar mass cutoff. The layer adsorbed at the air/liquid interface was examined by surface tension and ellipsometry kinetic measurements. Brewster angle microscopy demonstrated that the layer formed on polystyrene by adsorption or drop evaporation was heterogeneous, with a domain structure presenting similarities with the layer adsorbed at the air/liquid interface. The surface chemical composition of polystyrene with the adlayer was determined by X-ray photoelectron spectroscopy (XPS). The contribution of champagne constituents varied according to the liquid (native, UFch, and UCch) and to the procedure of adlayer formation (evaporation, adsorption, and adsorption + rinsing). However, their chemical composition was not significantly influenced either by ultrafiltration or by the procedure of deposition on polystyrene. Modeling this composition in terms of classes of model compounds gave approximately 35% (w/w) of proteins and 65% (w/w) of polysaccharides. In the adlayer, the carboxyl groups or esters represent about 18% of carbon due to nonpolypeptidic compounds, indicating the presence of either uronic acids in the complex structure of pectic polysaccharides or of polyphenolic esters. This structural and chemical information and its relationship with the experimental procedures indicate that proteins alone cannot be used as a realistic model for the macromolecules forming the adsorption layer of champagne. Polysaccharides, the other major macromolecular components of champagne wine, are assembled with proteins at the interfaces, in agreement with the heterogeneous character of the adsorbed layer at interfaces.

Tuning the surface morphology of aluminium doped zinc oxide thin films by arrayed nanorods through chemical growth process

NASA Astrophysics Data System (ADS)

Devasia, Sebin; Anila, E. I.

2018-04-01

Here we report the growth and characterization of chemically grown aluminium doped zinc oxide nanorods on seed layers. The seed layers were prepared by chemical spray pyrolysis which acted as the growth centers. The growth duration of nanorods were varied from 3h to 12h in steps of 3h. Further, investigations on their structural, morphological, electrical and optical properties. The SEM images confirmed the hexagonal shaped nanorod arrays grown on the seed layers. Later, the x-ray diffraction measurements revealed the pure zinc oxide phase of the samples. Photoluminescence and photoconductivity studies were carried out to analyze the potential of its optoelectronic properties.

Chemically Derived Dense Alumina-Zirconia Composites for Improved Mechanical and Wear Erosion Properties

NASA Technical Reports Server (NTRS)

1998-01-01

As a result of this funded project high purity Zirconia-Toughened Alumina (ZTA) ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and rheological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. This improved materials should have enhanced properties such strength, toughness, and wear resistance for advanced structural applications, for example engine components in high technology aerospace applications.

Magnetic stars with wide depressions in the continuum. 2. The silicon star with a complex field structure HD 27404

NASA Astrophysics Data System (ADS)

Semenko, E. A.; Romanyuk, I. I.; Semenova, E. S.; Moiseeva, A. V.; Kudryavtsev, D. O.; Yakunin, I. A.

2017-10-01

Observations of the chemically peculiar star HD 27404 with the 6-m SAO RAS telescope showed a strong magnetic field with the longitudinal field component varying in a complicated way in the range of -2.5 to 1 kG. Fundamental parameters of the star ( T eff = 11 300 K, log g = 3.9) were estimated analyzing photometric indices in the Geneva and in the Stro¨ mgren-Crawford photometric systems. We detected weak radial velocity variations which can be due to the presence of a close star companion or chemical spots in the photosphere. Rapid estimation of the key chemical element abundance allows us to refer HD 27404 to a SiCr or Si+ chemically peculiar A0-B9 star.

Mononuclear Cu/O2 Complexes

PubMed Central

Cramer, Christopher J.; Tolman, William B.

2008-01-01

Using interwoven experimental and theoretical methods, detailed studies of several structurally defined 1:1 Cu/O2 complexes have provided important fundamental chemical information useful for understanding the nature of intermediates involved in aerobic oxidations in synthetic and enzymatic copper-mediated catalysis. In particular, these studies have shed new light onto the factors that influence the mode of O2 coordination (end-on vs. side-on) and the electronic structure, which can vary between Cu(II)-superoxo and Cu(III)-peroxo extremes. PMID:17458929

Predicting ready biodegradability of premanufacture notice chemicals.

PubMed

Boethling, Robert S; Lynch, David G; Thom, Gary C

2003-04-01

Chemical substances other than pesticides, drugs, and food additives are regulated by the U.S. Environmental Protection Agency (U.S. EPA) under the Toxic Substances Control Act (TSCA), but the United States does not require that new substances be tested automatically for such critical properties as biodegradability. The resulting lack of submitted data has fostered the development of estimation methods, and the BioWIN models for predicting biodegradability from chemical structure have played a prominent role in premanufacture notice (PMN) review. Until now, validation efforts have used only the Japanese Ministry of International Trade and Industry (MITI) test data and have not included all models. To assess BioWIN performance with PMN substances, we assembled a database of PMNs for which ready biodegradation data had been submitted over the period 1995 through 2001. The 305 PMN structures are highly varied and pose major challenges to chemical property estimation. Despite the variability of ready biodegradation tests, the use of at least six different test methods, and widely varying quality of submitted data, accuracy of four of six BioWIN models (MITI linear, MITI nonlinear, survey ultimate, survey primary) was in the 80+% range for predicting ready biodegradability. Greater accuracy (>90%) can be achieved by using model estimates only when the four models agree (true for 3/4 of the PMNs). The BioWIN linear and nonlinear probability models did not perform as well even when classification criteria were optimized. The results suggest that the MITI and survey BioWIN models are suitable for use in screening-level applications.

Preparation of γ-Al2O3 films by laser chemical vapor deposition

NASA Astrophysics Data System (ADS)

Gao, Ming; Ito, Akihiko; Goto, Takashi

2015-06-01

γ- and α-Al2O3 films were prepared by chemical vapor deposition using CO2, Nd:YAG, and InGaAs lasers to investigate the effects of varying the laser wavelength and deposition conditions on the phase composition and microstructure. The CO2 laser was found to mostly produce α-Al2O3 films, whereas the Nd:YAG and InGaAs lasers produced γ-Al2O3 films when used at a high total pressure. γ-Al2O3 films had a cauliflower-like structure, while the α-Al2O3 films had a dense and columnar structure. Of the three lasers, it was the Nd:YAG laser that interacted most with intermediate gas species. This promoted γ-Al2O3 nucleation in the gas phase at high total pressure, which explains the cauliflower-like structure of nanoparticles observed.

Fractionation and physicochemical characterization of lignin from waste jute bags: Effect of process parameters on yield and thermal degradation.

PubMed

Ahuja, Dheeraj; Kaushik, Anupama; Chauhan, Ghanshyam S

2017-04-01

In this work lignin was extracted from waste jute bags using soda cooking method and effect of varying alkali concentration and pH on yield, purity, structure and thermal degradation of lignin were studied. The Lignin yield, chemical composition and purity were assessed using TAPPI method and UV-vis spectroscopy. Yield and purity of lignin ranged from 27 to 58% and 50-94%, respectively for all the samples and was maximum for 8% alkali concentration and at pH 2 giving higher thermal stability. Chemical structure, thermal stability and elementary analysis of lignin were studied using FTIR, H NMR, thermo gravimetric analysis (TGA) and Elemental analyzer. FTIR and H NMR results showed that core structure of lignin starts breaking beyond 10% alkali concentration. S/G ratio shows the dominance of Syringyl unit over guaiacyl unit. Copyright © 2017 Elsevier B.V. All rights reserved.

Properties of SnO2 thin films deposited by chemical spray pyrolysis using different precursor solutions

NASA Astrophysics Data System (ADS)

Abdul-Hamead, Alaa A.

2018-05-01

In this article single and double nozzle (SN, DN) chemical spray pyrolysis techniques(CSP) proved that tin dioxide SnO2 thin film can be fabricated with different structures. SnO2 prepared from three different salts of tin with a concentration of 0.05 M, with thicknesses were about 0.2 ±0.02 µm. Microstructures inspections were achieved on films, beside optical transparency addition to the contact angle CA. The results show that films have tetragonal crystalline with different micro-structures, from sheet to rod and flower-like aggregates, by the variation of the used salts by DN more than SN, also the value of the CA of the prepared films varies with different structures, reaching its highest value for flower-like aggregates of about 130°. Finally, the optical transparency was different corresponding to the disparity in surfaces roughness and topography.

The structure of partially-premixed methane/air flames under varying premixing

NASA Astrophysics Data System (ADS)

Kluzek, Celine; Karpetis, Adonios

2008-11-01

The present work examines the spatial and scalar structure of laminar, partially premixed methane/air flames with the objective of developing flamelet mappings that capture the effect of varying premixture strength (air addition in fuel.) Experimental databases containing full thermochemistry measurements within laminar axisymmetric flames were obtained at Sandia National Laboratories, and the measurements of all major species and temperature are compared to opposed-jet one-dimensional flow simulation using Cantera and the full chemical kinetic mechanism of GRI 3.0. Particular emphasis is placed on the scalar structure of the laminar flames, and the formation of flamelet mappings that capture all of the salient features of thermochemistry in a conserved scalar representation. Three different premixture strengths were examined in detail: equivalence ratios of 1.8, 2.2, and 3.17 resulted in clear differences in the flame scalar structure, particularly in the position of the rich premixed flame zone and the attendant levels of major and intermediate species (carbon monoxide and hydrogen).

Catalysis, nanostructure and macroscopic property triangle in bioactive calcium-containing ceramic systems.

PubMed

Meiszterics, Anikó; Havancsák, Károly; Sinkó, Katalin

2013-04-01

Calcium silicate ceramics are intended for application as long-term implant materials. In the present work, attention was paid to understand the correlations between the nanostructure (aggregate size, crystallinity, porosity) and the macroscopic properties (solubility in water and simulated body fluids, SBF; hardness) varying the chemical composition. Varying the catalyst (from a base to various acids) during the chemical synthesis was shown to significantly impact on the pore size, crystallinity and mechanical properties. The basic catalyst yields the ceramics with the highest mechanical strength. Ammonia used in 1.0 or 10.0 molar ratio results in bulk ceramics with parameters required for a biomedical application, good hardness (180-200 HV) and low solubility (1-3%) in water and in SBF. The fine porosity (~50 nm) and homogeneous amorphous structure induce good mechanical character. Copyright © 2012 Elsevier B.V. All rights reserved.

Physico-chemical characteristics of microwave-dried wheat distillers grain with solubles.

PubMed

Mosqueda, Maria Rosario P; Tabil, Lope G; Meda, Venkatesh

2013-01-01

Laboratory-prepared samples of wheat distillers grain with solubles with varying condensed distillers solubles (CDS) content were dried under varying microwave power, and microwave convection settings using a domestic microwave oven to examine their effect on the chemical, structural, color, flow, compression, thermal, and frictional properties of the product, which is dried distillers grain with solubles (DDGS). As CDS level increased, protein and ash content increased, while fat and fiber content decreased in wheat-based DDGS. Fat content was also markedly effected by the microwave oven drying conditions. While CDS level, microwave power or microwave convection setting, and/or their interactions significantly effected a number of physical properties; results indicated that CDS level had a stronger influence compared to the other factors. DDGS samples with high CDS levels were significantly denser, finer but more differentiated in size, less flowable, and less dispersible. These also produced denser and stronger pellets.

Laboratory glassware rack for seismic safety

NASA Technical Reports Server (NTRS)

Cohen, M. M. (Inventor)

1985-01-01

A rack for laboratory bottles and jars for chemicals and medicines has been designed to provide the maximum strength and security to the glassware in the event of a significant earthquake. The rack preferably is rectangular and may be made of a variety of chemically resistant materials including polypropylene, polycarbonate, and stainless steel. It comprises a first plurality of parallel vertical walls, and a second plurality of parallel vertical walls, perpendicular to the first. These intersecting vertical walls comprise a self-supporting structure without a bottom which sits on four legs. The top surface of the rack is formed by the top edges of all the vertical walls, which are not parallel but are skewed in three dimensions. These top edges form a grid matrix having a number of intersections of the vertical walls which define a number of rectangular compartments having varying widths and lengths and varying heights.

Chemical Frustration in the Protein Folding Landscape: Grand Canonical Ensemble Simulations of Cytochrome c

PubMed Central

Weinkam, Patrick; Romesberg, Floyd E.; Wolynes, Peter G.

2010-01-01

A grand canonical formalism is developed to combine discrete simulations for chemically distinct species in equilibrium. Each simulation is based on a perturbed funneled landscape. The formalism is illustrated using the alkaline-induced transitions of cytochrome c as observed by FTIR spectroscopy and with various other experimental approaches. The grand canonical simulation method accounts for the acid/base chemistry of deprotonation, the inorganic chemistry of heme ligation and misligation, and the minimally frustrated folding energy landscape, thus elucidating the physics of protein folding involved with an acid/base titration of a protein. The formalism combines simulations for each of the relevant chemical species, varying by protonation and ligation states. In contrast to models based on perfectly funneled energy landscapes that contain only contacts found in the native structure, the current study introduces “chemical frustration” from deprotonation and misligation that gives rise to many intermediates at alkaline pH. While the nature of these intermediates cannot be easily inferred from available experimental data, the current study provides specific structural details of these intermediates thus extending our understanding of how cytochrome c changes with increasing pH. The results demonstrate the importance of chemical frustration for understanding biomolecular energy landscapes. PMID:19199810

Linear and Branched PEIs (Polyethylenimines) and Their Property Space.

PubMed

Lungu, Claudiu N; Diudea, Mircea V; Putz, Mihai V; Grudziński, Ireneusz P

2016-04-13

A chemical property space defines the adaptability of a molecule to changing conditions and its interaction with other molecular systems determining a pharmacological response. Within a congeneric molecular series (compounds with the same derivatization algorithm and thus the same brute formula) the chemical properties vary in a monotonic manner, i.e., congeneric compounds share the same chemical property space. The chemical property space is a key component in molecular design, where some building blocks are functionalized, i.e., derivatized, and eventually self-assembled in more complex systems, such as enzyme-ligand systems, of which (physico-chemical) properties/bioactivity may be predicted by QSPR/QSAR (quantitative structure-property/activity relationship) studies. The system structure is determined by the binding type (temporal/permanent; electrostatic/covalent) and is reflected in its local electronic (and/or magnetic) properties. Such nano-systems play the role of molecular devices, important in nano-medicine. In the present article, the behavior of polyethylenimine (PEI) macromolecules (linear LPEI and branched BPEI, respectively) with respect to the glucose oxidase enzyme GOx is described in terms of their (interacting) energy, geometry and topology, in an attempt to find the best shape and size of PEIs to be useful for a chosen (nanochemistry) purpose.

Linear and Branched PEIs (Polyethylenimines) and Their Property Space

PubMed Central

Lungu, Claudiu N.; Diudea, Mircea V.; Putz, Mihai V.; Grudziński, Ireneusz P.

2016-01-01

A chemical property space defines the adaptability of a molecule to changing conditions and its interaction with other molecular systems determining a pharmacological response. Within a congeneric molecular series (compounds with the same derivatization algorithm and thus the same brute formula) the chemical properties vary in a monotonic manner, i.e., congeneric compounds share the same chemical property space. The chemical property space is a key component in molecular design, where some building blocks are functionalized, i.e., derivatized, and eventually self-assembled in more complex systems, such as enzyme-ligand systems, of which (physico-chemical) properties/bioactivity may be predicted by QSPR/QSAR (quantitative structure-property/activity relationship) studies. The system structure is determined by the binding type (temporal/permanent; electrostatic/covalent) and is reflected in its local electronic (and/or magnetic) properties. Such nano-systems play the role of molecular devices, important in nano-medicine. In the present article, the behavior of polyethylenimine (PEI) macromolecules (linear LPEI and branched BPEI, respectively) with respect to the glucose oxidase enzyme GOx is described in terms of their (interacting) energy, geometry and topology, in an attempt to find the best shape and size of PEIs to be useful for a chosen (nanochemistry) purpose. PMID:27089324

A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings.

PubMed

Hall, Colin J; Ponnusamy, Thirunavukkarasu; Murphy, Peter J; Lindberg, Mats; Antzutkin, Oleg N; Griesser, Hans J

2014-06-11

Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a low TMDSO-to-oxygen ratio had little to no singly substituted moieties, displayed a highly cross-linked structure, and showed less post-plasma reactions. However, these chemically more stable coatings are less compatible mechanically with plastic substrates, because of their high stiffness.

Ultrathin Pt xSn 1–x Nanowires for Methanol and Ethanol Oxidation Reactions: Tuning Performance by Varying Chemical Composition

DOE PAGES

Li, Luyao; Liu, Haiqing; Qin, Chao; ...

2018-02-28

Pt-based alloys denote promising catalysts for the methanol oxidation reaction (MOR) and the ethanol oxidation reaction (EOR), due to their enhanced activity toward alcohol-oxidation reactions and reduced cost as compared with Pt alone. Among all of these binary systems, PtSn has been reported to exhibit superior methanol/ethanol oxidation activity. In this paper, we deliberatively tailor chemical composition, reduce size, and optimize morphology of the catalyst in an effort to understand structure–property correlations that can be used to improve upon the electrocatalytic activity of these systems. Previous work performed by our group suggested that Pt-based catalysts, possessing an ultrathin one-dimensional (1D)more » structure, dramatically promote both cathodic and anodic reactions with respect to their zero-dimensional (0D) counterparts. Herein, a novel set of ultrathin binary Pt–Sn 1D nanowire (NW) catalysts with rationally controlled chemical compositions, i.e., Pt 9Sn 1, Pt 8Sn 2, and Pt 7Sn 3, has been synthesized using a facile, room-temperature, wet-solution-based method. The crystallinity and chemical composition of these as-prepared samples were initially characterized using XRD, XPS, and EDX. Results revealed that this synthetic protocol could successfully generate PtSn alloys with purposely tunable chemical compositions. TEM and HRTEM verified the structural integrity of our ultrathin 1D NW morphology for our Pt 9Sn 1, Pt 8Sn 2, and Pt 7Sn 3 samples. The effects of varying Sn content within these alloy samples toward the electro-oxidation reaction of methanol and ethanol were probed using cyclic voltammetry (CV) in acidic media. Finally, within this series, we find that the optimized chemical composition for both the MOR and the EOR is Pt 7Sn 3.« less

Ultrathin Pt xSn 1–x Nanowires for Methanol and Ethanol Oxidation Reactions: Tuning Performance by Varying Chemical Composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Luyao; Liu, Haiqing; Qin, Chao

Pt-based alloys denote promising catalysts for the methanol oxidation reaction (MOR) and the ethanol oxidation reaction (EOR), due to their enhanced activity toward alcohol-oxidation reactions and reduced cost as compared with Pt alone. Among all of these binary systems, PtSn has been reported to exhibit superior methanol/ethanol oxidation activity. In this paper, we deliberatively tailor chemical composition, reduce size, and optimize morphology of the catalyst in an effort to understand structure–property correlations that can be used to improve upon the electrocatalytic activity of these systems. Previous work performed by our group suggested that Pt-based catalysts, possessing an ultrathin one-dimensional (1D)more » structure, dramatically promote both cathodic and anodic reactions with respect to their zero-dimensional (0D) counterparts. Herein, a novel set of ultrathin binary Pt–Sn 1D nanowire (NW) catalysts with rationally controlled chemical compositions, i.e., Pt 9Sn 1, Pt 8Sn 2, and Pt 7Sn 3, has been synthesized using a facile, room-temperature, wet-solution-based method. The crystallinity and chemical composition of these as-prepared samples were initially characterized using XRD, XPS, and EDX. Results revealed that this synthetic protocol could successfully generate PtSn alloys with purposely tunable chemical compositions. TEM and HRTEM verified the structural integrity of our ultrathin 1D NW morphology for our Pt 9Sn 1, Pt 8Sn 2, and Pt 7Sn 3 samples. The effects of varying Sn content within these alloy samples toward the electro-oxidation reaction of methanol and ethanol were probed using cyclic voltammetry (CV) in acidic media. Finally, within this series, we find that the optimized chemical composition for both the MOR and the EOR is Pt 7Sn 3.« less

Atomic scale study of strain relaxation in Sn islands on Sn-induced Si(111)-(2√3 ×2√3 ) surface

NASA Astrophysics Data System (ADS)

Wang, L. L.; Ma, X. C.; Ning, Y. X.; Ji, S. H.; Fu, Y. S.; Jia, J. F.; Kelly, K. F.; Xue, Q. K.

2009-04-01

Surface structure of the Sn islands 5 ML high, prepared on Si(111)-(2√3 ×2√3 )-Sn substrate, is investigated by low temperature scanning tunneling microscopy/spectroscopy. Due to the elastic strain relaxation in the islands, the in-plane unit cell structure distorts and the apparent height of the surface atoms varies regularly to form an overall modulated strip structure. The quantum well states are observed to depend on the relative position within this structure, which implies the change of the surface chemical potential induced by the elastic strain relaxation as well.

Phase I Metabolic Stability and Electrophilic Reactivity of 2-Phenylaminophenylacetic Acid Derived Compounds.

PubMed

Pang, Yi Yun; Tan, Yee Min; Chan, Eric Chun Yong; Ho, Han Kiat

2016-07-18

Diclofenac and lumiracoxib are two highly analogous 2-phenylaminophenylacetic acid anti-inflammatory drugs exhibiting occasional dose-limiting hepatotoxicities. Prior data indicate that bioactivation and reactive metabolite formation play roles in the observed toxicity, but the exact chemical influence of the substituents remains elusive. In order to elucidate the role of chemical influence on metabolism related toxicity, metabolic stability and electrophilic reactivity were investigated for a series of structurally related analogues and their resulting metabolites. The resulting analogues embody progressive physiochemical changes through varying halogeno- and aliphatic substituents at two positions and were subjected to in vitro human liver microsomal metabolic stability and cell-based GSH depletion assays (to measure electrophilic reactivity). LC-MS/MS analysis of the GSH trapped reactive intermediates derived from the analogues was then used to identify the putative structures of reactive metabolites. We found that chemical modifications of the structural backbone led to noticeable perturbations of metabolic stability, electrophilic reactivity, and structures and composition of reactive metabolites. With the acquired data, the relationships between stability, reactivity, and toxicity were investigated in an attempt to correlate between Phase I metabolism and in vitro toxicity. A positive correlation was identified between reactivity and in vitro toxicity, indicating that electrophilic reactivity can be an indicator for in vitro toxicity. All in all, the effect of substituents on the structures and reactivity of the metabolites, however subtle the changes, should be taken into consideration during future drug design involving similar chemical features.

Structure and Chemical Composition of Prospheroplast Envelopes of Saccharomyces cerevisiae and Hansenula anomala

PubMed Central

Darling, Sven; Theilade, Jørgen; Birch-Andersen, Aksel

1972-01-01

Cells of Saccharomyces cerevisiae and Hansenula anomala were digested with snail enzyme under conditions yielding prospheroplasts. Surrounding envelopes were isolated after lysis of prospheroplasts in distilled water. The envelope material was embedded and sectioned for electron microscopy, and thin, hollow structures still retaining the elongated form of the original cells were seen. The envelopes were of low electron density in sections stained with uranyl magnesium acetate and lead citrate, but were more electron-dense when stained with phosphotungstic acid. Shadowed preparations of prospheroplast envelopes revealed structures resembling ghosts. These “ghosts” were similar to the original cells in form and size but seemed to be very thin. Varying numbers of anular structures (bud scars) were found on them. Chemical analyses of the envelope indicated that an alkali-soluble glucan was a major constituent. The results show that the prospheroplast envelope is part of the original cell wall of the yeast and is located in close apposition to the cytoplasmic membrane. Images PMID:4552997

Structural investigation of chemically synthesized ferrite magnetic nanomaterials

NASA Astrophysics Data System (ADS)

Uyanga, E.; Sangaa, D.; Hirazawa, H.; Tsogbadrakh, N.; Jargalan, N.; Bobrikov, I. A.; Balagurov, A. M.

2018-05-01

In recent times, interest in ferrite magnetic nanomaterials has considerably grown, mainly due to their highly promising medical and biological applications. Spinel ferrite powder samples, with high heat generation abilities in AC magnetic fields, were studied for their application to the hyperthermia treatment of cancer tumors. These properties of ferrites strongly depend on their chemical composition, ion distribution between crystallographic positions, magnetic structure and method of preparation. In this study, crystal and magnetic structures of several magnetic spinels were investigated by neutron diffraction. The explanation of the mechanism triggering the heat generation ability in the magnetic materials, and the electronic and magnetic states of ferrite-spinel type structures, were theoretically defined by a first-principles method. Ferrites with the composition of CuxMg1-xFe2O4 have been investigated as a heat generating magnetic nanomaterial. Atomic fraction of copper in ferrite was varied between 0 and 100% (that is, x between 0 and 1.0 with 0.2 steps), with the copper dope limit corresponding to appear a tetragonal phase.

Interfacial chemical reactions between MoS2 lubricants and bearing materials

NASA Technical Reports Server (NTRS)

Zabinski, J. S.; Tatarchuk, B. J.

1989-01-01

XPS and conversion-electron Moessbauer spectroscopy (CEMS) were used to examine iron that was deposited on the basal plane of MoS2 single crystals and subjected to vacuum annealing, oxidizing, and reducing environments. Iron either intercalated into the MoS2 structure or formed oriented iron sulfides, depending on the level of excess S in the MoS2 structure. CEMS data demonstrated that iron sulfide crystal structures preferentially aligned with respect to the MoS2 basal plane, and that alignment (and potentially adhesion) could be varied by appropriate high-temperature annealing procedures.

Diameter Tuning of β-Ga2O3 Nanowires Using Chemical Vapor Deposition Technique.

PubMed

Kumar, Mukesh; Kumar, Vikram; Singh, R

2017-12-01

Diameter tuning of [Formula: see text]-Ga 2 O 3 nanowires using chemical vapor deposition technique have been investigated under various experimental conditions. Diameter of root grown [Formula: see text]-Ga 2 O 3 nanowires having monoclinic crystal structure is tuned by varying separation distance between metal source and substrate. Effect of gas flow rate and mixer ratio on the morphology and diameter of nanowires has been studied. Nanowire diameter depends on growth temperature, and it is independent of catalyst nanoparticle size at higher growth temperature (850-900 °C) as compared to lower growth temperature (800 °C). These nanowires show changes in structural strain value with change in diameter. Band-gap of nanowires increases with decrease in the diameter.

Tungsten Incorporation into Gallium Oxide: Crystal Structure, Surface and Interface Chemistry, Thermal Stability and Interdiffusion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rubio, E. J.; Mates, T. E.; Manandhar, S.

Tungsten (W) incorporated gallium oxide (Ga2O3) (GWO) thin films were deposited by radio-frequency magnetron co-sputtering of W-metal and Ga2O3-ceramic targets. Films were produced by varying sputtering power applied to the W-target in order to achieve variable W-content (0-12 at%) into Ga2O3 while substrate temperature was kept constant at 500 °C. Chemical composition, chemical valence states, microstructure and crystal structure of as-deposited and annealed GWO films were evaluated as a function of W-content. The structural and chemical analyses indicate that the samples deposited without any W-incorporation are stoichiometric, nanocrystalline Ga2O3 films, which crystallize in β-phase monoclinic structure. While GWO films alsomore » crystallize in monoclinic β-Ga2O3 phase, W-incorporation induces surface amorphization as revealed by structural studies. The chemical valence state of Ga ions probed by X-ray photoelectron spectroscopic (XPS) analyses is characterized by the highest oxidation state i.e., Ga3+. No changes in Ga chemical state are noted for variable W-incorporation in the range of 0-12 at%. Rutherford backscattering spectrometry (RBS) analyses indicate the uniform distribution of W-content in the GWO films. However, XPS analyses indicate the formation of mixed valence states for W ions, which may be responsible for surface amorphization in GWO films. GWO films were stable up to 900 oC, at which point thermally induced secondary phase (W-oxide) formation was observed. A transition to mesoporous structure coupled with W interdiffusion occurs due to thermal annealing as derived from the chemical analyses at the GWO films’ surface as well as depth-profiling towards the GWO-Si interface. A model has been formulated to account for the mechanism of W-incorporation, thermal stability and interdiffusion via pore formation in GWO films.« less

High-throughput literature mining to support read-across ...

EPA Pesticide Factsheets

Building scientific confidence in the development and evaluation of read-across remains an ongoing challenge. Approaches include establishing systematic frameworks to identify sources of uncertainty and ways to address them. One source of uncertainty is related to characterizing biological similarity. Many research efforts are underway such as structuring mechanistic data in adverse outcome pathways and investigating the utility of high throughput (HT)/high content (HC) screening data. A largely untapped resource for read-across to date is the biomedical literature. This information has the potential to support read-across by facilitating the identification of valid source analogues with similar biological and toxicological profiles as well as providing the mechanistic understanding for any prediction made. A key challenge in using biomedical literature is to convert and translate its unstructured form into a computable format that can be linked to chemical structure. We developed a novel text-mining strategy to represent literature information for read across. Keywords were used to organize literature into toxicity signatures at the chemical level. These signatures were integrated with HT in vitro data and curated chemical structures. A rule-based algorithm assessed the strength of the literature relationship, providing a mechanism to rank and visualize the signature as literature ToxPIs (LitToxPIs). LitToxPIs were developed for over 6,000 chemicals for a varie

Contributions of chemical exchange to T1ρ dispersion in a tissue model.

PubMed

Cobb, Jared G; Xie, Jingping; Gore, John C

2011-12-01

Variations in T(1ρ) with locking-field strength (T(1ρ) dispersion) may be used to estimate proton exchange rates. We developed a novel approach utilizing the second derivative of the dispersion curve to measure exchange in a model system of cross-linked polyacrylamide gels. These gels were varied in relative composition of comonomers, increasing stiffness, and in pH, modifying exchange rates. Magnetic resonance images were recorded with a spin-locking sequence as described by Sepponen et al. These measurements were fit to a mono-exponential decay function yielding values for T(1ρ) at each locking-field measured. These values were then fit to a model by Chopra et al. for estimating exchange rates. For low stiffness gels, the calculated exchange values increased by a factor of 4 as pH increased, consistent with chemical exchange being the dominant contributor to T(1ρ) dispersion. Interestingly, calculated chemical exchange rates also increased with stiffness, likely due to modified side-chain exchange kinetics as the composition varied. This article demonstrates a new method to assess the structural and chemical effects on T(1ρ) relaxation dispersion with a suitable model. These phenomena may be exploited in an imaging context to emphasize the presence of nuclei of specific exchange rates, rather than chemical shifts. Copyright © 2011 Wiley Periodicals, Inc.

Spectroscopic, quantum chemical calculation and molecular docking of dipfluzine

NASA Astrophysics Data System (ADS)

Srivastava, Karnica; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Wang, Jing

2016-12-01

Molecular structure and vibrational analysis of dipfluzine (C27H29FN2O) were presented using FT-IR and FT-Raman spectroscopy and quantum chemical calculations. The theoretical ground state geometry and electronic structure of dipfluzine are optimized by the DFT/B3LYP/6-311++G (d,p) method and compared with those of the crystal data. The 1D potential energy scan was performed by varying the dihedral angle using B3LYP functional at 6-31G(d,p) level of theory and thus the most stable conformer of the compound were determined. Molecular electrostatic potential surface (MEPS), frontier orbital analysis and electronic reactivity descriptor were used to predict the chemical reactivity of molecule. Energies of intra- and inter-molecular hydrogen bonds in molecule and their electronic aspects were investigated by natural bond orbital (NBO). To find out the anti-apoptotic activity of the title compound molecular docking studies have been performed against protein Fas.

Prediction of biodegradability from chemical structure: Modeling or ready biodegradation test data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loonen, H.; Lindgren, F.; Hansen, B.

1999-08-01

Biodegradation data were collected and evaluated for 894 substances with widely varying chemical structures. All data were determined according to the Japanese Ministry of International Trade and Industry (MITI) I test protocol. The MITI I test is a screening test for ready biodegradability and has been described by Organization for Economic Cooperation and Development (OECD) test guideline 301 C and European Union (EU) test guideline C4F. The chemicals were characterized by a set of 127 predefined structural fragments. This data set was used to develop a model for the prediction of the biodegradability of chemicals under standardized OECD and EUmore » ready biodegradation test conditions. Partial least squares (PLS) discriminant analysis was used for the model development. The model was evaluated by means of internal cross-validation and repeated external validation. The importance of various structural fragments and fragment interactions was investigated. The most important fragments include the presence of a long alkyl chain; hydroxy, ester, and acid groups (enhancing biodegradation); and the presence of one or more aromatic rings and halogen substituents (regarding biodegradation). More than 85% of the model predictions were correct for using the complete data set. The not readily biodegradable predictions were slightly better than the readily biodegradable predictions (86 vs 84%). The average percentage of correct predictions from four external validation studies was 83%. Model optimization by including fragment interactions improve the model predicting capabilities to 89%. It can be concluded that the PLS model provides predictions of high reliability for a diverse range of chemical structures. The predictions conform to the concept of readily biodegradable (or not readily biodegradable) as defined by OECD and EU test guidelines.« less

Evaluation of the hypersensitivity potential of alternative butter flavorings

PubMed Central

Anderson, Stacey E.; Franko, Jennifer; Wells, J.R.; Lukomska, Ewa; Meade, B. Jean

2015-01-01

Concern has been raised over the association of diacetyl with lung disease clinically resembling bronchiolitis obliterans in food manufacturing workers. This has resulted in the need for identification of alternative chemicals to be used in the manufacturing process. Structurally similar chemicals, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione and 2,3-heptanedione, used as constituents of synthetic flavoring agents have been suggested as potential alternatives for diacetyl, however, immunotoxicity data on these chemicals are limited. The present study evaluated the dermal irritation and sensitization potential of diacetyl alternatives using a murine model. None of the chemicals were identified as dermal irritants when tested at concentrations up to 50%. Similar to diacetyl (EC3 = 17.9%), concentration-dependent increases in lymphocyte proliferation were observed following exposure to all four chemicals, with calculated EC3 values of 15.4% (2,3-pentanedione), 18.2% (2,3-hexanedione), 15.5% (3,4-hexanedione) and 14.1% (2,3-heptanedione). No biologically significant elevations in local or total serum IgE were identified after exposure to 25–50% concentrations of these chemicals. These results demonstrate the potential for development of hypersensitivity responses to these proposed alternative butter flavorings and raise concern about the use of structurally similar replacement chemicals. Additionally, a contaminant with strong sensitization potential was found in varying concentrations in diacetyl obtained from different producers. PMID:24007741

Evaluation of the hypersensitivity potential of alternative butter flavorings.

PubMed

Anderson, Stacey E; Franko, Jennifer; Wells, J R; Lukomska, Ewa; Meade, B Jean

2013-12-01

Concern has been raised over the association of diacetyl with lung disease clinically resembling bronchiolitis obliterans in food manufacturing workers. This has resulted in the need for identification of alternative chemicals to be used in the manufacturing process. Structurally similar chemicals, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione and 2,3-heptanedione, used as constituents of synthetic flavoring agents have been suggested as potential alternatives for diacetyl, however, immunotoxicity data on these chemicals are limited. The present study evaluated the dermal irritation and sensitization potential of diacetyl alternatives using a murine model. None of the chemicals were identified as dermal irritants when tested at concentrations up to 50%. Similar to diacetyl (EC3=17.9%), concentration-dependent increases in lymphocyte proliferation were observed following exposure to all four chemicals, with calculated EC3 values of 15.4% (2,3-pentanedione), 18.2% (2,3-hexanedione), 15.5% (3,4-hexanedione) and 14.1% (2,3-heptanedione). No biologically significant elevations in local or total serum IgE were identified after exposure to 25-50% concentrations of these chemicals. These results demonstrate the potential for development of hypersensitivity responses to these proposed alternative butter flavorings and raise concern about the use of structurally similar replacement chemicals. Additionally, a contaminant with strong sensitization potential was found in varying concentrations in diacetyl obtained from different producers. Published by Elsevier Ltd.

Saturated amine oxides: Part 8. Hydroacridines: Part 27. Effects of N-oxidation and of N-quaternization on the 15N NMR chemical shifts of N-methylpiperidine-derived mono-, bi-, and tricycloaliphatic tertiary amines.

PubMed

Potmischil, Francisc; Duddeck, Helmut; Nicolescu, Alina; Deleanu, Calin

2007-03-01

The (15)N chemical shifts of 13 N-methylpiperidine-derived mono-, bi- and tricycloaliphatic tertiary amines, their methiodides and their N-epimeric pairs of N-oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N-oxidation upon the (15)N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N(+)--O(-) oxygen atom, whereas the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The effects of quaternization vary from -3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N(+)--CH(3) methyl group, and the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The shift effects of the C-alkyl substituents in the amines, the N-oxides and the methiodides are discussed. Copyright (c) 2007 John Wiley & Sons, Ltd.

Identification and structural characterization of serobactins, a suite of lipopeptide siderophores produced by the grass endophyte Herbaspirillum seropedicae.

PubMed

Rosconi, Federico; Davyt, Danilo; Martínez, Verónica; Martínez, Marcela; Abin-Carriquiry, Juan Andrés; Zane, Hannah; Butler, Alison; de Souza, Emanuel M; Fabiano, Elena

2013-03-01

Herbaspirillum seropedicae Z67 is a diazotrophic endophyte able to colonize the interior of many economically relevant crops such as rice, wheat, corn and sorghum. Structures of siderophores produced by bacterial endophytes have not yet been elucidated. The aim of this work was to identify and characterize the siderophores produced by this bacterium. In a screening for mutants unable to produce siderophores we found a mutant that had a transposon insertion in a non-ribosomal peptide synthase (NRPS) gene coding for a putative siderophore biosynthetic enzyme. The chemical structure of the siderophore was predicted using computational genomic tools. The predicted structure was confirmed by chemical analysis. We found that siderophores produced by H. seropedicae Z67 are a suite of amphiphilic lipopeptides, named serobactin A, B and C, which vary by the length of the fatty acid chain. We also demonstrated the biological activity of serobactins as nutritional iron sources for H. seropedicae. These are the first structurally described siderophores produced by endophytic bacteria. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Structural and tribometric characterization of biomimetically inspired synthetic "insect adhesives"

PubMed Central

Speidel, Matthias W; Kleemeier, Malte; Hartwig, Andreas; Rischka, Klaus; Ellermann, Angelika; Daniels, Rolf

2017-01-01

Background: Based on previous chemical analyses of insect tarsal adhesives, we prepared 12 heterogeneous synthetic emulsions mimicking the polar/non-polar principle, analysed their microscopical structure and tested their adhesive, frictional, and rheological properties. Results: The prepared emulsions varied in their consistency from solid rubber-like, over soft elastic, to fluid (watery or oily). With droplet sizes >100 nm, all the emulsions belonged to the common type of macroemulsions. The emulsions of the first generation generally showed broader droplet-size ranges compared with the second generation, especially when less defined components such as petrolatum or waxes were present in the lipophilic fraction of the first generation of emulsions. Some of the prepared emulsions showed a yield point and were Bingham fluids. Tribometric adhesion was tested via probe tack tests. Compared with the "second generation" (containing less viscous components), the "first generation" emulsions were much more adhesive (31–93 mN), a finding attributable to their highly viscous components, i.e., wax, petrolatum, gelatin and poly(vinyl alcohol). In the second generation emulsions, we attained much lower adhesivenesses, ranging between 1–18 mN. The adhesive performance was drastically reduced in the emulsions that contained albumin as the protein component or that lacked protein. Tribometric shear tests were performed at moderate normal loads. Our measured friction forces (4–93 mN in the first and 0.1–5.8 mN in the second generation emulsions) were comparatively low. Differences in shear performance were related to the chemical composition and emulsion structure. Conclusion: By varying their chemical composition, synthetic heterogeneous adhesive emulsions can be adjusted to have diverse consistencies and are able to mimic certain rheological and tribological properties of natural tarsal insect adhesives. PMID:28144564

An ensemble model of QSAR tools for regulatory risk assessment.

PubMed

Pradeep, Prachi; Povinelli, Richard J; White, Shannon; Merrill, Stephen J

2016-01-01

Quantitative structure activity relationships (QSARs) are theoretical models that relate a quantitative measure of chemical structure to a physical property or a biological effect. QSAR predictions can be used for chemical risk assessment for protection of human and environmental health, which makes them interesting to regulators, especially in the absence of experimental data. For compatibility with regulatory use, QSAR models should be transparent, reproducible and optimized to minimize the number of false negatives. In silico QSAR tools are gaining wide acceptance as a faster alternative to otherwise time-consuming clinical and animal testing methods. However, different QSAR tools often make conflicting predictions for a given chemical and may also vary in their predictive performance across different chemical datasets. In a regulatory context, conflicting predictions raise interpretation, validation and adequacy concerns. To address these concerns, ensemble learning techniques in the machine learning paradigm can be used to integrate predictions from multiple tools. By leveraging various underlying QSAR algorithms and training datasets, the resulting consensus prediction should yield better overall predictive ability. We present a novel ensemble QSAR model using Bayesian classification. The model allows for varying a cut-off parameter that allows for a selection in the desirable trade-off between model sensitivity and specificity. The predictive performance of the ensemble model is compared with four in silico tools (Toxtree, Lazar, OECD Toolbox, and Danish QSAR) to predict carcinogenicity for a dataset of air toxins (332 chemicals) and a subset of the gold carcinogenic potency database (480 chemicals). Leave-one-out cross validation results show that the ensemble model achieves the best trade-off between sensitivity and specificity (accuracy: 83.8 % and 80.4 %, and balanced accuracy: 80.6 % and 80.8 %) and highest inter-rater agreement [kappa ( κ ): 0.63 and 0.62] for both the datasets. The ROC curves demonstrate the utility of the cut-off feature in the predictive ability of the ensemble model. This feature provides an additional control to the regulators in grading a chemical based on the severity of the toxic endpoint under study.

An ensemble model of QSAR tools for regulatory risk assessment

DOE PAGES

Pradeep, Prachi; Povinelli, Richard J.; White, Shannon; ...

2016-09-22

Quantitative structure activity relationships (QSARs) are theoretical models that relate a quantitative measure of chemical structure to a physical property or a biological effect. QSAR predictions can be used for chemical risk assessment for protection of human and environmental health, which makes them interesting to regulators, especially in the absence of experimental data. For compatibility with regulatory use, QSAR models should be transparent, reproducible and optimized to minimize the number of false negatives. In silico QSAR tools are gaining wide acceptance as a faster alternative to otherwise time-consuming clinical and animal testing methods. However, different QSAR tools often make conflictingmore » predictions for a given chemical and may also vary in their predictive performance across different chemical datasets. In a regulatory context, conflicting predictions raise interpretation, validation and adequacy concerns. To address these concerns, ensemble learning techniques in the machine learning paradigm can be used to integrate predictions from multiple tools. By leveraging various underlying QSAR algorithms and training datasets, the resulting consensus prediction should yield better overall predictive ability. We present a novel ensemble QSAR model using Bayesian classification. The model allows for varying a cut-off parameter that allows for a selection in the desirable trade-off between model sensitivity and specificity. The predictive performance of the ensemble model is compared with four in silico tools (Toxtree, Lazar, OECD Toolbox, and Danish QSAR) to predict carcinogenicity for a dataset of air toxins (332 chemicals) and a subset of the gold carcinogenic potency database (480 chemicals). Leave-one-out cross validation results show that the ensemble model achieves the best trade-off between sensitivity and specificity (accuracy: 83.8 % and 80.4 %, and balanced accuracy: 80.6 % and 80.8 %) and highest inter-rater agreement [kappa (κ): 0.63 and 0.62] for both the datasets. The ROC curves demonstrate the utility of the cut-off feature in the predictive ability of the ensemble model. In conclusion, this feature provides an additional control to the regulators in grading a chemical based on the severity of the toxic endpoint under study.« less

Some factors affecting efficiencies of n-CdS/p-CdTe thin film solar cells

NASA Astrophysics Data System (ADS)

Morris, G. C.; Das, S. K.; Tanner, P. G.

1992-02-01

Electrodeposited CdS and CdTe thin films have been fabricated into solar cells with a CdS/CdTe heterojunction. The CdTe films were made by varying two parameters, viz. the concentration of tellurium ions in the deposition solution and the quasi-rest potential (QRP) of the deposit. The properties of the completed cells were examined as a function of those preparation variables. Cell efficiency varied with both QRP and tellurium ion concentration. Whilst chemical analytic methods showed no compositional variation between cells, morphological studies showed that the most efficient cells had the largest grain size. Electrical and capacitance measurements were used to show that the density of interband states and of junction interface states increased with structural imperfection. The major losses in the solar cell parameters increased with increased polycrystalline structure.

X-ray circular dichroism signals: a unique probe of local molecular chirality

DOE PAGES

Zhang, Yu; Rouxel, Jeremy R.; Autschbach, Jochen; ...

2017-06-26

Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. As a result, clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.

X-ray circular dichroism signals: a unique probe of local molecular chirality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yu; Rouxel, Jeremy R.; Autschbach, Jochen

Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. As a result, clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.

Prediction of the Formulation Dependence of the Glass Transition Temperature for Amine-Epoxy Copolymers Using a Quantitative Structure-Property Relationship Based on the AM1 Method

DTIC Science & Technology

2004-02-01

Products and Chemicals , Inc . The stoichiometry of the DGEBA-PACM polymerization reaction was varied to yield epoxy/amine ratios ranging from ~2:1 through...equivalent). The DGEBA epoxy resin was cured with bis(p-aminocyclohexyl)methane (PACM) (EEW = 52.5 g/equivalent), which was acquired from Air

Ab Initio Molecular-Dynamics Simulation of Neuromorphic Computing in Phase-Change Memory Materials.

PubMed

Skelton, Jonathan M; Loke, Desmond; Lee, Taehoon; Elliott, Stephen R

2015-07-08

We present an in silico study of the neuromorphic-computing behavior of the prototypical phase-change material, Ge2Sb2Te5, using ab initio molecular-dynamics simulations. Stepwise changes in structural order in response to temperature pulses of varying length and duration are observed, and a good reproduction of the spike-timing-dependent plasticity observed in nanoelectronic synapses is demonstrated. Short above-melting pulses lead to instantaneous loss of structural and chemical order, followed by delayed partial recovery upon structural relaxation. We also investigate the link between structural order and electrical and optical properties. These results pave the way toward a first-principles understanding of phase-change physics beyond binary switching.

Electron irradiation effects on partially fluorinated polymer films: Structure-property relationships

NASA Astrophysics Data System (ADS)

Nasef, Mohamed Mahmoud; Dahlan, Khairul Zaman M.

2003-04-01

The effects of electron beam irradiation on two partially fluorinated polymer films i.e. poly(vinylidene fluoride) (PVDF) and poly(ethylene-tetrafluoroethylene) copolymer (ETFE) are studied at doses ranging from 100 to 1200 kGy in air at room temperature. Chemical structure, thermal and mechanical properties of irradiated films are investigated. FTIR show that both PVDF and ETFE films undergo similar changes in their chemical structures including the formation of carbonyl groups and double bonding. The changes in melting and crystallisation temperatures ( Tm and Tc) in both irradiated films are functions of irradiation dose and reflect the disorder in the chemical structure caused by the competition between crosslinking and chain scission. The heat of melting (Δ Hm) and the degree of crystallinity ( Xc) of PVDF films show no significant changes with the dose increase, whereas those of ETFE films are reduced rapidly after the first 100 kGy. The tensile strength of PVDF films is improved by irradiation compared to its rapid deterioration in ETFE films, which stemmed from the degradation prompted by the presence of radiation sensitive tetrafluoroethylene (TFE) comonomer units. The elongation at break of both films drops gradually with the dose increase indicating the formation of predominant crosslinked structures at high doses. However, the response of each polymer to crosslinking and main chain scission at various irradiation doses varies from PVDF to ETFE films.

Quantification of microscopic surface features of single point diamond turned optics with subsequent chemical polishing

NASA Astrophysics Data System (ADS)

Cardenas, Nelson; Kyrish, Matthew; Taylor, Daniel; Fraelich, Margaret; Lechuga, Oscar; Claytor, Richard; Claytor, Nelson

2015-03-01

Electro-Chemical Polishing is routinely used in the anodizing industry to achieve specular surface finishes of various metals products prior to anodizing. Electro-Chemical polishing functions by leveling the microscopic peaks and valleys of the substrate, thereby increasing specularity and reducing light scattering. The rate of attack is dependent of the physical characteristics (height, depth, and width) of the microscopic structures that constitute the surface finish. To prepare the sample, mechanical polishing such as buffing or grinding is typically required before etching. This type of mechanical polishing produces random microscopic structures at varying depths and widths, thus the electropolishing parameters are determined in an ad hoc basis. Alternatively, single point diamond turning offers excellent repeatability and highly specific control of substrate polishing parameters. While polishing, the diamond tool leaves behind an associated tool mark, which is related to the diamond tool geometry and machining parameters. Machine parameters such as tool cutting depth, speed and step over can be changed in situ, thus providing control of the spatial frequency of the microscopic structures characteristic of the surface topography of the substrate. By combining single point diamond turning with subsequent electro-chemical etching, ultra smooth polishing of both rotationally symmetric and free form mirrors and molds is possible. Additionally, machining parameters can be set to optimize post polishing for increased surface quality and reduced processing times. In this work, we present a study of substrate surface finish based on diamond turning tool mark spatial frequency with subsequent electro-chemical polishing.

Using pig manure to promote fermentation of sugarcane molasses alcohol wastewater and its effects on microbial community structure.

PubMed

Shen, Peihong; Han, Fei; Su, Shuquan; Zhang, Junya; Chen, Zhineng; Li, Junfang; Gan, Jiayi; Feng, Bin; Wu, Bo

2014-03-01

Molasses alcohol wastewater (MAW) is difficult to be bio-treated and converted into biogas. In this study, MAW mixed with pig manure (PM) in different ratios was co-digested. Biogas production, chemical oxygen demand (COD) removal and the structure of microbial communities were monitored in the process. Our results showed that under the optimal COD ratio of PM:MAW (1.0:1.5), CODremoval and biogas yield were the highest. And in fermentation tanks with different PM to MAW ratios, the structure and composition of bacterial communities varied in the early and late stage. Furthermore, the type of main bacterial operational taxonomic units (OTUs) have no differences, yet the relative abundance of OTUs varied. The current research showed that there was a good potential to the use of PM as a co-digested material to anaerobic treatment of MAW and provided references for further improving bio-treatment of MAW. Copyright © 2014 Elsevier Ltd. All rights reserved.

Controlled Chemical Patterns with ThermoChemical NanoLithography (TCNL)

NASA Astrophysics Data System (ADS)

Carroll, Keith; Giordano, Anthony; Wang, Debin; Kodali, Vamsi; King, W. P.; Marder, S. R.; Riedo, E.; Curtis, J. E.

2012-02-01

Many research areas, both fundamental and applied, rely upon the ability to organize non-trivial assemblies of molecules on surfaces. In this work, we introduce a significant extension of ThermoChemical NanoLithography (TCNL), a high throughput chemical patterning technique that uses temperature-driven chemical reactions localized near the tip of a thermal cantilever. By combining a chemical kinetics based model with experiments, we have developed a protocol for varying the concentration of surface bound molecules. The result is an unprecedented ability to fabricate extremely complex patterns comprised of varying chemical concentrations, as demonstrated by sinusoidal patterns of amine groups with varying pitches (˜5-15 μm) and the replication of Leonardo da Vinci's Mona Lisa with dimensions of ˜30 x 40 μm^2. Programmed control of the chemical reaction rate should have widespread applications for a technique which has already been shown to nanopattern various substrates including graphene nanowires, piezoelectric crystals, and optoelectronic materials.

Zn–Se–Cd–S Interlayer Formation at the CdS/Cu 2 ZnSnSe 4 Thin-Film Solar Cell Interface

DOE PAGES

Bär, Marcus; Repins, Ingrid; Weinhardt, Lothar; ...

2017-06-14

The chemical structure of the CdS/Cu 2ZnSnSe 4 (CZTSe) interface was studied by a combination of electron and X-ray spectroscopies with varying surface sensitivity. We find the CdS chemical bath deposition causes a 'redistribution' of elements in the proximity of the CdS/CZTSe interface. In detail, our data suggest that Zn and Se from the Zn-terminated CZTSe absorber and Cd and S from the buffer layer form a Zn-Se-Cd-S interlayer. Here, we find direct indications for the presence of Cd-S, Cd-Se, and Cd-Se-Zn bonds at the buffer/absorber interface. Thus, we propose the formation of a mixed Cd(S,Se)-(Cd,Zn)Se interlayer. We also suggestmore » the underlying chemical mechanism is an ion exchange mediated by the amine complexes present in the chemical bath.« less

The effect of pulping concentration treatment on the properties of microcrystalline cellulose powder obtained from waste paper.

PubMed

Okwonna, Okumneme O

2013-10-15

Microcrystalline cellulose (MCC) powder was isolated from three grades of waste paper: book, Groundwood/Newsprint and paperboard, through the processes of pulping and hydrolysis. Pulping treatment on these grades of waste paper was done using varying concentrations of caustic soda. Effects of the concentration of the pulping medium on the thermal and kinetic properties were investigated. Also determined were the effects of this on the physico-chemical properties. The chemical structure was characterized using an infrared spectroscopy (FTIR). Results showed these properties to be affected by the concentration of the pulping medium. Copyright © 2013 Elsevier Ltd. All rights reserved.

Theoretical study of orbital ordering induced structural phase transition in iron pnictides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jena, Sushree Sangita, E-mail: sushree@iopb.res.in; Rout, G. C., E-mail: gcr@iopb.res.in; Panda, S. K., E-mail: skp@iopb.res.in

2016-05-06

We attribute the structural phase transition (SPT) in the parent compounds of the iron pnictides to orbital ordering. Due to anisotropy of the d{sub xz} and d{sub yz} orbitals in the xy plane, orbital ordering makes the orthorhombic structure more favorable and thus inducing the SPT. We consider a one band model Hamiltonian consisting of first and second-nearest-neighbor hopping of the electrons. We introduce Jahn-Tellar (JT) distortion in the system arising due to the orbital ordering present in this system. We calculate the electron Green’s function by using Zuvareb’s Green’s function technique and hence calculate an expression for the temperaturemore » dependent lattice strain which is computed numerically and self-consistently. The temperature dependent electron specific heat is calculated by minimizing the free energy of the system. The lattice strain is studied by varying the JT coupling and elastic constant of the system. The structural anomaly is studied through the electron occupation number and the specific heat by varying the physical parameters like JT coupling, lattice constant, chemical potential and hopping integrals of the system.« less

Attenuated Total Reflection Mid-Infrared (ATR-MIR) Spectroscopy and Chemometrics for the Identification and Classification of Commercial Tannins.

PubMed

Ricci, Arianna; Parpinello, Giuseppina P; Olejar, Kenneth J; Kilmartin, Paul A; Versari, Andrea

2015-11-01

Attenuated total reflection Fourier transform infrared (FT-IR) spectroscopy was used to characterize 40 commercial tannins, including condensed and hydrolyzable chemical classes, provided as powder extracts from suppliers. Spectral data were processed to detect typical molecular vibrations of tannins bearing different chemical groups and of varying botanical origin (univariate qualitative analysis). The mid-infrared region between 4000 and 520 cm(-1) was analyzed, with a particular emphasis on the vibrational modes in the fingerprint region (1800-520 cm(-1)), which provide detailed information about skeletal structures and specific substituents. The region 1800-1500 cm(-1) contained signals due to hydrolyzable structures, while bands due to condensed tannins appeared at 1300-900 cm(-1) and exhibited specific hydroxylation patterns useful to elucidate the structure of the flavonoid monomeric units. The spectra were investigated further using principal component analysis for discriminative purposes, to enhance the ability of infrared spectroscopy in the classification and quality control of commercial dried extracts and to enhance their industrial exploitation.

Synthesis and Physical Properties Characterization of CdSe1-ySy Nanolayers Deposited by Chemical Bath Deposition at Low-Temperature Treatment

NASA Astrophysics Data System (ADS)

Flores-Mena, J. E.; Contreras-Rascón, J. I.; Diaz-Reyes, J.; Castillo-Ojeda, R. S.

In this work, we present the synthesis and structural and optical characterizations of CdSe1-y S y deposited by chemical bath deposition (CBD) technique on corning glass at a temperature of 20 ± 2 °C. The sulfur molar fraction was varied from 0 to 42.13 %, which was realized by varying the thiourea volume added to the growth solution in the range from 0 to 30 mL. The chemical stoichiometry was estimated by energy dispersive spectrometry (EDS). The CdSe1-y S y showed hexagonal wurtzite crystalline phase that was found by X-ray diffraction (XRD) analysis and Raman spectroscopy. The average grain size range of the films was 1.48-1.68 nm that was determined using the Debye-Scherrer equation W(002) direction and was confirmed by high-resolution transmission electron microscopy (HRTEM). Raman scattering shows that the lattice dynamics is characteristic of bimodal behavior and the multipeaks adjust to the first optical longitudinal mode for the CdSeS, in all cases, Raman spectra show two dominant vibrational bands about 208 and 415 cm-1 associated at CdSe-1LO-like and CdSe-2LO-like. CdSe1-y S y band gap energy can be varied from 1.86 to 2.16 eV by varying the thiourea volume added in growth solution in the investigated range obtained by transmittance measurements at room temperature. The room temperature photoluminescence shows a dominant radiation band at about 3.0 eV that can be associated with exciton bonded to donor impurity and the quantum confinement because of the grain size is less than the Bohr radius.

JPRS Report, Science & Technology, China

DTIC Science & Technology

1992-10-09

the nation’s first inert gas evaporation apparatus for fabrication of nanoparticles and have fabricated bulk test samples of nanostructures via...CAS researchers have employed chemical techniques to fabricate A1203 nanoparticles and bulk structures in the 8-10-nm range, with controllable vari...ability of nanoparticle size. CAS Beijing Vacuum Physics Laboratory 92P60435B Shanghai JIEFANG RIBAO in Chinese 17 Aug 92 p 3 [Article by Jiang

Certain Chemical Substances Containing Varying Carbon Chain Lengths (Alkyl Ranges Using the Cx-y Notation) on the TSCA Inventory

EPA Pesticide Factsheets

This paper explains the conventions that are applied to certain listings of chemical substances containing ranges of alkyl chain lengths (i.e., carbon chains of varying lengths) for chemical substances on the Toxic Substances Control Act (TSCA)

Chemical control of electrical contact to sp² carbon atoms.

PubMed

Frederiksen, Thomas; Foti, Giuseppe; Scheurer, Fabrice; Speisser, Virginie; Schull, Guillaume

2014-04-16

Carbon-based nanostructures are attracting tremendous interest as components in ultrafast electronics and optoelectronics. The electrical interfaces to these structures play a crucial role for the electron transport, but the lack of control at the atomic scale can hamper device functionality and integration into operating circuitry. Here we study a prototype carbon-based molecular junction consisting of a single C60 molecule and probe how the electric current through the junction depends on the chemical nature of the foremost electrode atom in contact with the molecule. We find that the efficiency of charge injection to a C60 molecule varies substantially for the considered metallic species, and demonstrate that the relative strength of the metal-C bond can be extracted from our transport measurements. Our study further suggests that a single-C60 junction is a basic model to explore the properties of electrical contacts to meso- and macroscopic sp(2) carbon structures.

Chemical control of electrical contact to sp2 carbon atoms

NASA Astrophysics Data System (ADS)

Frederiksen, Thomas; Foti, Giuseppe; Scheurer, Fabrice; Speisser, Virginie; Schull, Guillaume

2014-04-01

Carbon-based nanostructures are attracting tremendous interest as components in ultrafast electronics and optoelectronics. The electrical interfaces to these structures play a crucial role for the electron transport, but the lack of control at the atomic scale can hamper device functionality and integration into operating circuitry. Here we study a prototype carbon-based molecular junction consisting of a single C60 molecule and probe how the electric current through the junction depends on the chemical nature of the foremost electrode atom in contact with the molecule. We find that the efficiency of charge injection to a C60 molecule varies substantially for the considered metallic species, and demonstrate that the relative strength of the metal-C bond can be extracted from our transport measurements. Our study further suggests that a single-C60 junction is a basic model to explore the properties of electrical contacts to meso- and macroscopic sp2 carbon structures.

Efficiency at maximum power for an isothermal chemical engine with particle exchange at varying chemical potential

NASA Astrophysics Data System (ADS)

Koning, Jesper; Koga, Kenichiro; Indekeu, Joseph. O.

2017-02-01

We calculate the efficiency at maximum power (EMP) of an isothermal chemical cycle in which particle uptake occurs at a fixed chemical potential but particle release takes place at varying chemical potential. We obtain the EMP as a function of Δμ/ kT, where Δμ is the difference between the highest and lowest reservoir chemical potentials and T is the absolute temperature. In the linear response limit, Δμ ≪ kT, the EMP tends to the expected universal value 1/2.

Exoskeletons of Bougainvilliidae and other Hydroidolina (Cnidaria, Hydrozoa): structure and composition

PubMed Central

Marian, José Eduardo A.R.; Migotto, Alvaro Esteves; Marques, Antonio Carlos

2017-01-01

The exoskeleton is an important source of characters for the taxonomy of Hydroidolina. It originates as epidermal secretions and, among other functions, protects the coenosarc of the polypoid stage. However, comparative studies on the exoskeletal tissue origin, development, chemical, and structural characteristics, as well as its evolution and homology, are few and fragmented. This study compares the structure and composition of the exoskeleton and underlying coenosarc in members of “Anthoathecata” and some Leptothecata, but does so mainly in bougainvilliid polyps histological analyses. We also studied the development of the exoskeleton under experimental conditions. We identified three types of glandular epidermal cells related to the origin of the exoskeleton and the secretion of its polysaccharides component. The exoskeleton of the species studied is either bilayered (perisarc and exosarc, especially in bougainvilliids) or corneous (perisarc). The exoskeleton varies in chemical composition, structural rigidity, thickness, extension, and coverage in the different regions of the colony. In bilayered exoskeletons, the exosarc is produced first and appears to be a key step in the formation of the rigid exoskeleton. The exoskeleton contains anchoring structures such as desmocytes and “perisarc extensions.” PMID:28224050

Frequent Prescribed Burning as a Long-term Practice in Longleaf Pine Forests Does Not Affect Detrital Chemical Composition.

PubMed

Coates, T Adam; Chow, Alex T; Hagan, Donald L; Wang, G Geoff; Bridges, William C; Dozier, James H

2017-09-01

The O horizon, or detrital layer, of forest soils is linked to long-term forest productivity and health. Fuel reduction techniques, such as prescribed fire, can alter the thickness and composition of this essential ecosystem component. Developing an understanding of the changes in the chemical composition of forest detritus due to prescribed fire is essential for forest managers and stakeholders seeking sustainable, resilient, and productive ecosystems. In this study, we evaluated fuel quantity, fuel structure, and detrital chemical composition in longleaf pine ( Miller) forests that have been frequently burned for the last 40 yr at the Tom Yawkey Wildlife Center in Georgetown, SC. Our results suggest that frequent prescribed fire reduces forest fuel quantity ( < 0.01) and vertical structure ( = 0.01). Using pyrolysis-gas chromatography/mass spectrometry as a molecular technique to analyze detrital chemical composition, including aromatic compounds and polycyclic aromatic hydrocarbons, we found that the chemical composition of forest detritus was nearly uniform for both unburned and burned detritus. Our burning activities varied in the short term, consisting of annual dormant, annual growing, and biennial dormant season burns. Seasonal distinctions were present for fuel quantity and vertical fuel structure, but these differences were not noted for the benzene/phenol ratio. These results are significant as more managers consider burning existing longleaf stands while determining effective management practices for longleaf stands yet to be established. Managers of such stands can be confident that frequent, low-intensity, low-severity prescribed burns in longleaf pine forests do little to affect the long-term chemical composition of forest detritus. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Microstructural, Magnetic Anisotropy, and Magnetic Domain Structure Correlations in Epitaxial FePd Thin Films with Perpendicular Magnetic Anisotropy

NASA Technical Reports Server (NTRS)

Skuza, J. R.; Clavero, C.; Yang, K.; Wincheski, B.; Lukaszew, R. A.

2009-01-01

L1(sub 0)-ordered FePd epitaxial thin films were prepared using dc magnetron sputter deposition on MgO (001) substrates. The films were grown with varying thickness and degree of chemical order to investigate the interplay between the microstructure, magnetic anisotropy, and magnetic domain structure. The experimentally measured domain size/period and magnetic anisotropy in this high perpendicular anisotropy system were found to be correlated following the analytical energy model proposed by Kooy and Enz that considers a delicate balance between the domain wall energy and the demagnetizing stray field energy.

Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides with Discrete Metal Complexes: Structure-Property Relationships.

PubMed

Longo, Julie M; Sanford, Maria J; Coates, Geoffrey W

2016-12-28

Polyesters synthesized through the alternating copolymerization of epoxides and cyclic anhydrides compose a growing class of polymers that exhibit an impressive array of chemical and physical properties. Because they are synthesized through the chain-growth polymerization of two variable monomers, their syntheses can be controlled by discrete metal complexes, and the resulting materials vary widely in their functionality and physical properties. This polymer-focused review gives a perspective on the current state of the field of epoxide/anhydride copolymerization mediated by discrete catalysts and the relationships between the structures and properties of these polyesters.

[Studies on the growth and reproduction of bacterial communities on structural materials of the international space station].

PubMed

Rakova, N M; Svistunova, Iu V; Novikova, N D

2005-01-01

Probability of microbial growth and reproduction on the ISS interior and equipment materials varying in chemical composition was studied with the strains of Bacillus subtilis, Staphylococcus epidermidis, Staphylococcus saprophyticus, Pseudomonas putida etc. sampled from the ISS environment. Controls were ground reference strains of same bacterial species. Based on our results, some of the microorganisms are able to survive and proliferate on structural materials; the ability was greater in space isolates as compared with their ground analogs. The greatest ability to grow and proliferate on materials was demonstrated by Bacillus subtilis.

Engineering of routes to heparin and related polysaccharides.

PubMed

Bhaskar, Ujjwal; Sterner, Eric; Hickey, Anne Marie; Onishi, Akihiro; Zhang, Fuming; Dordick, Jonathan S; Linhardt, Robert J

2012-01-01

Anticoagulant heparin has been shown to possess important biological functions that vary according to its fine structure. Variability within heparin's structure occurs owing to its biosynthesis and animal tissue-based recovery and adds another dimension to its complex polymeric structure. The structural variations in chain length and sulfation patterns mediate its interaction with many heparin-binding proteins, thereby eliciting complex biological responses. The advent of novel chemical and enzymatic approaches for polysaccharide synthesis coupled with high throughput combinatorial approaches for drug discovery have facilitated an increased effort to understand heparin's structure-activity relationships. An improved understanding would offer potential for new therapeutic development through the engineering of polysaccharides. Such a bioengineering approach requires the amalgamation of several different disciplines, including carbohydrate synthesis, applied enzymology, metabolic engineering, and process biochemistry.

Structural flexibility in magnetocaloric RE 5T 4 (RE=rare-earth; T=Si,Ge,Ga) materials: Effect of chemical substitution on structure, bonding and properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Misra, Sumohan

The binary, ternary and multicomponent intermetallic compounds of rare-earth metals (RE) with group 14 elements (Tt) at the RE 5Tt 4 stoichiometry have been known for over 30 years, but only in the past decade have these materials become a gold mine for solid-state chemistry, materials science and condensed matter physics. It all started with the discovery of a giant magnetocaloric effect in Gd 5Si 2Ge 2, along with other extraordinary magnetic properties, such as a colossal magnetostriction and giant magnetoresistance. The distinctiveness of this series is in the remarkable flexibility of the chemical bonding between well-defined, subnanometer-thick slabs andmore » the resultant magnetic, transport, and thermodynamic properties of these materials. This can be controlled by varying either or both RE and Tt elements, including mixed rare-earth elements on the RE sites and different group 14 (or T = group 13 or 15) elements occupying the Tt sites. In addition to chemical means, the interslab interactions are also tunable by temperature, pressure, and magnetic field. Thus, this system provides a splendid 'playground' to investigate the interrelationships among composition, structure, physical properties, and chemical bonding. The work presented in this dissertation involving RE 5T 4 materials has resulted in the successful synthesis, characterization, property measurements, and theoretical analyses of various new intermetallic compounds. The results provide significant insight into the fundamental magnetic and structural behavior of these materials and help us better understand the complex link between a compound's composition, its observed structure, and its properties.« less

Growth and characterization of n-AlGaN 1-D structures with varying Al composition using u-GaN seeds

NASA Astrophysics Data System (ADS)

Kang, San; Chatterjee, Uddipta; Um, Dae-Young; Seo, In Seok; Lee, Cheul-Ro

2017-12-01

Like all the ternary alloys in III-nitride materials family, aluminum gallium nitride (AlGaN) has unique band gap tuning property which enables the alloy to be suitable for many opto-electronic applications. The direct band gap of AlGaN can be tuned from 3.4 to 6.2 eV by changing the composition. In this article, the growth of ternary n-AlGaN micro and nano structures on Si (1 1 1) substrate is demonstrated via 2-step growth method employing metal organic chemical vapor deposition. During the growth flow of Trimethygallium is varied to modulate the final Al/Ga ratio. After the growth, various morphological, crystalline and optical characterizations are carried out to probe in the properties of the grown structures. Recorded X-ray diffraction patterns reveal that the realized structures are wurtzite single crystalline n-AlGaN having a near homogeneous Al distribution and validated by energy dispersive X-ray spectroscopy. Low temperature cathodoluminescence spectra show band edge emission in deep UV region which enables the grown n-AlGaN structures to efficiently find opto-electronic applications in the aforementioned region. Finally, planar photoconductive devices are fabricated using the grown 1-D structures and photocurrent evolution is measured. Structure bearing highest Al content shows a manifold enhancement in photo activity compared to other grown samples. Absolute photoresponsivities of the grown samples are calculated to be 301.47, 116 and 38.13 mA/W which is in accord with the findings of low temperature cathodoluminescence investigation. Therefore, it can be concluded that the successful realization of n-AlGaN 1-D structures varying Al content facilitates the further developments of the field concerning nano- and opto-electronic devices.

Nitrous oxide emission and denitrifier communities in drip-irrigated calcareous soil as affected by chemical and organic fertilizers.

PubMed

Tao, Rui; Wakelin, Steven A; Liang, Yongchao; Hu, Baowei; Chu, Guixin

2018-01-15

The effects of consecutive application of chemical fertilizer with or without organic fertilizer on soil N 2 O emissions and denitrifying community structure in a drip-irrigated field were determined. The four fertilizer treatments were (i) unfertilized, (ii) chemical fertilizer, (iii) 60% chemical fertilizer plus cattle manure, and (iv) 60% chemical fertilizer plus biofertilizer. The treatments with organic amendments (i.e. cattle manure and biofertilizer) reduced cumulative N 2 O emissions by 4.9-9.9%, reduced the N 2 O emission factor by 1.3-42%, and increased denitrifying enzyme activities by 14.3-56.2%. The nirK gene copy numbers were greatest in soil which received only chemical fertilizer. In contrast, nirS- and nosZ-copy numbers were greatest in soil amended with chemical fertilizer plus biofertilizer. Chemical fertilizer application with or without organic fertilizer significantly changed the community structure of nirK-type denitrifiers relative to the unfertilized soil. In comparison, the nirS- and nosZ-type denitrifier genotypes varied in treatments receiving organic fertilizer but not chemical fertilizer alone. The changes in the denitrifier communities were closely associated with soil organic carbon (SOC), NO 3 - , NH 4 + , water holding capacity, and soil pH. Modeling indicated that N 2 O emissions in this soil were primarily associated with the abundance of nirS type denitrifying bacteria, SOC, and NO 3 - . Overall, our findings indicate that (i) the organic fertilizers increased denitrifying enzyme activity, increased denitrifying-bacteria gene copy numbers, but reduced N 2 O emissions, and (ii) nirS- and nosZ-type denitrifiers were more sensitive than nirK-type denitrifiers to the organic fertilizers. Copyright © 2017. Published by Elsevier B.V.

Biological and Chemical Aspects of Natural Biflavonoids from Plants: A Brief Review.

PubMed

Gontijo, Vanessa Silva; Dos Santos, Marcelo Henrique; Viegas, Claudio

2017-01-01

Biflavonoids belong to a subclass of the plant flavonoids family and are limited to several species in the plant kingdom. In the literature, biflavonoids are extensively reported for their pharmacological properties including anti-inflammatory, antioxidant, inhibitory activity against phospholipase A2 (PLA2) and antiprotozoal activity. These activities have been discovered from the small number of biflavonoid structures that have been investigated, although the natural biflavonoids library is likely to be large. In addition, many medicinal properties and traditional use of plants are attributed to the presence of bioflavonoids among their secondary metabolites. Structurally, biflavonoids are polyphenol compounds comprising of two identical or non-identical flavonflavonoid units joined in a symmetrical or unsymmetrical manner through an alkyl or an alkoxy-based linker of varying length. Due to their chemical and biological importance, several bioprospective phytochemical studies and chemical approaches using coupling and molecular rearrangement strategies have been developed to identify and synthesize new bioactive biflavonoids. In this brief review, we present some basic structural aspects for classification and nomenclature of bioflavonoids and a compilation of the literature data published in the last 7 years, concerning the discovery of new natural biflavonoids of plant origin and their pharmacological and biological properties. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Gallium assisted plasma enhanced chemical vapor deposition of silicon nanowires.

PubMed

Zardo, I; Yu, L; Conesa-Boj, S; Estradé, S; Alet, Pierre Jean; Rössler, J; Frimmer, M; Roca I Cabarrocas, P; Peiró, F; Arbiol, J; Morante, J R; Fontcuberta I Morral, A

2009-04-15

Silicon nanowires have been grown with gallium as catalyst by plasma enhanced chemical vapor deposition. The morphology and crystalline structure has been studied by electron microscopy and Raman spectroscopy as a function of growth temperature and catalyst thickness. We observe that the crystalline quality of the wires increases with the temperature at which they have been synthesized. The crystalline growth direction has been found to vary between <111> and <112>, depending on both the growth temperature and catalyst thickness. Gallium has been found at the end of the nanowires, as expected from the vapor-liquid-solid growth mechanism. These results represent good progress towards finding alternative catalysts to gold for the synthesis of nanowires.

Biosolubilization of coal by Candida in glucose limited cultures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitter, J.; Guillory, L.; Bose, N.K.

1990-01-01

Coal biodegradation is attracting the attention of many workers because of its significance for efficient bioconversion of coal into useful chemicals. The authors work is based upon the beneficiation of a fungus (candida) on subbituminous coal. Candida was grown on both solid and liquid sabouraud medium and the coal solubilizing activity was studied at varying glucose concentration and temperature. Lower glucose concentration and higher temperature enhanced coal solubilizing activity by this fungus. Preliminary work has begun on analyzing organic extractions (alumina chromatography) of the liquid produced after microbial solubilization, including elemental analysis, solubility, molecular weights and chemical structure. This preliminarymore » work suggests that the candida could metabolize naturally occurring coal as substrate.« less

Tuning reactivity of diphenylpropynone derivatives with metal-associated amyloid-β species via structural modifications.

PubMed

Liu, Yuzhong; Kochi, Akiko; Pithadia, Amit S; Lee, Sanghyun; Nam, Younwoo; Beck, Michael W; He, Xiaoming; Lee, Dongkuk; Lim, Mi Hee

2013-07-15

A diphenylpropynone derivative, DPP2, has been recently demonstrated to target metal-associated amyloid-β (metal-Aβ) species implicated in Alzheimer's disease (AD). DPP2 was shown to interact with metal-Aβ species and subsequently control Aβ aggregation (reactivity) in vitro; however, its cytotoxicity has limited further biological applications. In order to improve reactivity toward Aβ species and lower cytotoxicity, along with gaining an understanding of a structure-reactivity-cytotoxicity relationship, we designed, prepared, and characterized a series of small molecules (C1/C2, P1/P2, and PA1/PA2) as structurally modified DPP2 analogues. A similar metal binding site to that of DPP2 was contained in these compounds while their structures were varied to afford different interactions and reactivities with metal ions, Aβ species, and metal-Aβ species. Distinct reactivities of our chemical family toward in vitro Aβ aggregation in the absence and presence of metal ions were observed. Among our chemical series, the compound (C2) with a relatively rigid backbone and a dimethylamino group was observed to noticeably regulate both metal-free and metal-mediated Aβ aggregation to different extents. Using our compounds, cell viability was significantly improved, compared to that with DPP2. Lastly, modifications on the DPP framework maintained the structural properties for potential blood-brain barrier (BBB) permeability. Overall, our studies demonstrated that structural variations adjacent to the metal binding site of DPP2 could govern different metal binding properties, interactions with Aβ and metal-Aβ species, reactivity toward metal-free and metal-induced Aβ aggregation, and cytotoxicity of the compounds, establishing a structure-reactivity-cytotoxicity relationship. This information could help gain insight into structural optimization for developing nontoxic chemical reagents toward targeting metal-Aβ species and modulating their reactivity in biological systems.

Dynamic Chemically Driven Dewetting, Spreading, and Self-Running of Sessile Droplets on Crystalline Silicon.

PubMed

Arscott, Steve

2016-12-06

A chemically driven dewetting effect is demonstrated using sessile droplets of dilute hydrofluoric acid on chemically oxidized silicon wafers. The dewetting occurs as the thin oxide is slowly etched by the droplet and replaced by a hydrogen-terminated surface; the result of this is a gradual increase in the contact angle of the droplet with time. The time-varying work of adhesion is calculated from the time-varying contact angle; this corresponds to the changing chemical nature of the surface during dewetting and can be modeled by the well-known logistic (sigmoid) function often used for the modeling of restricted growth, in this case, the transition from an oxidized surface to a hydrogen-terminated silicon surface. The observation of the time-varying contact angle allows one to both measure the etch rate of the silicon oxide and estimate the hydrogenation rate as a function of HF concentration and wafer type. In addition to this, at a certain HF concentration, a self-running droplet effect is observed. In contrast, on hydrogen-terminated silicon wafers, a chemically induced spreading effect is observed using sessile droplets of nitric acid. The droplet spreading can also be modeled using a logistical function, where the restricted growth is the transition from hydrogen-terminated to a chemically induced oxidized silicon surface. The chemically driven dewetting and spreading observed here add to the methods available to study dynamic wetting (e.g., the moving three-phase contact line) of sessile droplets on surfaces. By slowing down chemical kinetics of the wetting, one is able to record the changing profile of the sessile droplet with time and gather information concerning the time-varying surface chemistry. The data also indicates a chemical interface hysteresis (CIH) that is compared to contact angle hysteresis (CAH). The approach can also be used to study the chemical etching and deposition behavior of thin films using liquids by monitoring the macroscopic droplet profile and relating this to the time-varying physical and chemical interface phenomena.

Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns

DOE PAGES

Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.; ...

2016-08-16

Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyreneblock-poly(methyl methacrylate). Faster assembly kinetics aremore » observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. Lastly, the rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.« less

High Pressure EPR for Probing the Magnetic Anisotropy in Single Molecule Magnets

NASA Astrophysics Data System (ADS)

Bhaskaran, Lakshmi; Trociewitz, Bianca; Dubroca, Thierry; Hill, Stephen

Single-molecule magnets (SMM) are potential candidates for nanoscale magnetic information storage, and a platform for studying classical and quantum behaviors at the mesoscopic scale. Varying the structures of these molecules by chemical modification can give rise to changes in their magnetic properties. However, this approach can be unpredictable, leaving very little control via chemical synthesis. An alternate approach is to exert physical pressure. This convenient tool can be used to vary crystal packing, local coordination geometries, as well as inter-ion and intermolecular interactions without changing the chemical composition of a SMM. Moreover, pressure in combination with Electron Paramagnetic Resonance (EPR), can be employed to better understand the factors that control magnetic anisotropy, both at the single-ion level and in exchange-coupled molecules. Here we present a microwave cavity integrated with a diamond anvil cell with a pressure range up to 1.5 GPa. As an example we show results from single crystal high field EPR experiments performed on an exchange coupled system, [Fe8O2(OH)12(tacn)6] Br8.9H2O, better known as Fe8 with a giant spin of S =10. The obtained pressure-dependent results will be discussed. National High Magnetic Field Laboratory.

Inorganic SnIP-Type Double Helices in Main-Group Chemistry.

PubMed

Baumgartner, Maximilian; Weihrich, Richard; Nilges, Tom

2017-05-05

Inspired by the synthesis of the first atomic-scale double-helix semiconductor SnIP, this study deals with the question of whether more atomistic, inorganic double-helix compounds are accessible. With the aid of quantum chemical calculations, we have identified 31 candidates by a homoatomic substitution in MXPn, varying the Group 14 M-element from Si to Pb, the Group 17 X-element from F to I and replacing the pnictide (Pn) phosphorus by arsenic. The double-helical structure of SnIP has been used as the starting model for all candidates and the electronic structure and vibrational spectra were determined within the framework of density functional theory (DFT). Varying the outer MX or the inner Pn helix led to the conclusion that iodide- and bromide-containing MXPn compounds show similar structures to SnIP. Here, the calculations indicate interesting effects for electronic band-gap tuning. For the highly polarized fluorides, a segregation of the helices to more complex MX substructures is predicted. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alcohol vapor sensing by cadmium-doped zinc oxide thick films based chemical sensor

NASA Astrophysics Data System (ADS)

Zargar, R. A.; Arora, M.; Chackrabarti, S.; Ahmad, S.; Kumar, J.; Hafiz, A. K.

2016-04-01

Cadmium-doped zinc oxide nanoparticles were derived by simple chemical co-precipitation route using zinc acetate dihydrate and cadmium acetate dihydrate as precursor materials. The thick films were casted from chemical co-precipitation route prepared nanoparticles by economic facile screen printing method. The structural, morphological, optical and electrical properties of the film were characterized relevant to alcohol vapor sensing application by powder XRD, SEM, UV-VIS and DC conductivity techniques. The response and sensitivity of alcohol (ethanol) vapor sensor are obtained from the recovery curves at optimum working temperature range from 20∘C to 50∘C. The result shows that maximum sensitivity of the sensor is observed at 25∘C operating temperature. On varying alcohol vapor concentration, minor variation in resistance has been observed. The sensing mechanism of sensor has been described in terms of physical adsorption and chemical absorption of alcohol vapors on cadmium-doped zinc oxide film surface and inside film lattice network through weak hydrogen bonding, respectively.

Complementary Split-Ring Resonator-Loaded Microfluidic Ethanol Chemical Sensor.

PubMed

Salim, Ahmed; Lim, Sungjoon

2016-10-28

In this paper, a complementary split-ring resonator (CSRR)-loaded patch is proposed as a microfluidic ethanol chemical sensor. The primary objective of this chemical sensor is to detect ethanol's concentration. First, two tightly coupled concentric CSRRs loaded on a patch are realized on a Rogers RT/Duroid 5870 substrate, and then a microfluidic channel engraved on polydimethylsiloxane (PDMS) is integrated for ethanol chemical sensor applications. The resonant frequency of the structure before loading the microfluidic channel is 4.72 GHz. After loading the microfluidic channel, the 550 MHz shift in the resonant frequency is ascribed to the dielectric perturbation phenomenon when the ethanol concentration is varied from 0% to 100%. In order to assess the sensitivity range of our proposed sensor, various concentrations of ethanol are tested and analyzed. Our proposed sensor exhibits repeatability and successfully detects 10% ethanol as verified by the measurement set-up. It has created headway to a miniaturized, non-contact, low-cost, reliable, reusable, and easily fabricated design using extremely small liquid volumes.

Complementary Split-Ring Resonator-Loaded Microfluidic Ethanol Chemical Sensor

PubMed Central

Salim, Ahmed; Lim, Sungjoon

2016-01-01

In this paper, a complementary split-ring resonator (CSRR)-loaded patch is proposed as a microfluidic ethanol chemical sensor. The primary objective of this chemical sensor is to detect ethanol’s concentration. First, two tightly coupled concentric CSRRs loaded on a patch are realized on a Rogers RT/Duroid 5870 substrate, and then a microfluidic channel engraved on polydimethylsiloxane (PDMS) is integrated for ethanol chemical sensor applications. The resonant frequency of the structure before loading the microfluidic channel is 4.72 GHz. After loading the microfluidic channel, the 550 MHz shift in the resonant frequency is ascribed to the dielectric perturbation phenomenon when the ethanol concentration is varied from 0% to 100%. In order to assess the sensitivity range of our proposed sensor, various concentrations of ethanol are tested and analyzed. Our proposed sensor exhibits repeatability and successfully detects 10% ethanol as verified by the measurement set-up. It has created headway to a miniaturized, non-contact, low-cost, reliable, reusable, and easily fabricated design using extremely small liquid volumes. PMID:27801842

Chemical variations among L-chondrites. IV - Analyses, with petrographic notes, of 13 L-group and 3 LL-group chondrites

NASA Astrophysics Data System (ADS)

Jarosewich, E.; Dodd, R. T.

1985-03-01

Procedures are reviewed for selecting, preparing and analyzing meteorite samples, present new analyses of 16 ordinary chondrites, and discuss variations of Fe, S and Si in the L-group. A tendency for Fe/Mg, S/Mg and Si/Mg to be low in L chondrites of facies d to f testifies that post-metamorphic shock melting played a significant role in the chemical diversification of the L-group. However, these ratios also vary widely and sympathetically in melt-free chondrites, indicating that much of the L-group's chemical variation arose prior to thermal metamorphism and is in that sense primary. If all L chondrites come from one parent body, type-correlated chemical trends suggest: (1) that the body had a tradiational 'onion skin' structure, with metamorphic intensity increasing with depth; and (2) that it formed from material that became more homogeneous, slightly poorer in iron, and significantly richer in sulfur as accretion proceeded.

Chemical Variations Among L-Chondrites--IV. Analyses, with Petrographic Notes, of 13 L-group and 3 LL-group Chondrites

NASA Astrophysics Data System (ADS)

Jarosewich, E.; Dodd, R. T.

1985-03-01

We review our procedures for selecting, preparing and analyzing meteorite samples, present new analyses of 16 ordinary chondrites, and discuss variations of Fe, S and Si in the L-group. A tendency for Fe/Mg, S/Mg and Si/Mg to be low in L chondrites of facies d to f testifies that post-metamorphic shock melting played a significant role in the chemical diversification of the L-group. However, these ratios also vary widely and sympathetically in melt-free chondrites, indicating that much of the L-group's chemical variation arose prior to thermal metamorphism and is in that sense primary. If all L chondrites come from one parent body, type-correlated chemical trends suggest: 1) that the body had a traditional "onion skin" structure, with metamorphic intensity increasing with depth; and 2) that it formed from material that became more homogeneous, slightly poorer in iron, and significantly richer in sulfur as accretion proceeded.

Electromagnetic modelling of Raman enhancement from nanoscale substrates: a route to estimation of the magnitude of the chemical enhancement mechanism in SERS.

PubMed

Brown, Richard J C; Wang, Jian; Tantra, Ratna; Yardley, Rachel E; Milton, Martin J T

2006-01-01

Despite widespread use for more than two decades, the SERS phenomenon has defied accurate physical and chemical explanation. The relative contributions from electronic and chemical mechanisms are difficult to quantify and are often not reproduced under nominally similar experimental conditions. This work has used electromagnetic modelling to predict the Raman enhancement expected from three configurations: metal nanoparticles, structured metal surfaces, and sharp metal tips interacting with metal surfaces. In each case, parameters such as artefact size, artefact separation and incident radiation wavelength have been varied and the resulting electromagnetic field modelled. This has yielded an electromagnetic description of these configurations with predictions of the maximum expected Raman enhancement, and hence a prediction of the optimum substrate configuration for the SERS process. When combined with experimental observations of the dependence of Raman enhancement with changing ionic strength, the modelling results have allowed a novel estimate of the size of the chemical enhancement mechanism to be produced.

Nonlinear control of high-frequency phonons in spider silk

NASA Astrophysics Data System (ADS)

Schneider, Dirk; Gomopoulos, Nikolaos; Koh, Cheong Y.; Papadopoulos, Periklis; Kremer, Friedrich; Thomas, Edwin L.; Fytas, George

2016-10-01

Spider dragline silk possesses superior mechanical properties compared with synthetic polymers with similar chemical structure due to its hierarchical structure comprised of partially crystalline oriented nanofibrils. To date, silk’s dynamic mechanical properties have been largely unexplored. Here we report an indirect hypersonic phononic bandgap and an anomalous dispersion of the acoustic-like branch from inelastic (Brillouin) light scattering experiments under varying applied elastic strains. We show the mechanical nonlinearity of the silk structure generates a unique region of negative group velocity, that together with the global (mechanical) anisotropy provides novel symmetry conditions for gap formation. The phononic bandgap and dispersion show strong nonlinear strain-dependent behaviour. Exploiting material nonlinearity along with tailored structural anisotropy could be a new design paradigm to access new types of dynamic behaviour.

Chemical Bonding in Sulfide Minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaughan, David J.; Rosso, Kevin M.

An understanding of chemical bonding and electronic structure in sulfide minerals is central to any attempt at understanding their crystal structures, stabilities and physical properties. It is also an essential precursor to understanding reactivity through modeling surface structure at the molecular scale. In recent decades, there have been remarkable advances in first principles (ab initio) methods for the quantitative calculation of electronic structure. These advances have been made possible by the very rapid development of high performance computers. Several review volumes that chart the applications of these developments in mineralogy and geochemistry are available (Tossell and Vaughan, 1992; Cygan andmore » Kubicki, 2001). An important feature of the sulfide minerals is the diversity of their electronic structures, as evidenced by their electrical and magnetic properties (see Pearce et al. 2006, this volume). Thus, sulfide minerals range from insulators through semiconductors to metals, and exhibit every type of magnetic behavior. This has presented problems for those attempting to develop bonding models for sulfides, and also led to certain misconceptions regarding the kinds of models that may be appropriate. In this chapter, chemical bonding and electronic structure models for sulfides are reviewed with emphasis on more recent developments. Although the fully ab initio quantitative methods are now capable of a remarkable degree of sophistication in terms of agreement with experiment and potential to interpret and predict behavior with varying conditions, both qualitative and more simplistic quantitative approaches will also be briefly discussed. This is because we believe that the insights which they provide are still helpful to those studying sulfide minerals. In addition to the application of electronic structure models and calculations to solid sulfides, work on sulfide mineral surfaces (Rosso and Vaughan 2006a,b) and solution complexes and clusters (Rickard and Luther, 2006) are discussed in detail later in this volume.« less

Effect of the KOH chemical treatment on the optical and photocatalytic properties of BiVO4 thin films

NASA Astrophysics Data System (ADS)

Mirabal-Rojas, R.; Depablos-Rivera, O.; Thalluri, S. M.; Medina, J. C.; Bizarro, M.; Perez-Alvarez, J.; Rodil, S. E.; Zeinert, A.

2016-04-01

In this work, we present the structural, optical and photocatalytic properties of BiVO4 thin films produced by a dual-magnetron sputtering process using both Bi2O3 (α-phase, 99.98 % purity) and V (99.9 % purity) targets under Ar/O2 atmosphere with a ratio of 18:2. The films were deposited varying the power applied to the targets to obtain stoichiometric films, and the monoclinic structure was achieved by post-deposition annealing. The dual process was chosen to better control the Bi/V ratio since Bi and V have very different sputtering yields. In particular, the influence of a chemical treatment using potassium hydroxide (KOH) on the optical properties and different dye discolorations (acid blue 113 and methyl orange) is discussed. The optical properties were studied by reflectance and transmittance spectroscopy, where the spectra were fitted to obtain the refractive index dispersion and the optical band gap of the BiVO4 as a function of the film structure, as determined by X-ray diffraction and Raman spectroscopy.

Structural and electrical characterization of microcrystalline silicon films prepared by a layer-by-layer technique with a plasma-enhanced chemical-vapor deposition system

NASA Astrophysics Data System (ADS)

Hong, J. P.; Kim, C. O.; Nahm, T. U.; Kim, C. M.

2000-02-01

Microcrystalline silicon films have been prepared on indium-coated glass utilizing a layer-by-layer technique with a plasma-enhanced chemical-vapor deposition system. The microcrystalline films were fabricated by varying the number of cycles from 10 to 60 under a fixed H2 time (t2) of 120 s, where the corresponding deposition time (t1) of amorphous silicon thin film was 60 s. Structural properties, such as the crystalline volume fraction (Xc) and grain sizes were analyzed by using Raman spectroscopy and a scanning electron microscopy. The carrier transport was characterized by the temperature dependence of dark conductivity, giving rise to the calculation of activation energy (Ea). Optical energy gaps (Eg) were also investigated using an ultraviolet spectrophotometer. In addition, the process under different hydrogen plasma time (t2) at a fixed number of 20 cycles was extensively carried out to study the dominant role of hydrogen atoms in layer-by-layer deposition. Finally, the correlation between structural and electrical properties has been discussed on the basis of experimental results.

Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering.

PubMed

Ho, Tuan Anh; Greathouse, Jeffery A; Wang, Yifeng; Criscenti, Louise J

2017-11-10

The porosity of clay aggregates is an important property governing chemical reactions and fluid flow in low-permeability geologic formations and clay-based engineered barrier systems. Pore spaces in clays include interlayer and interparticle pores. Under compaction and dewatering, the size and geometry of such pore spaces may vary significantly (sub-nanometer to microns) depending on ambient physical and chemical conditions. Here we report a molecular dynamics simulation method to construct a complex and realistic clay-like nanoparticle aggregate with interparticle pores and grain boundaries. The model structure is then used to investigate the effect of dewatering and water content on micro-porosity of the aggregates. The results suggest that slow dewatering would create more compact aggregates compared to fast dewatering. Furthermore, the amount of water present in the aggregates strongly affects the particle-particle interactions and hence the aggregate structure. Detailed analyses of particle-particle and water-particle interactions provide a molecular-scale view of porosity and texture development of the aggregates. The simulation method developed here may also aid in modeling the synthesis of nanostructured materials through self-assembly of nanoparticles.

Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering

DOE PAGES

Ho, Tuan Anh; Greathouse, Jeffery A.; Wang, Yifeng; ...

2017-11-10

The porosity of clay aggregates is an important property governing chemical reactions and fluid flow in low-permeability geologic formations and clay-based engineered barrier systems. Pore spaces in clays include interlayer and interparticle pores. Under compaction and dewatering, the size and geometry of such pore spaces may vary significantly (sub-nanometer to microns) depending on ambient physical and chemical conditions. Here we report a molecular dynamics simulation method to construct a complex and realistic clay-like nanoparticle aggregate with interparticle pores and grain boundaries. The model structure is then used to investigate the effect of dewatering and water content on micro-porosity of themore » aggregates. The results suggest that slow dewatering would create more compact aggregates compared to fast dewatering. Furthermore, the amount of water present in the aggregates strongly affects the particle-particle interactions and hence the aggregate structure. Detailed analyses of particle-particle and water-particle interactions provide a molecular-scale view of porosity and texture development of the aggregates. The simulation method developed here may also aid in modeling the synthesis of nanostructured materials through self-assembly of nanoparticles.« less

Bio-Based Nano Composites from Plant Oil and Nano Clay

NASA Astrophysics Data System (ADS)

Lu, Jue; Hong, Chang K.; Wool, Richard P.

2003-03-01

We explored the combination of nanoclay with new chemically functionalized, amphiphilic, plant oil resins to form bio-based nanocomposites with improved physical and mechanical properties. These can be used in many new applications, including the development of self-healing nanocomposites through controlled reversible exfoliation/intercalation, and self-assembled nano-structures. Several chemically modified triglyceride monomers of varying polarity, combined with styrene (ca 30include acrylated epoxidized soybean oil (AESO), maleated acrylated epoxidized soybean oil (MAESO) and soybean oil pentaerythritol glyceride maleates (SOPERMA), containing either hydroxyl group or acid functionality or both. The clay used is a natural montmorillonite modified with methyl tallow bis-2-hydroxyethyl quaternary ammonium chloride, which has hydroxyl groups. Both XRD and TEM showed a completely exfoliated structure at 3 wtwhen the clay content is above 5 wtconsidered a mix of intercalated and partially exfoliated structure. The controlled polarity of the monomer has a major effect on the reversible dispersion of clay in the polymer matrix. The bio-based nanocomposites showed a significant increase in flexural modulus and strength. Supported by EPA and DoE

Chemical probes and engineered constructs reveal a detailed unfolding mechanism for a solvent-free multi-domain protein

PubMed Central

Eschweiler, Joseph D.; Martini, Rachel M.; Ruotolo, Brandon T.

2017-01-01

Despite the growing application of gas-phase measurements in structural biology and drug discovery, the factors that govern protein stabilities and structures in a solvent-free environment are still poorly understood. Here, we examine the solvent-free unfolding pathway for a group of homologous serum albumins. Utilizing a combination of chemical probes and non-covalent reconstructions, we draw new specific conclusions regarding the unfolding of albumins in the gas-phase, as well as more-general inferences regarding the sensitivity of collision induced unfolding to changes in protein primary and tertiary structure. Our findings suggest that the general unfolding pathway of low charge state albumin ions is largely unaffected by changes in primary structure; however, the stabilities of intermediates along these pathways vary widely as sequences diverge. Additionally, we find that human albumin follows a domain associated unfolding pathway, and are able to assign each unfolded form observed in our gas-phase dataset to the disruption of specific domains within the protein. The totality of our data informs the first detailed mechanism for multi-domain protein unfolding in the gas phase, and highlights key similarities and differences from the known the solution-phase pathway. PMID:27959526

2D materials integrated in Si3N4 photonics platform

NASA Astrophysics Data System (ADS)

Faneca, Joaquin; Hogan, Benjamin T.; Torres Alonso, E.; Craciun, Monica; Baldycheva, Anna

2018-02-01

In this paper, we discuss a back-end CMOS fabrication process for the large-scale integration of 2D materials on SOI (siliconon-insulator) platform and present a complete theoretical study of the change in the effective refractive index of 2D materialsenabled silicon nitride waveguide structures. The chemical vapour deposition (CVD) and liquid exfoliation fabrication methods are described for the fabrication of graphene, WS2 and MoS2 thin films. Finite-difference frequency-domain (FDFD) approach and the Transfer Matrix Method were used in order to mathematically describe these structures. The introduction of thin films of 2D material onto Si3N4 waveguide structures allows manipulation of the optical characteristics to a high degree of precision by varying the Fermi-level through the engineering of the number of atomically thin layers or by electrical tuning, for example. Based on the proposed tuning approach, designs of graphene, WS2 and MoS2 enabled Si3N4 micro-ring structures are presented for the visible and NIR range, which demonstrate versatility and desirable properties for a wide range of applications, such as bio-chemical sensing and optical communications.

Phosphorylated Derivatives of Alkaloids and Nitrogen-containing Heterocycles — Cholinesterase Inhibitors

NASA Astrophysics Data System (ADS)

Sadykov, Abid S.; Dalimov, D. N.; Godovikov, Nikolai N.

1983-10-01

The review deals with the synthesis and anticholinesterase activities of phosphorylated derivatives of certain alkaloids and nitrogen-containing heterocycles. It is shown that the conformational properties of the alkaloid and nitrogen-containing heterocycle residues in the composition of the organophosphorus inhibitor (OPI) molecule play an important role in the inhibition of the catalytic activity of cholinesterases. The type of inhibition of cholinesterases also varies as a function of chemical structure. The bibliography includes 45 references.

Nano-Bio Interactions of Porous and Nonporous Silica Nanoparticles of Varied Surface Chemistry: A Structural, Kinetic, and Thermodynamic Study of Protein Adsorption from RPMI Culture Medium.

PubMed

Lehman, Sean E; Mudunkotuwa, Imali A; Grassian, Vicki H; Larsen, Sarah C

2016-01-26

Understanding complex chemical changes that take place at nano-bio interfaces is of great concern for being able to sustainably implement nanomaterials in key applications such as drug delivery, imaging, and environmental remediation. Typical in vitro assays use cell viability as a proxy to understanding nanotoxicity but often neglect how the nanomaterial surface can be altered by adsorption of solution-phase components in the medium. Protein coronas form on the nanomaterial surface when incubated in proteinaceous solutions. Herein, we apply a broad array of techniques to characterize and quantify protein corona formation on silica nanoparticle surfaces. The porosity and surface chemistry of the silica nanoparticles have been systematically varied. Using spectroscopic tools such as FTIR and circular dichroism, structural changes and kinetic processes involved in protein adsorption were evaluated. Additionally, by implementing thermogravimetric analysis, quantitative protein adsorption measurements allowed for the direct comparison between samples. Taken together, these measurements enabled the extraction of useful chemical information on protein binding onto nanoparticles in solution. Overall, we demonstrate that small alkylamines can increase protein adsorption and that even large polymeric molecules such as poly(ethylene glycol) (PEG) cannot prevent protein adsorption in these systems. The implications of these results as they relate to further understanding nano-bio interactions are discussed.

Survey of Lignin-Structure Changes and Depolymerization during Ionic Liquid Pretreatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Tanmoy; Isern, Nancy G.; Sun, Jian

A detailed study of chemical changes in lignin structure during the ionic liquid (IL) pretreatment process is not only pivotal for understanding and overcoming biomass recalcitrance during IL pretreatment, but also is necessary for designing new routes for lignin valorization. Chemical changes in lignin were systematically studied as a function of pretreatment temperature, time and type of IL used. Kraft lignin was used as the lignin source and common pretreatment conditions were employed using three different ILs of varying chemical structure in terms of acidic or basic character. The chemical changes in the lignin structure due to IL pretreatment processesmore » were monitored using 1H-13C HSQC NMR, 31P NMR, elemental analysis, GPC, FT-IR, and the depolymerized products were analyzed using GC-MS. Although pretreatment in acidic IL, triethylammonium hydrogensulfate ([TEA][HSO4]) results in maximum decrease in β-aryl ether bond, maximum dehydration and recondensation pathways were also evident, with the net process showing a minimum decrease in the molecular weight of regenerated lignin. However, 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) pretreatment yields a smaller decrease in the β-aryl ether content along with minimum evidence of recondensation, resulting in the maximum decrease in the molecular weight. Cholinium lysinate ([Ch][Lys]) pretreatment shows an intermediate result, with moderate depolymerization, dehydration and recondensation observed. The depolymerization products after IL pretreatment are found to be a function of the pretreatment temperature and the specific chemical nature of the IL used. At higher pretreatment temperature, [Ch][Lys] pretreatment yields guaiacol, [TEA][HSO4] yields guaiacylacetone, and [C2C1Im][OAc] yields both guaiacol and guaiacylacetone as major products. These results clearly indicate that the changes in lignin structure as well as the depolymerized product profile depend on the pretreatment conditions and the nature of the ILs. The insight gained on lignin structure changes and possible depolymerized products during IL pretreatment process would help future lignin valorization efforts in a potential IL-based lignocellulosic biorefinery.« less

Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

PubMed

Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

2015-03-28

Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution.

Inside out: Speed-dependent barriers to reactive mixing

NASA Astrophysics Data System (ADS)

Kelley, Douglas; Nevins, Thomas

2015-11-01

Reactive mixing occurs wherever fluid flow and chemical or biological growth interact over time and space. Those interactions often lead to steep gradients in reactant and product concentration, arranged in complex spatial structures that can cause wide variation in the global reaction rate and concentrations. By simultaneously measuring fluid velocity and reaction front locations in laboratory experiments with the Belousov-Zhabotinsky reaction, we find that the barriers defining those structures vary dramatically with speed. In particular, we find that increasing flow speed causes reacted regions to move from vortex edges to vortex cores, thus turning the barriers ``inside out''. This observation has implications for reactive mixing of phytoplankton in global oceans.

Ion-beam assisted laser printing of porous nanorings

NASA Astrophysics Data System (ADS)

Syubaev, S.; Kuchmizhak, A.; Nepomnyashchiy, A.

2017-09-01

Pulsed-laser fabrication of noble-metal nanorings with a tunable internal porous structure, which can be further uncapped by using an ion-beam etching procedure, was demonstrated for the first time. Density and average size of the pores were shown to be tuned in a wide range by varying an applied pulse energy and a chemical composition of the metal film controlled via the film magnetron deposition in the appropriate gaseous environment. According to our preliminary numerical simulations, the controlled porosity provides multifold near-field enhancement of the electromagnetic fields, making such structures promising for spectroscopic bioidentification based on a surface-enhanced Raman scattering.

Laser Tailoring the Surface Chemistry and Morphology for Wear, Scale and Corrosion Resistant Superhydrophobic Coatings.

PubMed

Boinovich, Ludmila B; Emelyanenko, Kirill A; Domantovsky, Alexander G; Emelyanenko, Alexandre M

2018-06-04

A strategy, combining laser chemical modification with laser texturing, followed by chemisorption of the fluorinated hydrophobic agent was used to fabricate the series of superhydrophobic coatings on an aluminum alloy with varied chemical compositions and parameters of texture. It was shown that high content of aluminum oxynitride and aluminum oxide formed in the surface layer upon laser treatment allows solving the problem of enhancement of superhydrophobic coating resistance to abrasive loads. Besides, the multimodal structure of highly porous surface layer leads to self-healing ability of fabricated coatings. Long-term behavior of designed coatings in "hard" hot water with an essential content of calcium carbonate demonstrated high antiscaling resistance with self-cleaning potential against solid deposits onto the superhydrophobic surfaces. Study of corrosion protection properties and the behavior of coatings at long-term contact with 0.5 M NaCl solution indicated extremely high chemical stability and remarkable anticorrosion properties.

Exploiting mineral data: applications to the diversity, distribution, and social networks of copper mineral

NASA Astrophysics Data System (ADS)

Morrison, S. M.; Downs, R. T.; Golden, J. J.; Pires, A.; Fox, P. A.; Ma, X.; Zednik, S.; Eleish, A.; Prabhu, A.; Hummer, D. R.; Liu, C.; Meyer, M.; Ralph, J.; Hystad, G.; Hazen, R. M.

2016-12-01

We have developed a comprehensive database of copper (Cu) mineral characteristics. These data include crystallographic, paragenetic, chemical, locality, age, structural complexity, and physical property information for the 689 Cu mineral species approved by the International Mineralogical Association (rruff.info/ima). Synthesis of this large, varied dataset allows for in-depth exploration of statistical trends and visualization techniques. With social network analysis (SNA) and cluster analysis of minerals, we create sociograms and chord diagrams. SNA visualizations illustrate the relationships and connectivity between mineral species, which often form cliques associated with rock type and/or geochemistry. Using mineral ecology statistics, we analyze mineral-locality frequency distribution and predict the number of missing mineral species, visualized with accumulation curves. By assembly of 2-dimensional KLEE diagrams of co-existing elements in minerals, we illustrate geochemical trends within a mineral system. To explore mineral age and chemical oxidation state, we create skyline diagrams and compare trends with varying chemistry. These trends illustrate mineral redox changes through geologic time and correlate with significant geologic occurrences, such as the Great Oxidation Event (GOE) or Wilson Cycles.

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

[Effects of different organic manure sources and their combinations with chemical fertilization on soil nematode community structure in a paddy field of East China].

PubMed

Liu, Ting; Ye, Cheng-Long; Chen, Xiao-Yun; Ran, Wei; Shen, Qi-Rong; Hu, Feng; Li, Hui-Xin

2013-12-01

A comparative study was conducted to investigate the effects of different fertilization modes on the soil nematode community structure in a paddy field with paddy rice and wheat rotation in Jintan County (31 degrees 39'41.8" N, 119 degrees 28'23.5" E) of Jiangsu Province, East China. Six treatments were installed, i. e., no fertilization (CK), 100% chemical NPK fertilization (F), pig manure compost plus 50% chemical fertilization (PF), straw returning plus 100% chemical fertilization (SF), pig manure compost and straw returning plus 50% chemical fertilization (PSF), and application of commercial pig manure-inorganic complex fertilizer (PMF). The soil samples were collected from the field after the paddy rice harvested in autumn. The two continuous years study showed that the soil nematode community structure varied with fertilization treatments and years. The combined application of chemical fertilizers and organic manures increased the total number of soil nematodes, decreased the abundance of soil bacterivorous nematodes, and made the abundance of predator- and omnivore nematodes increased significantly. No significant differences were observed in the abundance of soil fungivorous nematodes among all the treatments. Chemical fertilization alone and the application of commercial pig manure-inorganic complex fertilizer had no obvious suppression effect on the soil phytophagous nematodes. The abundance of soil bacteriavorous nematodes under the combined application of chemical fertilizers and organic manures was relatively increased in the second year, as compared with that in the first year, while the abundance of soil phytophagous nematodes (Hirschmanniella) was relatively decreased in the second year. From the aspect of nematode ecological indices, the Margalef diversity index (H) under the combined application of chemical fertilizers and organic manures in the second year had an increasing trend, while the NCR index had less change. The Wasilewka index had a relative increase in the second year, while the plant-parasitic index had a relative decrease. It was suggested that the application of organic manure could increase the abundance of soil microbivorous nematodes, and made the soil environment tend to be healthy.

Relationships between chemical structure and rat repellency. II. Compounds screened between 1950 and 1960

USGS Publications Warehouse

Bowles, W.A.; Adomaitis, V.A.; DeWitt, J.B.; Pratt, J.J.

1974-01-01

Over 4,600 compounds, chiefly organic types, were evaluated using both a food acceptance test (Part A) and a barrier penetration bioassay (Part B), to correlate relationships between chemical structure and rodent repellency.These chemicals are indexed and classified according to the functional groups present and to the degree of substitution within their molecular structures. The results of reduction in foot consumption for each compound appraised are calculated and their K values listed in Table I.The repellent activities of the functional groups represented, alone or in combinations, are expressed in Table II by a Functional Group Repellency Index. A ranking of these indices suggests that acyclic and heteroyclic compounds containing tri- or pentavalent nitrogen would be a parent compound of choice for synthesizing novel repellents. Other molecular arrangements, spatial configurations and combinations of functional groups are compared.There were 123 active, interesting or promising compounds included in the 699 having K values of 85 or greater, which were selected for the barrier appraisal study. These chemicals were formulated in selective solvents at several concentrations and applied to burlap. Small foot bags were fashioned using the fabric impregnated with the candidate formulation, and exposed to rodent attack following storage periods of varying intervals. The results of these tests are listed in Table III. Again, those compounds containing nitrogen in the functional groupings indicated a high order of effectiveness. Several commercial patents covering rodent repellents were issued using the data from the food acceptance and barrier studies.Organizations and cooperators which supplied samples for the program are listed in Appendix I. The Wiswesser cipher for compounds in Table I is used in Appendix II to facilitate location of chemicals by sample code number as they appear under the index headings, and for computer storage and analysis.

Relationships between chemical structure and rat repellency: II. compounds screened between 1950 and 1960

USGS Publications Warehouse

Bowles, Walter A.; Adomaitis, V.A.; DeWitt, J.B.; Pratt, J.J.

1974-01-01

Over 4,600 compounds, chiefly organic types, were evaluated using both a food acceptance test (Part A) and a barrier penetration bioassay (Part B), to correlate relationships between chemical structure and rodent repellency. These chemicals are indexed and classified according to the functional groups present and to the degree of substitution within their molecular structures. The results of reduction in food consumption for each compound appraised are calculated and their K values listed in Table 1. The repellent activities of the functional groups represented, alone or in combinations, are expressed in Table II by a Functional Group Repellency Index.. A ranking of these indices suggests that acyclic and heteroyclic compounds containing tri- or pentavalent nitrogen would be a parent compound of choice for synthesizing novel repellents. Other molecular arrangements, spatial configurations and combinations of functional groups are compared. There were 123 active, interesting or promising compounds included in the 699 having K values of 85 or greater, which were selected for the barrier appraisal study. These chemicals were formulated in selective solvents at several concentrations and applied to burlap. Small food bags were fashioned using the fabric impregnated with the candidate formulation, and exposed to rodent attack following storage periods of varying intervals. The results of these tests are listed in Table III. Again, those compounds containing nitrogen in the functional groupings indicated a high order of effectiveness. Several commercial patents covering rodent repellents were issued using the data from the food acceptance and barrier studies. Organizations and cooperators which supplied samples for the program are listed in Appendix I. The Wiswesser cipher for compounds in Table I is used in Appendix II to facilitate location of chemicals by sample code number as they appear under the index headings, and for computer storage and analysis.

Differential growth responses of soil bacterial taxa to carbon substrates of varying chemical recalcitrance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldfarb, K.C.; Karaoz, U.; Hanson, C.A.

2011-04-18

Soils are immensely diverse microbial habitats with thousands of co-existing bacterial, archaeal, and fungal species. Across broad spatial scales, factors such as pH and soil moisture appear to determine the diversity and structure of soil bacterial communities. Within any one site however, bacterial taxon diversity is high and factors maintaining this diversity are poorly resolved. Candidate factors include organic substrate availability and chemical recalcitrance, and given that they appear to structure bacterial communities at the phylum level, we examine whether these factors might structure bacterial communities at finer levels of taxonomic resolution. Analyzing 16S rRNA gene composition of nucleotide analog-labeledmore » DNA by PhyloChip microarrays, we compare relative growth rates on organic substrates of increasing chemical recalcitrance of >2,200 bacterial taxa across 43 divisions/phyla. Taxa that increase in relative abundance with labile organic substrates (i.e., glycine, sucrose) are numerous (>500), phylogenetically clustered, and occur predominantly in two phyla (Proteobacteria and Actinobacteria) including orders Actinomycetales, Enterobacteriales, Burkholderiales, Rhodocyclales, Alteromonadales, and Pseudomonadales. Taxa increasing in relative abundance with more chemically recalcitrant substrates (i.e., cellulose, lignin, or tannin-protein) are fewer (168) but more phylogenetically dispersed, occurring across eight phyla and including Clostridiales, Sphingomonadalaes, Desulfovibrionales. Just over 6% of detected taxa, including many Burkholderiales increase in relative abundance with both labile and chemically recalcitrant substrates. Estimates of median rRNA copy number per genome of responding taxa demonstrate that these patterns are broadly consistent with bacterial growth strategies. Taken together, these data suggest that changes in availability of intrinsically labile substrates may result in predictable shifts in soil bacterial composition.« less

New Chemicals Program under TSCA Chemical Categories Document

EPA Pesticide Factsheets

The categories included in this compilation represent chemicals for which sufficient assessment experience has been accumulated so that hazard concerns and testing recommendations vary little from chemical to chemical within the category.

Ion beam sputtering of fluoropolymers

NASA Technical Reports Server (NTRS)

Sovey, J. S.

1978-01-01

Etching and deposition of fluoropolymers are of considerable industrial interest for applications dealing with adhesion, chemical inertness, hydrophobicity, and dielectric properties. This paper describes ion beam sputter processing rates as well as pertinent characteristics of etched targets and films. An argon ion beam source was used to sputter etch and deposit the fluoropolymers PTFE, FEP, and CTFE. Ion beam energy, current density, and target temperature were varied to examine effects on etch and deposition rates. The ion etched fluoropolymers yield cone or spire-like surface structures which vary depending upon the type of polymer, ion beam power density, etch time, and target temperature. Also presented are sputter target and film characteristics which were documented by spectral transmittance measurements, X-ray diffraction, ESCA, and SEM photomicrographs.

The relationship between bond ionicity, lattice energy, coefficient of thermal expansion and microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics.

PubMed

Zhang, Ping; Zhao, Yonggui; Wang, Xiuyu

2015-06-28

The crystalline structure refinement, chemical bond ionicity, lattice energy and coefficient of thermal expansion were carried out for Nd(Nb(1-x)Sb(x))O4 ceramics with a monoclinic fergusonite structure to investigate the correlations between the crystalline structure, phase stability, bond ionicity, lattice energy, coefficient of thermal expansion, and microwave dielectric properties. The bond ionicity, lattice energy, and coefficient of thermal expansion of Nd(Nb(1-x)Sb(x))O4 ceramics were calculated using a semiempirical method based on the complex bond theory. The phase structure stability varied with the lattice energy which was resulted by the substitution constant of Sb(5+). With the increasing of the Sb(5+) contents, the decrease of Nb/Sb-O bond ionicity was observed, which could be contributed to the electric polarization. The ε(r) had a close relationship with the Nb/Sb-O bond ionicity. The increase of the Q×f and |τ(f)| values could be attributed to the lattice energy and the coefficient of thermal expansion. The microwave dielectric properties of Nd(Nb(1-x)Sb(x))O4 ceramics with the monoclinic fergusonite structure were strongly dependent on the chemical bond ionicity, lattice energy and coefficient of thermal expansion.

Anatomy, Ultrastructure and Chemical Composition of Food Bodies of Hovenia dulcis (Rhamnaceae)

PubMed Central

Buono, Rafael Andrade; de Oliveira, Alaíde Braga; Paiva, Elder Antonio Sousa

2008-01-01

Background and Aims Food bodies (FBs) are structures that promote mutualism between plants and ants, which help protect them against herbivores. The present study aims to describe the anatomical organization, ultrastructure and chemical composition of the FBs in Hovenia dulcis, which represent the first structures of this type described in Rhamnaceae. Methods Leaves in various stages of development were collected and fixed for examination under light, transmission and scanning electron microscopy. Samples of FBs were subjected to chemical analysis using thin-layer chromatography and nuclear magnetic resonance of 1H and 13C. Key Results The FBs vary from globose to conical and are restricted to the abaxial leaf surface, having a mixed origin, including epidermis and parenchyma. The FB epidermis is uniseriate, slightly pilose and has a thin cuticle. The epidermal cells are vacuolated and pigments or food reserves are absent. The parenchyma cells of immature FBs have dense cytoplasm showing mitochondria, endoplasmic reticulum and plastids. Mature FB cells store oils, which are free in the cytosol and occupy a large portion of the cell lumen. In these cells the plastids accumulate starch. Conclusions The lipids present in FBs are glycerin esters characteristic of plant energy reserves. Ants were observed collecting these FBs, which allows us to infer that these structures mediate plant–ant interactions and can help protect the young plants against herbivores, as these structures are prevalent at this developmental stage. PMID:18413656

Spectroscopic Analysis of Temporal Changes in Leaf Moisture and Dry Matter Content

NASA Astrophysics Data System (ADS)

Qi, Y.; Dennison, P. E.; Brewer, S.; Jolly, W. M.; Kropp, R.

2013-12-01

Live fuel moisture (LFM), the ratio of water content to dry matter content (DMC) in live fuel, is critical for determining fire danger and behavior. Remote sensing estimation of LFM often relies on an assumption of changing water content and stable DMC over time. In order to advance understanding of temporal variation in LFM and DMC, we collected field samples and spectroscopic data for two species, lodgepole pine (Pinus contorta) and big sagebrush (Artemisia tridentata), to explore seasonal trends and spectral expression of these trends. New and old needles were measured separately for lodgepole pine. All samples were measured using a visible/NIR/SWIR spectrometer, and coincident samples were processed to provide LFM, DMC, water content and chemical components including structural and non-structural carbohydrates. New needles initially exhibited higher LFM and a smaller proportion of DMC, but differences between new and old needles converged as the new needles hardened. DMC explained more variation in LFM than water content for new pine needles and sagebrush leaves. Old pine needles transported non-structural carbohydrates to new needles to accumulate DMC during the growth season, resulting decreasing LFM in new needles. DMC and water content co-varied with vegetation chemical components and physical structure. Spectral variation in response to changing DMC is difficulty to isolate from the spectral signatures of multiple chemical components. Partial least square regression combined with hyperspectral data may increase modeling performance in LFM estimation.

Mechanical coupling limits the density and quality of self-organized carbon nanotube growth

NASA Astrophysics Data System (ADS)

Bedewy, Mostafa; Hart, A. John

2013-03-01

Aligned carbon nanotube (CNT) structures are promising for many applications; however, as-grown CNT "forests" synthesized by chemical vapor deposition (CVD) are typically low-density and mostly comprise tortuous defective CNTs. Here, we present evidence that the density and alignment of self-organized CNT growth is limited by mechanical coupling among CNTs in contact, in combination with their diameter-dependent growth rates. This study is enabled by comprehensive X-ray characterization of the spatially and temporally-varying internal morphology of CNT forests. Based on this data, we model the time evolution and diameter-dependent scaling of the ensuing mechanical forces on catalyst nanoparticles during CNT growth, which arise from the mismatch between the collective lengthening rate of the forest and the diameter-dependent growth rates of individual CNTs. In addition to enabling self-organization of CNTs into forests, time-varying forces between CNTs in contact dictate the hierarchical tortuous morphology of CNT forests, and may be sufficient to influence the structural quality of CNTs. These forces reach a maximum that is coincident with the maximum density observed in our growth process, and are proportional to CNT diameter. Therefore, we propose that improved manufacturing strategies for self-organized CNTs should consider both chemical and mechanical effects. This may be especially necessary to achieve high density CNT forests with low defect density, such as for improved thermal interfaces and high-permeability membranes.Aligned carbon nanotube (CNT) structures are promising for many applications; however, as-grown CNT "forests" synthesized by chemical vapor deposition (CVD) are typically low-density and mostly comprise tortuous defective CNTs. Here, we present evidence that the density and alignment of self-organized CNT growth is limited by mechanical coupling among CNTs in contact, in combination with their diameter-dependent growth rates. This study is enabled by comprehensive X-ray characterization of the spatially and temporally-varying internal morphology of CNT forests. Based on this data, we model the time evolution and diameter-dependent scaling of the ensuing mechanical forces on catalyst nanoparticles during CNT growth, which arise from the mismatch between the collective lengthening rate of the forest and the diameter-dependent growth rates of individual CNTs. In addition to enabling self-organization of CNTs into forests, time-varying forces between CNTs in contact dictate the hierarchical tortuous morphology of CNT forests, and may be sufficient to influence the structural quality of CNTs. These forces reach a maximum that is coincident with the maximum density observed in our growth process, and are proportional to CNT diameter. Therefore, we propose that improved manufacturing strategies for self-organized CNTs should consider both chemical and mechanical effects. This may be especially necessary to achieve high density CNT forests with low defect density, such as for improved thermal interfaces and high-permeability membranes. Electronic supplementary information (ESI) available: Detailed description of the cold-wall CVD reactor used for growing CNTs; fitting the diameter-dependent model-predicted CNT growth kinetics; time evolution of compressive stresses as a function of CNT diameter; time evolution of the diameter dependent variations in CNT number density; cumulative forest mass kinetics normalized to the number of CNTs. See DOI: 10.1039/c3nr34067h

Photocatalytic and antibacterial activity of cadmium sulphide/zinc oxide nanocomposite with varied morphology.

PubMed

Jana, T K; Maji, S K; Pal, A; Maiti, R P; Dolai, T K; Chatterjee, K

2016-10-15

Nanocomposites with multifunctional application prospects have already dragged accelerating interests of materials scientists. Here we present CdS/ZnO nanocomposites with different morphology engineering the precursor molar ratio in a facile wet chemical synthesis route. The materials were structurally and morphologically characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX) and high-resolution transmission electron microscopy (HRTEM). The growth mechanism of the composite structure with varying molar ratio is delineated with oriented attachment self assemble techniques. Photocatalytic activity of CdS/ZnO nanocomposites with varying morphology were explored for the degradation of rhodamine B (RhB) dye in presence of visible light irradiation and the results reveal that the best catalytic performance arises in CdS/ZnO composite with 1: 1 ratio. The antibacterial efficiency of all nanocomposites were investigated on Escherichia coli, Staphylococcus aureus and Klebsiella pneumonia without light irradiation. Antibacterial activity of CdS/ZnO nanocomposites were studied using the bacteriological test-well diffusion agar method and results showed significant antibacterial activity in CdS/ZnO composite with 1:3 ratio. Overall, CdS/ZnO nanocomposites excel in different potential applications, such as visible light photocatalysis and antimicrobial activity with their tuneable structure. Copyright © 2016 Elsevier Inc. All rights reserved.

Structural, morphological, and thermal characterization of kraft lignin and its charcoals obtained at different heating rates

NASA Astrophysics Data System (ADS)

Rodrigues Brazil, Tayra; Nunes Costa, Rogeria; Massi, Marcos; Cerqueira Rezende, Mirabel

2018-04-01

Biomass is a renewable resource that is becoming more import due to environmental concerns and possible oil crisis. Thus, optimizing its use is a current challenge for many researchers. Lignin, which is a macromolecule with complex chemical structure, valuable physicochemical properties, and varied chemical composition, is available in large quantities in pulp and paper companies. The objective of this work is the physicochemical characterization of two Kraft lignin samples with different purities, and the study of its thermal conversion into charcoal. The lignin characterization was based on chemical, TGA, DSC, FT-IR, particle sizes, and FEG-SEM analyses. These analyses show that the lignins are mainly composed of guaiacyl and syringyl units, with residues of 30–36 wt.%, in inert atmosphere, depending on the lignin purity. From these results, the more purified lignin with higher carbon yield (%C) was selected for charcoal production. The heat treatment (HT) for carbonization of lignin, at different times (90, 180, and 420 min), resulted in different %C (41–44 wt.%). Longer HT resulted in higher %C and in charcoals with smaller pore sizes. Nanopores (∼50 nm) are observed for the charcoal obtained with the longest HT.

Engineering the oxygen coordination in digital superlattices

NASA Astrophysics Data System (ADS)

Cook, Seyoung; Andersen, Tassie K.; Hong, Hawoong; Rosenberg, Richard A.; Marks, Laurence D.; Fong, Dillon D.

2017-12-01

The oxygen sublattice in complex oxides is typically composed of corner-shared polyhedra, with transition metals at their centers. The electronic and chemical properties of the oxide depend on the type and geometric arrangement of these polyhedra, which can be controlled through epitaxial synthesis. Here, we use oxide molecular beam epitaxy to create SrCoOx:SrTiO3 superlattices with tunable oxygen coordination environments and sublattice geometries. Using synchrotron X-ray scattering in combination with soft X-ray spectroscopy, we find that the chemical state of Co can be varied with the polyhedral arrangement, with higher Co oxidation states increasing the valence band maximum. This work demonstrates a new strategy for engineering unique electronic structures in the transition metal oxides using short-period superlattices.

Physico-chemical effects of supercritical carbon dioxide post polymerization treatment on HCl-doped polyaniline prepared via oxidative chemical polymerization

NASA Astrophysics Data System (ADS)

Fernando, J. G.; Vequizo, R. M.; Odarve, M. K. G.; Sambo, B. R. B.; Alguno, A. C.; Malaluan, R. M.; Candidato, R. T., Jr.; Gambe, J. E.; Jabian, M.; Paylaga, G. J.; Bagsican, F. R. G.; Miyata, H.

2015-06-01

Polyanilinefilms doped with varying HClconcentrations (0.2 M, 0.6 M and 1.0 M) were synthesized on glass substrates via oxidative polymerization of aniline. The films were treated with supercritical carbon dioxide (SC-CO2) at 30 MPa and 40°C for 30 minutes. Their structural, optical and morphological properties were studied and compared to conventionally prepared polyanilinefilms using FTIR analysis, UVVisspectroscopy and scanning electron microscopy. It was observed that supercritical carbon dioxide (SC-CO2) could interact with PANI films that consequently altered the bandgapsand changed the film thickness. SC-CO2 treatment also increased the oxidation level of polyanilinefilms and modified the morphology of polyanilinefilm doped with 1M HCl.

Micro-light-emitting diodes with III-nitride tunnel junction contacts grown by metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Hwang, David; Mughal, Asad J.; Wong, Matthew S.; Alhassan, Abdullah I.; Nakamura, Shuji; DenBaars, Steven P.

2018-01-01

Micro-light-emitting diodes (µLEDs) with tunnel junction (TJ) contacts were grown entirely by metalorganic chemical vapor deposition. A LED structure was grown, treated with UV ozone and hydrofluoric acid, and reloaded into the reactor for TJ regrowth. The silicon doping level of the n++-GaN TJ was varied to examine its effect on voltage. µLEDs from 2.5 × 10-5 to 0.01 mm2 in area were processed, and the voltage penalty of the TJ for the smallest µLED at 20 A/cm2 was 0.60 V relative to that for a standard LED with indium tin oxide. The peak external quantum efficiency of the TJ LED was 34%.

Exploring Reaction Conditions to Improve the Magnetic Response of Cobalt-Doped Ferrite Nanoparticles

PubMed Central

Galarreta, Itziar; Gil de Muro, Izaskun; Lezama, Luis

2018-01-01

With the aim of studying the influence of synthesis parameters in structural and magnetic properties of cobalt-doped magnetite nanoparticles, Fe3−xCoxO4 (0 < x < 0.15) samples were synthetized by thermal decomposition method at different reaction times (30–120 min). The Co ferrite nanoparticles are monodisperse with diameters between 6 and 11 nm and morphologies depending on reaction times, varying from spheric, cuboctahedral, to cubic. Chemical analysis and X-ray diffraction were used to confirm the composition, high crystallinity, and pure-phase structure. The investigation of the magnetic properties, both magnetization and electronic magnetic resonance, has led the conditions to improve the magnetic response of doped nanoparticles. Magnetization values of 86 emu·g−1 at room temperature (R.T.) have been obtained for the sample with the highest Co content and the highest reflux time. Magnetic characterization also displays a dependence of the magnetic anisotropy constant with the varying cobalt content. PMID:29370104

Porous Organic Nanolayers for Coating of Solid-state Devices

PubMed Central

2011-01-01

Background Highly hydrophobic surfaces can have very low surface energy and such low surface energy biological interfaces can be obtained using fluorinated coatings on surfaces. Deposition of biocompatible organic films on solid-state surfaces is attained with techniques like plasma polymerization, biomineralization and chemical vapor deposition. All these require special equipment or harsh chemicals. This paper presents a simple vapor-phase approach to directly coat solid-state surfaces with biocompatible films without any harsh chemical or plasma treatment. Hydrophilic and hydrophobic monomers were used for reaction and deposition of nanolayer films. The monomers were characterized and showed a very consistent coating of 3D micropore structures. Results The coating showed nano-textured surface morphology which can aid cell growth and provide rich molecular functionalization. The surface properties of the obtained film were regulated by varying monomer concentrations, reaction time and the vacuum pressure in a simple reaction chamber. Films were characterized by contact angle analysis for surface energy and with profilometer to measure the thickness. Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed the chemical composition of the coated films. Variations in the FTIR results with respect to different concentrations of monomers showed the chemical composition of the resulting films. Conclusion The presented approach of vapor-phase coating of solid-state structures is important and applicable in many areas of bio-nano interface development. The exposure of coatings to the solutions of different pH showed the stability of the coatings in chemical surroundings. The organic nanocoating of films can be used in bio-implants and many medical devices. PMID:21569579

Development of antimicrobial coating by later-by-layer dip coating of chlorhexidine-loaded micelles.

PubMed

Tambunlertchai, Supreeda; Srisang, Siriwan; Nasongkla, Norased

2017-06-01

Layer-by-layer (LbL) dip coating, accompanying with the use of micelle structure, allows hydrophobic molecules to be coated on medical devices' surface via hydrogen bonding interaction. In addition, micelle structure also allows control release of encapsulated compound. In this research, we investigated methods to coat and maximize the amount of chlorhexidine (CHX) on silicone surface through LbL dip coating method utilizing hydrogen bonding interaction between PEG on micelle corona and PAA. The number of coated cycles was varied in the process and 90 coating cycles provided the maximum amount of CHX loaded onto the surface. In addition, pre-coating the surface with PAA enhanced the amount of coated CHX by 20%. Scanning electron microscope (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) were used to validate and characterize the coating. For control release aspect, the coated film tended to disrupt at physiological condition; hence chemical crosslinking was performed to minimize the disruption and maximize the release time. Chemical crosslinking at pH 2.5 and 4.5 were performed in the process. It was found that chemical crosslinking could help extend the release period up to 18 days. This was significantly longer when compared to the non-crosslinking silicone tube that could only prolong the release for 5 days. In addition, chemical crosslinking at pH 2.5 gave higher and better initial burst release, release period and antimicrobial properties than that of pH 4.5 or the normal used pH for chemical crosslinking process.

A method for probing the mutational landscape of amyloid structure.

PubMed

O'Donnell, Charles W; Waldispühl, Jérôme; Lis, Mieszko; Halfmann, Randal; Devadas, Srinivas; Lindquist, Susan; Berger, Bonnie

2011-07-01

Proteins of all kinds can self-assemble into highly ordered β-sheet aggregates known as amyloid fibrils, important both biologically and clinically. However, the specific molecular structure of a fibril can vary dramatically depending on sequence and environmental conditions, and mutations can drastically alter amyloid function and pathogenicity. Experimental structure determination has proven extremely difficult with only a handful of NMR-based models proposed, suggesting a need for computational methods. We present AmyloidMutants, a statistical mechanics approach for de novo prediction and analysis of wild-type and mutant amyloid structures. Based on the premise of protein mutational landscapes, AmyloidMutants energetically quantifies the effects of sequence mutation on fibril conformation and stability. Tested on non-mutant, full-length amyloid structures with known chemical shift data, AmyloidMutants offers roughly 2-fold improvement in prediction accuracy over existing tools. Moreover, AmyloidMutants is the only method to predict complete super-secondary structures, enabling accurate discrimination of topologically dissimilar amyloid conformations that correspond to the same sequence locations. Applied to mutant prediction, AmyloidMutants identifies a global conformational switch between Aβ and its highly-toxic 'Iowa' mutant in agreement with a recent experimental model based on partial chemical shift data. Predictions on mutant, yeast-toxic strains of HET-s suggest similar alternate folds. When applied to HET-s and a HET-s mutant with core asparagines replaced by glutamines (both highly amyloidogenic chemically similar residues abundant in many amyloids), AmyloidMutants surprisingly predicts a greatly reduced capacity of the glutamine mutant to form amyloid. We confirm this finding by conducting mutagenesis experiments. Our tool is publically available on the web at http://amyloid.csail.mit.edu/. lindquist_admin@wi.mit.edu; bab@csail.mit.edu.

Biogeography of soil organic matter molecular structure across multiple soil size fractions

NASA Astrophysics Data System (ADS)

Meier, C. L.; Neff, J.

2009-12-01

Recent work suggests that there is a common soil decomposition sequence whereby plant inputs are metabolized into a physiologically constrained set of compounds originating from microbes that may persist in soil over relatively long time-scales. Plant inputs tend to be found in coarse particulate fractions (>180 μm) with relatively fast turnover times, while microbially derived compounds tend to accrue in the finer silt + clay fractions (<53 μm) with relatively long turnover times. To investigate whether a common decomposition sequence exists, we used pyrolysis gas chromatography/mass spectrometry (py-GC/MS) to characterize the molecular structure of soil organic matter (SOM) in three size fractions (590-180 μm, 180-53 μm, and <53 μm), using soils sampled from multiple biomes (alpine tundra, sub-alpine forest, boreal forest, temperate coniferous, temperate deciduous, dry desert/savannah, and tropical forest). We hypothesized that: 1) regardless of biome, fractions >180 μm would be chemically similar, and would be characterized by lignin and other plant-derived compounds; and 2) fractions <53 μm would also be similar across biomes but would be dominated by microbially-derived compounds like polysaccharides. Across all biomes, we found that there was significantly less lignin in <53 μm fractions compared to >180 μm fractions (p<0.0001), providing some support for the idea that plant material is not incorporated into soil C pools with relatively long turnover times. However, a principal components analysis (PCA) showed that the >180 μm coarse particulate fractions also contained compounds associated with microbial origins, indicating that microbial C is not limited to <53 μm size fractions. The PCA also revealed that samples within each of the three size fractions did not cluster together (i.e. they did not share a common molecular structure), but we did note that: 1) cold alpine and sub-alpine sites were unique and chemically similar; and 2) tropical forest soils were unique and chemically similar. Moreover, we observed large differences in molecular structure for dry desert/savannah sites with varying vegetation types (trees vs. grass) and varying geologic substrates. Taken together, these observations argue that temperature, vegetation, and underlying geology influence soil molecular structure, but support for a common decomposition sequence is mixed.

Structural, magnetic and impedance spectroscopic analysis of LaFeO3 nano-particles

NASA Astrophysics Data System (ADS)

Rao, T. Lakshmana; Pradhan, M. K.; Dash, S.

2018-04-01

Physical properties are known to be drastically varied with crystallite size and in a multifunctional material this size reduction is seem to be interesting. One such material is chosen as LaFeO3 nanoparticles which have been prepared by wet-chemical route. The average particle size found to be in the order of 45nm in which the chemical content of the unit cell has been verified. A distorted orthorhombic structure with Pbnm space group is possessed by this nanoparticle. From the bifurcation of ZFC and FC in low field, behavior of inverse susceptibility and the small hysteresis loop favors the material to be in a weak FM state well below the Neel temperature. The electrical behavior and the conduction mechanism above room temperature have been studied by cole-cole plot of the Impedance spectra. The high frequency depressed semi circles represent the grain conduction while the intermediate frequency semi circles appear may be due to grain boundary effect.

Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot.

PubMed

Waskasi, Morteza M; Kodis, Gerdenis; Moore, Ana L; Moore, Thomas A; Gust, Devens; Matyushov, Dmitry V

2016-07-27

The Marcus theory of electron transfer predicts a bell-shaped dependence of the reaction rate on the reaction free energy. The top of the "inverted parabola" corresponds to zero activation barrier when the electron-transfer reorganization energy and the reaction free energy add up to zero. Although this point has traditionally been reached by altering the chemical structures of donors and acceptors, the theory suggests that it can also be reached by varying other parameters of the system including temperature. We find here dramatic evidence of this phenomenon from experiments on a fullerene-porphyrin dyad. Following photoinduced electron transfer, the rate of charge recombination shows a bell-shaped dependence on the inverse temperature, first increasing with cooling and then decreasing at still lower temperatures. This non-Arrhenius rate law is a result of a strong, approximately hyperbolic temperature variation of the reorganization energy and the reaction free energy. Our results provide potentially the cleanest confirmation of the Marcus energy gap law so far since no modification of the chemical structure is involved.

Borophene as a prototype for synthetic 2D materials development.

PubMed

Mannix, Andrew J; Zhang, Zhuhua; Guisinger, Nathan P; Yakobson, Boris I; Hersam, Mark C

2018-06-01

The synthesis of 2D materials with no analogous bulk layered allotropes promises a substantial breadth of physical and chemical properties through the diverse structural options afforded by substrate-dependent epitaxy. However, despite the joint theoretical and experimental efforts to guide materials discovery, successful demonstrations of synthetic 2D materials have been rare. The recent synthesis of 2D boron polymorphs (that is, borophene) provides a notable example of such success. In this Perspective, we discuss recent progress and future opportunities for borophene research. Borophene combines unique mechanical properties with anisotropic metallicity, which complements the canon of conventional 2D materials. The multi-centre characteristics of boron-boron bonding lead to the formation of configurationally varied, vacancy-mediated structural motifs, providing unprecedented diversity in a mono-elemental 2D system with potential for electronic applications, chemical functionalization, materials synthesis and complex heterostructures. With its foundations in computationally guided synthesis, borophene can serve as a prototype for ongoing efforts to discover and exploit synthetic 2D materials.

Borophene as a prototype for synthetic 2D materials development

NASA Astrophysics Data System (ADS)

Mannix, Andrew J.; Zhang, Zhuhua; Guisinger, Nathan P.; Yakobson, Boris I.; Hersam, Mark C.

2018-06-01

The synthesis of 2D materials with no analogous bulk layered allotropes promises a substantial breadth of physical and chemical properties through the diverse structural options afforded by substrate-dependent epitaxy. However, despite the joint theoretical and experimental efforts to guide materials discovery, successful demonstrations of synthetic 2D materials have been rare. The recent synthesis of 2D boron polymorphs (that is, borophene) provides a notable example of such success. In this Perspective, we discuss recent progress and future opportunities for borophene research. Borophene combines unique mechanical properties with anisotropic metallicity, which complements the canon of conventional 2D materials. The multi-centre characteristics of boron-boron bonding lead to the formation of configurationally varied, vacancy-mediated structural motifs, providing unprecedented diversity in a mono-elemental 2D system with potential for electronic applications, chemical functionalization, materials synthesis and complex heterostructures. With its foundations in computationally guided synthesis, borophene can serve as a prototype for ongoing efforts to discover and exploit synthetic 2D materials.

Density change and viscous flow during structural relaxation of plasma-enhanced chemical-vapor-deposited silicon oxide films

NASA Astrophysics Data System (ADS)

Cao, Zhiqiang; Zhang, Xin

2004-10-01

The structural relaxation of plasma-enhanced chemical-vapor-deposited (PECVD) silane-based silicon oxide films during thermal cycling and annealing has been studied using wafer curvature measurements. These measurements, which determine stress in the amorphous silicon oxide films, are sensitive to both plastic deformation and density changes. A quantitative case study of such changes has been done based upon the experimental results. A microstructure-based mechanism elucidates seams as a source of density change and voids as a source of plastic deformation, accompanied by a viscous flow. This theory was then used to explain a series of experimental results that are related to thermal cycling as well as annealing of PECVD silicon oxide films including stress hysteresis generation and reduction and coefficient of thermal-expansion changes. In particular, the thickness effect was examined; PECVD silicon oxide films with a thickness varying from 1to40μm were studied, as certain demanding applications in microelectromechanical systems require such thick films serving as heat/electrical insulation layers.

Diverse Molecular Targets for Chalcones with Varied Bioactivities

PubMed Central

Zhou, Bo; Xing, Chengguo

2015-01-01

Natural or synthetic chalcones with different substituents have revealed a variety of biological activities that may benefit human health. The underlying mechanisms of action, particularly with respect to the direct cellular targets and the modes of interaction with the targets, have not been rigorously characterized, which imposes challenges to structure-guided rational development of therapeutic agents or chemical probes with acceptable target-selectivity profile. This review summarizes literature evidence on chalcones’ direct molecular targets in the context of their biological activities. PMID:26798565

Ultrasonic imaging of textured alumina

NASA Technical Reports Server (NTRS)

Stang, David B.; Salem, Jonathan A.; Generazio, Edward R.

1989-01-01

Ultrasonic images representing the bulk attenuation and velocity of a set of alumina samples were obtained by a pulse-echo contact scanning technique. The samples were taken from larger bodies that were chemically similar but were processed by extrusion or isostatic processing. The crack growth resistance and fracture toughness of the larger bodies were found to vary with processing method and test orientation. The results presented here demonstrate that differences in texture that contribute to variations in structural performance can be revealed by analytic ultrasonic techniques.

Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baba, Shintaro; Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Oku, Takeo

2016-02-01

Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in {sup 13}C-nuclear magnetic resonance ({sup 13}C-NMR), principle g-tensor, A-tensor, V-tensor of electricmore » field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.« less

Spectroscopic and microscopic investigation of MBE-grown CdTe (211)B epitaxial thin films on GaAs (211)B substrates

NASA Astrophysics Data System (ADS)

Özden, Selin; Koc, Mumin Mehmet

2018-03-01

CdTe epitaxial thin films, for use as a buffer layer for HgCdTe defectors, were grown on GaAs (211)B using the molecular beam epitaxy method. Wet chemical etching (Everson method) was applied to the epitaxial films using various concentrations and application times to quantify the crystal quality and dislocation density. Surface characterization of the epitaxial films was achieved using Atomic force microscopy and Scanning electron microscopy (SEM) before and after each treatment. The Energy Dispersive X-Ray apparatus of SEM was used to characterize the chemical composition. Untreated CdTe films show smooth surface characteristics with root mean square (RMS) roughnesses of 1.18-3.89 nm. The thicknesses of the CdTe layers formed were calculated via FTIR spectrometry and obtained by ex situ spectroscopic ellipsometry. Raman spectra were obtained for various temperatures. Etch pit densities (EPD) were measured, from which it could be seen that EPD changes between 1.7 × 108 and 9.2 × 108 cm-2 depending on the concentration of the Everson etch solution and treatment time. Structure, shape and depth of pits resulting from each etch pit implementation were also evaluated. Pit widths varying between 0.15 and 0.71 µm with heights varying between 2 and 80 nm were observed. RMS roughness was found to vary by anything from 1.56 to 26 nm.

Substrate-Specific Development of Thermophilic Bacterial Consortia by Using Chemically Pretreated Switchgrass.

PubMed

Eichorst, Stephanie A; Joshua, Chijioke; Sathitsuksanoh, Noppadon; Singh, Seema; Simmons, Blake A; Singer, Steven W

2014-12-01

Microbial communities that deconstruct plant biomass have broad relevance in biofuel production and global carbon cycling. Biomass pretreatments reduce plant biomass recalcitrance for increased efficiency of enzymatic hydrolysis. We exploited these chemical pretreatments to study how thermophilic bacterial consortia adapt to deconstruct switchgrass (SG) biomass of various compositions. Microbial communities were adapted to untreated, ammonium fiber expansion (AFEX)-pretreated, and ionic-liquid (IL)-pretreated SG under aerobic, thermophilic conditions using green waste compost as the inoculum to study biomass deconstruction by microbial consortia. After microbial cultivation, gravimetric analysis of the residual biomass demonstrated that both AFEX and IL pretreatment enhanced the deconstruction of the SG biomass approximately 2-fold. Two-dimensional nuclear magnetic resonance (2D-NMR) experiments and acetyl bromide-reactive-lignin analysis indicated that polysaccharide hydrolysis was the dominant process occurring during microbial biomass deconstruction, and lignin remaining in the residual biomass was largely unmodified. Small-subunit (SSU) rRNA gene amplicon libraries revealed that although the dominant taxa across these chemical pretreatments were consistently represented by members of the Firmicutes, the Bacteroidetes, and Deinococcus-Thermus, the abundance of selected operational taxonomic units (OTUs) varied, suggesting adaptations to the different substrates. Combining the observations of differences in the community structure and the chemical and physical structure of the biomass, we hypothesize specific roles for individual community members in biomass deconstruction. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Chemical and structural investigation of lipid nanoparticles: drug-lipid interaction and molecular distribution

NASA Astrophysics Data System (ADS)

Anantachaisilp, Suranan; Meejoo Smith, Siwaporn; Treetong, Alongkot; Pratontep, Sirapat; Puttipipatkhachorn, Satit; Rungsardthong Ruktanonchai, Uracha

2010-03-01

Lipid nanoparticles are a promising alternative to existing carriers in chemical or drug delivery systems. A key challenge is to determine how chemicals are incorporated and distributed inside nanoparticles, which assists in controlling chemical retention and release characteristics. This study reports the chemical and structural investigation of γ-oryzanol loading inside a model lipid nanoparticle drug delivery system composed of cetyl palmitate as solid lipid and Miglyol 812® as liquid lipid. The lipid nanoparticles were prepared by high pressure homogenization at varying liquid lipid content, in comparison with the γ-oryzanol free systems. The size of the lipid nanoparticles, as measured by the photon correlation spectroscopy, was found to decrease with increased liquid lipid content from 200 to 160 nm. High-resolution proton nuclear magnetic resonance (1H-NMR) measurements of the medium chain triglyceride of the liquid lipid has confirmed successful incorporation of the liquid lipid in the lipid nanoparticles. Differential scanning calorimetric and powder x-ray diffraction measurements provide complementary results to the 1H-NMR, whereby the crystallinity of the lipid nanoparticles diminishes with an increase in the liquid lipid content. For the distribution of γ-oryzanol inside the lipid nanoparticles, the 1H-NMR revealed that the chemical shifts of the liquid lipid in γ-oryzanol loaded systems were found at rather higher field than those in γ-oryzanol free systems, suggesting incorporation of γ-oryzanol in the liquid lipid. In addition, the phase-separated structure was observed by atomic force microscopy for lipid nanoparticles with 0% liquid lipid, but not for lipid nanoparticles with 5 and 10% liquid lipid. Raman spectroscopic and mapping measurements further revealed preferential incorporation of γ-oryzanol in the liquid part rather than the solid part of in the lipid nanoparticles. Simple models representing the distribution of γ-oryzanol and lipids (solid and liquid) inside the lipid nanoparticle systems are proposed.

Association between airborne PM2.5 chemical constituents and birth weight—implication of buffer exposure assignment

NASA Astrophysics Data System (ADS)

Ebisu, Keita; Belanger, Kathleen; Bell, Michelle L.

2014-08-01

Several papers reported associations between airborne fine particulate matter (PM2.5) and birth weight, though findings are inconsistent across studies. Conflicting results might be due to (1) different PM2.5 chemical structure across locations, and (2) various exposure assignment methods across studies even among the studies that use ambient monitors to assess exposure. We investigated associations between birth weight and PM2.5 chemical constituents, considering issues arising from choice of buffer size (i.e. distance between residence and pollution monitor). We estimated the association between each pollutant and term birth weight applying buffers of 5 to 30 km in Connecticut (2000-2006), in the New England region of the USA. We also investigated the implication of the choice of buffer size in relation to population characteristics, such as socioeconomic status. Results indicate that some PM2.5 chemical constituents, such as nitrate, are associated with lower birth weight and appear more harmful than other constituents. However, associations vary with buffer size and the implications of different buffer sizes may differ by pollutant. A homogeneous pollutant level within a certain distance is a common assumption in many environmental epidemiology studies, but the validity of this assumption may vary by pollutant. Furthermore, we found that areas close to monitors reflect more minority and lower socio-economic populations, which implies that different exposure approaches may result in different types of study populations. Our findings demonstrate that choosing an exposure method involves key tradeoffs of the impacts of exposure misclassification, sample size, and population characteristics.

Structural diversity requires individual optimization of ethanol concentration in polysaccharide precipitation.

PubMed

Xu, Jun; Yue, Rui-Qi; Liu, Jing; Ho, Hing-Man; Yi, Tao; Chen, Hu-Biao; Han, Quan-Bin

2014-06-01

Ethanol precipitation is one of the most widely used methods for preparing natural polysaccharides, in which ethanol concentration significantly affects the precipitate yield, however, is usually set at 70-80%. Whether the standardization of ethanol concentration is appropriate has not been investigated. In the present study, the precipitation yields produced in varied ethanol concentrations (10-90%) were qualitatively and quantitatively evaluated by HPGPC (high-performance gel-permeation chromatography), using two series of standard glucans, namely dextrans and pullulans, as reference samples, and then eight natural samples. The results indicated that the response of a polysaccharide's chemical structure, with diversity in structural features and molecular sizes, to ethanol concentration is the decisive factor in precipitation of these glucans. Polysaccharides with different structural features, even though they have similar molecular weights, exhibit significantly different precipitation behaviors. For a specific glucan, the lower its molecular size, the higher the ethanol concentration needed for complete precipitation. The precipitate yield varied from 10% to 100% in 80% ethanol as the molecular size increased from 1kDa to 270kDa. This paper aims to draw scientists' attention to the fact that, in extracting natural polysaccharides by ethanol precipitation, the ethanol concentration must be individually optimized for each type of material. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of samarium substitution on structural, dielectric, and piezoelectric properties of PZT ceramics

NASA Astrophysics Data System (ADS)

Juneja, J. K.; Thakur, O. P.; Prakash, Chandra

2003-10-01

The structural, dielectric and piezoelectric properties have been studied in detail for the samarium modified PZT system. The samples, with chemical formula Pb1-xSmxZr0.52Ti0.48O3 with x varying from 0 to 0.02 in steps of 0.0025, were prepared by standard double sintering ceramic method. XRD analysis showed all the samples to be of single phase with tetragonal structure. Tetragonality (c/a) decreases gradually with samarium concentration (x) and the experimental density increases with x. Dielectric properties were studied as a function of temperature and frequency. All the samples show well-defined ferroelectric behavior. The remanance ratio (Pr/Ps) was found to increase with increasing Sm3+ concentration. Piezoelectric charge coefficient d33 decreases with x.

Cinema audiences reproducibly vary the chemical composition of air during films, by broadcasting scene specific emissions on breath

NASA Astrophysics Data System (ADS)

Williams, Jonathan; Stönner, Christof; Wicker, Jörg; Krauter, Nicolas; Derstroff, Bettina; Bourtsoukidis, Efstratios; Klüpfel, Thomas; Kramer, Stefan

2016-05-01

Human beings continuously emit chemicals into the air by breath and through the skin. In order to determine whether these emissions vary predictably in response to audiovisual stimuli, we have continuously monitored carbon dioxide and over one hundred volatile organic compounds in a cinema. It was found that many airborne chemicals in cinema air varied distinctively and reproducibly with time for a particular film, even in different screenings to different audiences. Application of scene labels and advanced data mining methods revealed that specific film events, namely “suspense” or “comedy” caused audiences to change their emission of specific chemicals. These event-type synchronous, broadcasted human chemosignals open the possibility for objective and non-invasive assessment of a human group response to stimuli by continuous measurement of chemicals in air. Such methods can be applied to research fields such as psychology and biology, and be valuable to industries such as film making and advertising.

Cinema audiences reproducibly vary the chemical composition of air during films, by broadcasting scene specific emissions on breath.

PubMed

Williams, Jonathan; Stönner, Christof; Wicker, Jörg; Krauter, Nicolas; Derstroff, Bettina; Bourtsoukidis, Efstratios; Klüpfel, Thomas; Kramer, Stefan

2016-05-10

Human beings continuously emit chemicals into the air by breath and through the skin. In order to determine whether these emissions vary predictably in response to audiovisual stimuli, we have continuously monitored carbon dioxide and over one hundred volatile organic compounds in a cinema. It was found that many airborne chemicals in cinema air varied distinctively and reproducibly with time for a particular film, even in different screenings to different audiences. Application of scene labels and advanced data mining methods revealed that specific film events, namely "suspense" or "comedy" caused audiences to change their emission of specific chemicals. These event-type synchronous, broadcasted human chemosignals open the possibility for objective and non-invasive assessment of a human group response to stimuli by continuous measurement of chemicals in air. Such methods can be applied to research fields such as psychology and biology, and be valuable to industries such as film making and advertising.

Cinema audiences reproducibly vary the chemical composition of air during films, by broadcasting scene specific emissions on breath

PubMed Central

Williams, Jonathan; Stönner, Christof; Wicker, Jörg; Krauter, Nicolas; Derstroff, Bettina; Bourtsoukidis, Efstratios; Klüpfel, Thomas; Kramer, Stefan

2016-01-01

Human beings continuously emit chemicals into the air by breath and through the skin. In order to determine whether these emissions vary predictably in response to audiovisual stimuli, we have continuously monitored carbon dioxide and over one hundred volatile organic compounds in a cinema. It was found that many airborne chemicals in cinema air varied distinctively and reproducibly with time for a particular film, even in different screenings to different audiences. Application of scene labels and advanced data mining methods revealed that specific film events, namely “suspense” or “comedy” caused audiences to change their emission of specific chemicals. These event-type synchronous, broadcasted human chemosignals open the possibility for objective and non-invasive assessment of a human group response to stimuli by continuous measurement of chemicals in air. Such methods can be applied to research fields such as psychology and biology, and be valuable to industries such as film making and advertising. PMID:27160439

Growth, microstructure and electrical properties of sputter-deposited hafnium oxide (HfO2) thin films grown using HfO2 ceramic target

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aguirre, B.; Vemuri, R. S.; Zubia, David

2011-01-01

Hafnium oxide (HfO₂) thin films have been made by radio-frequency (rf) magnetron-sputtering onto Si(100) substrates under varying growth temperature (Ts). HfO₂ ceramic target has been employed for sputtering while varying the Ts from room temperature to 500⁰C during deposition. The effect of Ts on the growth and microstructure of deposited HfO₂ films has been studied using grazing incidence x-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), and high-resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive x-ray spectrometry (EDS). The results indicate that the effect of Ts is significant on the growth, surface and interface structure, morphology and chemical composition ofmore » the HfO₂ films. Structural characterization indicates that the HfO₂ films grown at Ts<200 ⁰C are amorphous while films grown at Ts>200 ⁰C are nanocrystalline. An amorphous-to-crystalline transition occurs at Ts=200 ⁰C. Nanocrystalline HfO₂ films crystallized in a monoclinic structure with a (-111) orientation. XPS measurements indicated the high surface-chemical quality and stoichiometric nature of the grown HfO₂ films. An interface layer (IL) formation occurs due to reaction at the HfO₂-Si interface for HfO₂ films deposited at Ts>200 ⁰C. The thickness of IL increases with increasing Ts. XPS and EDS at the HfO₂-Si cross-section indicate the IL is a (Hf, Si)-O compound. The electrical characterization using capacitance-voltage measurements indicate that the dielectric constant decreases from 25 to 16 with increasing Ts.« less

A universal reduced glass transition temperature for liquids

NASA Technical Reports Server (NTRS)

Fedors, R. F.

1979-01-01

Data on the dependence of the glass transition temperature on the molecular structure for low-molecular-weight liquids are analyzed in order to determine whether Boyer's reduced glass transition temperature (1952) is a universal constant as proposed. It is shown that the Boyer ratio varies widely depending on the chemical nature of the molecule. It is pointed out that a characteristic temperature ratio, defined by the ratio of the sum of the melting temperature and the boiling temperature to the sum of the glass transition temperature and the boiling temperature, is a universal constant independent of the molecular structure of the liquid. The average value of the ratio obtained from data for 65 liquids is 1.15.

Study the effect of nitrogen flow rate on tribological properties of tantalum nitride based coatings

NASA Astrophysics Data System (ADS)

Chauhan, Dharmesh B.; Chauhan, Kamlesh V.; Sonera, Akshay L.; Makwana, Nishant S.; Dave, Divyeshkumar P.; Rawal, Sushant K.

2018-05-01

Tantalum Nitride (TaN) based coatings are well-known for their high temperature stability and chemical inertness. We have studied the effect of nitrogen flow rate variation on the structural and tribological properties of TaN based coating deposited by RF magnetron sputtering process. The nitrogen flow rate was varied from 5 to 30 sccm. X-ray diffractometer (XRD) and Atomic Force Microscopy (AFM) were used to determine structure and surface topography of coating. Pin on disc tribometer was used to determine tribological properties of coating. TaN coated brass and mild steel substrates shows higher wear resistance compared to uncoated substrates of brass and mild steel.

Inertial Effects on Flow and Transport in Heterogeneous Porous Media.

PubMed

Nissan, Alon; Berkowitz, Brian

2018-02-02

We investigate the effects of high fluid velocities on flow and tracer transport in heterogeneous porous media. We simulate fluid flow and advective transport through two-dimensional pore-scale matrices with varying structural complexity. As the Reynolds number increases, the flow regime transitions from linear to nonlinear; this behavior is controlled by the medium structure, where higher complexity amplifies inertial effects. The result is, nonintuitively, increased homogenization of the flow field, which leads in the context of conservative chemical transport to less anomalous behavior. We quantify the transport patterns via a continuous time random walk, using the spatial distribution of the kinetic energy within the fluid as a characteristic measure.

Effect of Mo-doping concentration on the physical behaviour of sprayed ZnO layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, T. Sreenivasulu; Reddy, M. Vasudeva; Reddy, K. T. Ramakrishna, E-mail: ktrkreddy@gmail.com

2015-06-24

Mo-doped zinc oxide layers (MZO) have been prepared on cleaned glass substrates by chemical spray pyrolysis technique by varying Mo-doping concentration in the range, 0 – 5 at. %. The X-ray diffraction studies revealed that all the as prepared layers were polycrystalline in nature and exhibited wurtzite structure. The layers prepared with lower Mo-doping concentration (<2 at. %) were preferably oriented along the (100) plane, whereas in the case of higher Mo-doping concentration (>2 at. %), the films showed the (002) plane as the dominant peak. The optical analysis indicated that all the layers had an average optical transmittance ofmore » 80% in the visible region and the evaluated band gap varied in the range, 3.28 - 3.50 eV.« less

AAuAl (A = Ca, Sc, and Ti): Peierls Distortion, Atomic Coloring, and Structural Competition

DOE PAGES

Pham, Joyce; Miller, Gordon J.

2018-04-02

Using density functional theory, the crystal structure variation of AAuAl (A = Ca, Sc, and Ti) from orthorhombic Co 2Si-type to distorted hexagonal Fe 2P-type and then Ni 2In-type structures is shown to correlate with their electronic structures and valence electron counts, sizes of the active metals A, and site preferences for Au and Al atoms, which are arranged to maximize Au–Al nearest neighbor contacts. An evaluation of chemical pressure imposed by the varying A metals using total energy vs volume calculations indicates that larger unit cell volumes favor the orthorhombic structure, whereas smaller volumes favor the hexagonal structures. Themore » electronic origin of the Mg 2Ga-type crystal structure of ScAuAl, refined as a distorted Fe 2P-type supercell doubled along the c-axis, indicates a Peierls-type distortion mechanism of the Au chains along the c-axis.« less

AAuAl (A = Ca, Sc, and Ti): Peierls Distortion, Atomic Coloring, and Structural Competition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Joyce; Miller, Gordon J.

Using density functional theory, the crystal structure variation of AAuAl (A = Ca, Sc, and Ti) from orthorhombic Co 2Si-type to distorted hexagonal Fe 2P-type and then Ni 2In-type structures is shown to correlate with their electronic structures and valence electron counts, sizes of the active metals A, and site preferences for Au and Al atoms, which are arranged to maximize Au–Al nearest neighbor contacts. An evaluation of chemical pressure imposed by the varying A metals using total energy vs volume calculations indicates that larger unit cell volumes favor the orthorhombic structure, whereas smaller volumes favor the hexagonal structures. Themore » electronic origin of the Mg 2Ga-type crystal structure of ScAuAl, refined as a distorted Fe 2P-type supercell doubled along the c-axis, indicates a Peierls-type distortion mechanism of the Au chains along the c-axis.« less

Study of transmission function and electronic transport in one dimensional silver nanowire: Ab-initio method using density functional theory (DFT)

NASA Astrophysics Data System (ADS)

Thakur, Anil; Kashyap, Rajinder

2018-05-01

Single nanowire electrode devices have their application in variety of fields which vary from information technology to solar energy. Silver nanowires, made in an aqueous chemical reduction process, can be reacted with gold salt to create bimetallic nanowires. Silver nanowire can be used as electrodes in batteries and have many other applications. In this paper we investigated structural and electronic transport properties of Ag nanowire using density functional theory (DFT) with SIESTA code. Electronic transport properties of Ag nanowire have been studied theoretically. First of all an optimized geometry for Ag nanowire is obtained using DFT calculations, and then the transport relations are obtained using NEGF approach. SIESTA and TranSIESTA simulation codes are used in the calculations respectively. The electrodes are chosen to be the same as the central region where transport is studied, eliminating current quantization effects due to contacts and focusing the electronic transport study to the intrinsic structure of the material. By varying chemical potential in the electrode regions, an I-V curve is traced which is in agreement with the predicted behavior. Bulk properties of Ag are in agreement with experimental values which make the study of electronic and transport properties in silver nanowires interesting because they are promising materials as bridging pieces in nanoelectronics. Transmission coefficient and V-I characteristic of Ag nano wire reveals that silver nanowire can be used as an electrode device.

Label-free imaging of mammalian cell nucleoli by Raman microspectroscopy.

PubMed

Schulze, H Georg; Konorov, Stanislav O; Piret, James M; Blades, Michael W; Turner, Robin F B

2013-06-21

The nucleolus is a prominent subnuclear structure whose major function is the transcription and assembly of ribosome subunits. The size of the nucleolus varies with the cell cycle, proliferation rate and stress. Changes in nucleolar size, number, chemical composition, and shape can be used to characterize malignant cells. We used spontaneous Raman microscopy as a label-free technique to examine nucleolar spatial and chemical features. Raman images of the 1003 cm(-1) phenylalanine band revealed large, well-defined subnuclear protein structures in MFC-7 breast cancer cells. The 783 cm(-1) images showed that nucleic acids were similarly distributed, but varied more in intensity, forming observable high-intensity regions. High subnuclear RNA concentrations were observed within some of these regions as shown by 809 cm(-1) Raman band images. Principal component analyses of sub-images and library spectra validated the subnuclear presence of RNA. They also revealed that an actin-like protein covaried with DNA within the nucleolus, a combination that accounted for 64% or more of the spectral variance. Embryonic stem cells are another rapidly proliferating cell type, but their nucleoli were not as large or well defined. Estimating the size of the larger MCF-7 nucleolus was used to show the utility of Raman microscopy for morphometric analyses. It was concluded that imaging based on Raman microscopy provides a promising new method for the study of nucleolar function and organization, in the evaluation of drug and experimental effects on the nucleolus, and in clinical diagnostics and prognostics.

A MODELING AND SIMULATION LANGUAGE FOR BIOLOGICAL CELLS WITH COUPLED MECHANICAL AND CHEMICAL PROCESSES

PubMed Central

Somogyi, Endre; Glazier, James A.

2017-01-01

Biological cells are the prototypical example of active matter. Cells sense and respond to mechanical, chemical and electrical environmental stimuli with a range of behaviors, including dynamic changes in morphology and mechanical properties, chemical uptake and secretion, cell differentiation, proliferation, death, and migration. Modeling and simulation of such dynamic phenomena poses a number of computational challenges. A modeling language describing cellular dynamics must naturally represent complex intra and extra-cellular spatial structures and coupled mechanical, chemical and electrical processes. Domain experts will find a modeling language most useful when it is based on concepts, terms and principles native to the problem domain. A compiler must then be able to generate an executable model from this physically motivated description. Finally, an executable model must efficiently calculate the time evolution of such dynamic and inhomogeneous phenomena. We present a spatial hybrid systems modeling language, compiler and mesh-free Lagrangian based simulation engine which will enable domain experts to define models using natural, biologically motivated constructs and to simulate time evolution of coupled cellular, mechanical and chemical processes acting on a time varying number of cells and their environment. PMID:29303160

Penetration of chemicals into the oocyte, uterine fluid, and preimplantation blastocyst

PubMed Central

Fabro, Sergio

1978-01-01

Chemicals, including commonly used drugs (e.g., penicillin, meprobamate, pyridium, and mercaptomerin) penetrate and persist for some time in the ovarian follicular fluid at concentrations approximately similar to that of the serum. Information as to the penetration of chemicals into the granulosa cells and into the oocyte is scanty, although there are some indications that these structures are also permeable to foreign chemicals. Similarly, caffeine, nicotine, thiopental, salicylic acid, antipyrine, barbital, and isoniazid enter the uterine secretion and penetrate the preimplantation blastocyst of mice, rats and rabbits. The pattern of distribution of compounds among ovarian follicular fluid, uterine luminal fluid, blastocyst and plasma varies from compound to compound and appears to be related to the molecular weight and degree of ionization of the compound and differs in pregnant and nonpregnant animals. Thus, nicotine and DDT accumulate in the uterine luminal fluid of pregnant but not in that of nonpregnant rabbits. The penetration of foreign chemicals into the oocyte, uterine luminal fluid, and preimplantation blastocyst may exert adverse effects on fertilization, implantation, and/or further development of the conceptus. The possible toxicological importance of this process to eutherian reproduction is discussed. PMID:17539150

The electrical properties of low pressure chemical vapor deposition Ga doped ZnO thin films depending on chemical bonding configuration

NASA Astrophysics Data System (ADS)

Jung, Hanearl; Kim, Doyoung; Kim, Hyungjun

2014-04-01

The electrical and chemical properties of low pressure chemical vapor deposition (LP-CVD) Ga doped ZnO (ZnO:Ga) films were systematically investigated using Hall measurement and X-ray photoemission spectroscopy (XPS). Diethylzinc (DEZ) and O2 gas were used as precursor and reactant gas, respectively, and trimethyl gallium (TMGa) was used as a Ga doping source. Initially, the electrical properties of undoped LP-CVD ZnO films depending on the partial pressure of DEZ and O2 ratio were investigated using X-ray diffraction (XRD) by changing partial pressure of DEZ from 40 to 140 mTorr and that of O2 from 40 to 80 mTorr. The resistivity was reduced by Ga doping from 7.24 × 10-3 Ω cm for undoped ZnO to 2.05 × 10-3 Ω cm for Ga doped ZnO at the TMG pressure of 8 mTorr. The change of electric properties of Ga doped ZnO with varying the amount of Ga dopants was systematically discussed based on the structural crystallinity and chemical bonding configuration, analyzed by XRD and XPS, respectively.

A MODELING AND SIMULATION LANGUAGE FOR BIOLOGICAL CELLS WITH COUPLED MECHANICAL AND CHEMICAL PROCESSES.

PubMed

Somogyi, Endre; Glazier, James A

2017-04-01

Biological cells are the prototypical example of active matter. Cells sense and respond to mechanical, chemical and electrical environmental stimuli with a range of behaviors, including dynamic changes in morphology and mechanical properties, chemical uptake and secretion, cell differentiation, proliferation, death, and migration. Modeling and simulation of such dynamic phenomena poses a number of computational challenges. A modeling language describing cellular dynamics must naturally represent complex intra and extra-cellular spatial structures and coupled mechanical, chemical and electrical processes. Domain experts will find a modeling language most useful when it is based on concepts, terms and principles native to the problem domain. A compiler must then be able to generate an executable model from this physically motivated description. Finally, an executable model must efficiently calculate the time evolution of such dynamic and inhomogeneous phenomena. We present a spatial hybrid systems modeling language, compiler and mesh-free Lagrangian based simulation engine which will enable domain experts to define models using natural, biologically motivated constructs and to simulate time evolution of coupled cellular, mechanical and chemical processes acting on a time varying number of cells and their environment.

North Atlantic Oscillation modulates total ozone winter trends

NASA Astrophysics Data System (ADS)

Appenzeller, Christof; Weiss, Andrea K.; Staehelin, Johannes

2000-04-01

The North Atlantic Oscillation (NAO) is modulating the Earth's ozone shield such that the calculated anthropogenic total ozone decrease is enhanced over Europe whereas over the North Atlantic region it is reduced (for the last 30 years). Including the NAO in a statistical model suggests a more uniform chemical winter trend compared to the strong longitudinal variation reported earlier. At Arosa (Switzerland) the trend is reduced to -2.4% per decade compared to -3.2% and at Reykjavik (Iceland) it is enhanced to -3.8% compared to 0%. The revised trend is slightly below the predictions by 2D chemical models. Decadal ozone variability is linked to variations in the dynamical structure of the atmosphere, as reflected in the tropopause pressure. The latter varies in concert with the NAO index with a distinct geographical pattern.

Morphological, structural, and chemical effects in response of novel carbide derived carbon sensor to NH3, N2O, and air.

PubMed

Adu, Kofi W; Li, Qixiu; Desai, Sharvil C; Sidorov, Anton N; Sumanasekera, Gamini U; Lueking, Angela D

2009-01-06

The response of two carbide derived carbons (CDCs) films to NH(3), N(2)O, and room air is investigated by four probe resistance at room temperature and pressures up to 760 Torr. The two CDC films were synthesized at 600 (CDC-600) and 1000 degrees C (CDC-1000) to vary the carbon morphology from completely amorphous to more ordered, and determine the role of structure, surface area, and porosity on sensor response. Sensor response time followed kinetic diameter and indicated a more ordered carbon structure slowed response due to increased tortuosity caused by the formation of graphitic layers at the particle fringe. Steady state sensor response was greater for the less-ordered material, despite its decreased surface area, decreased micropore volume, and less favorable surface chemistry, suggesting carbon structure is a stronger predictor of sensor response than surface chemistry. The lack of correlation between adsorption of the probe gases and sensor response suggests chemical interaction (charge transfer) drive sensor response within the material; N(2)O response, in particular, did not follow simple adsorption behavior. Based on Raman and FTIR characterization, carbon morphology (disorder) appeared to be the determining factor in overall sensor response, likely due to increased charge transfer between gases and carbon defects of amorphous or disordered regions. The response of the amorphous CDC-600 film to NH(3) was 45% without prior oxidation, showing amorphous CDCs have promise as chemical sensors without additional pretreatment common to other carbon sensors.

The clays of the United States east of the Mississippi River

USGS Publications Warehouse

Ries, Henrich

1903-01-01

Since clays vary mineralogically they vary also chemically, but the plasticity may remain the same through a wide range of chemical composition, and this property is evidently not dependent on the chemical composition alone, but is due rather to some physical cause. The plasticity may be destroyed by heating the clay to a sufficiently high temperature to drive off the chemically combined water. Although varying in their mineral composition, most clays are supposed to contain more or less of the mineral kaolinite (a hydrated silicate of alumina), which is commonly referred to as the clay base or clay substance. The adoption of the latter term has probably arisen from the fact that many have 'considered this mineral to be the cause of plasticity, an idea now known to be somewhat incorrect, because some of the most plastic clays contain but small quantities of kaolinite, and vice versa. 

Modulation of the Extent of Cooperative Structural Change During Protein Folding by Chemical Denaturant.

PubMed

Jethva, Prashant N; Udgaonkar, Jayant B

2017-09-07

Protein folding and unfolding reactions invariably appear to be highly cooperative reactions, but the structural and sequence determinants of cooperativity are poorly understood. Importantly, it is not known whether cooperative structural change occurs throughout the protein, or whether some parts change cooperatively and other parts change noncooperatively. In the current study, hydrogen exchange mass spectrometry has been used to show that the mechanism of unfolding of the PI3K SH3 domain is similar in the absence and presence of 5 M urea. The data are well described by a four state N ↔ I N ↔ I 2 ↔ U model, in which structural changes occur noncooperatively during the N ↔ I N and I N ↔ I 2 transitions, and occur cooperatively during the I 2 ↔ U transition. The nSrc-loop and RT-loop, as well as β strands 4 and 5 undergo noncooperative unfolding, while β strands 1, 2, and 3 unfold cooperatively in the absence of urea. However, in the presence of 5 M urea, the unfolding of β strand 4 switches to become cooperative, leading to an increase in the extent of cooperative structural change. The current study highlights the relationship between protein stability and cooperativity, by showing how the extent of cooperativity can be varied, using chemical denaturant to alter protein stability.

Role of solvent-mediated carbodiimide cross-linking in fabrication of electrospun gelatin nanofibrous membranes as ophthalmic biomaterials.

PubMed

Chou, Shih-Feng; Luo, Li-Jyuan; Lai, Jui-Yang; Ma, David Hui-Kang

2017-02-01

Due to their ability to mimic the structure of extracellular matrix, electrospun gelatin nanofibers are promising cell scaffolding materials for tissue engineering applications. However, the hydrophilic gelatin molecules usually need stabilization before use in aqueous physiological environment. Considering that biomaterials cross-linked via film immersion technique may have a more homogeneous cross-linked structure than vapor phase cross-linking, this work aims to investigate the chemical modification of electrospun gelatin nanofibrous membranes by liquid phase carbodiimide in the presence of ethanol/water co-solvents with varying ethanol concentrations ranging from 80 to 99.5vol%. The results of characterization showed that increasing water content in the binary reaction solvent system increases the extent of cross-linking of gelatin nanofibers, but simultaneously promotes the effect of biopolymer swelling and distortion in fiber mat structure. As compared to non-cross-linked counterparts, carbodiimide treated gelatin nanofibrous mats exhibited better thermal and biological stability where the shrinkage temperature and resistance to enzymatic degradation varied in response to ethanol/water solvent composition-mediated generation of cross-links. Irrespective of their cross-linking density, all studied membrane samples did not induce any responses in ocular epithelial cell cultures derived from cornea, lens, and retina. Unlike many other cross-linking agents and/or methods (e.g., excessive vapor phase cross-linking) that may pose a risk of toxicity, our study demonstrated that these nanofibrous materials are well tolerated by anterior segment tissues. These findings also indicate the safety of using ethanol/water co-solvents for chemical cross-linking of gelatin to engineer nanofibrous materials with negligible biological effects. In summary, the present results suggest the importance of solvent-mediated carbodiimide cross-linking in modulating structure-property relationship without compromising in vitro and in vivo biocompatibility of electrospun gelatin nanofibers for future ophthalmic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Chemically doped three-dimensional porous graphene monoliths for high-performance flexible field emitters.

PubMed

Kim, Ho Young; Jeong, Sooyeon; Jeong, Seung Yol; Baeg, Kang-Jun; Han, Joong Tark; Jeong, Mun Seok; Lee, Geon-Woong; Jeong, Hee Jin

2015-03-12

Despite the recent progress in the fabrication of field emitters based on graphene nanosheets, their morphological and electrical properties, which affect their degree of field enhancement as well as the electron tunnelling barrier height, should be controlled to allow for better field-emission properties. Here we report a method that allows the synthesis of graphene-based emitters with a high field-enhancement factor and a low work function. The method involves forming monolithic three-dimensional (3D) graphene structures by freeze-drying of a highly concentrated graphene paste and subsequent work-function engineering by chemical doping. Graphene structures with vertically aligned edges were successfully fabricated by the freeze-drying process. Furthermore, their number density could be controlled by varying the composition of the graphene paste. Al- and Au-doped 3D graphene emitters were fabricated by introducing the corresponding dopant solutions into the graphene sheets. The resulting field-emission characteristics of the resulting emitters are discussed. The synthesized 3D graphene emitters were highly flexible, maintaining their field-emission properties even when bent at large angles. This is attributed to the high crystallinity and emitter density and good chemical stability of the 3D graphene emitters, as well as to the strong interactions between the 3D graphene emitters and the substrate.

Chemical differences between voided and bladder urine in the aye-aye (Daubentonia madagascariensis): implications for olfactory communication studies.

PubMed

Delbarco-Trillo, Javier; Harelimana, Innocent H; Goodwin, Thomas E; Drea, Christine M

2013-07-01

Urine serves a communicative function in many mammalian species. In some species, the signaling function of urine can be enhanced by the addition of chemical compounds from glands along the distal portion of the urogenital tract. Although urine marking is the main mode of chemical communication in many primate species, there has been no study of the contribution of urogenital secretions to the chemical complexity of primate urine. Here, we compared the chemical composition of bladder urine versus voided urine in the aye-aye, Daubentonia madagascariensis, a strepsirrhine primate that relies on urine in intraspecific communication. Both types of urine, collected from each of 11 aye-ayes representing both sexes of varying adult ages, underwent headspace analysis via gas chromatography and mass spectrometry. Although the average number of compounds was similar in bladder and voided urine, 17% of the compounds detected occurred exclusively in voided urine (but only in a subset of individuals). An overall measure of chemical complexity (using a nonmetric multidimensional scaling analysis) showed that both types of urine were chemically different at the individual level. There was no apparent sex or age differences in the chemical components found in aye-aye urine. Nonetheless, the individual dissimilarities between bladder urine and voided urine indicate chemical contributions from structures along the urogenital tract and offer further support for the relevance of urinary communication in the aye-aye. © 2012 Wiley Periodicals, Inc.

Determination of chemical changes in heat-treated wood using ATR-FTIR and FT Raman spectrometry

NASA Astrophysics Data System (ADS)

Özgenç, Özlem; Durmaz, Sefa; Boyaci, Ismail Hakki; Eksi-Kocak, Haslet

2017-01-01

In this study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Fourier-transform Raman (FT-Raman) spectroscopy techniques were used to determine changes in the chemical structure of heat-treated woods. For this purpose, scots pine (Pinus sylvestris L.), oriental beech (Fagus orientalis L.), and oriental spruce (Picea orientalis L.) wood species were heat-treated at different temperatures. The effect of chemical changes on the FT-Raman and ATR-FTIR bands or ratios of heat-treated wood was related with the OH association of cellulose, functional groups, and the aromatic system of lignin. The effects of heat treatment on the carbohydrate and lignin peaks varied depending on the wood species. The spectral changes that occurred after heat treatment reflected the progress of the condensation reaction of lignin. Degradation of hemicelluloses led to a decrease in free hydroxyl groups. High temperature caused crystalline cellulose to increase due to the degradation of amorphous cellulose.

Determination of chemical changes in heat-treated wood using ATR-FTIR and FT Raman spectrometry.

PubMed

Özgenç, Özlem; Durmaz, Sefa; Boyaci, Ismail Hakki; Eksi-Kocak, Haslet

2017-01-15

In this study, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and Fourier-transform Raman (FT-Raman) spectroscopy techniques were used to determine changes in the chemical structure of heat-treated woods. For this purpose, scots pine (Pinus sylvestris L.), oriental beech (Fagus orientalis L.), and oriental spruce (Picea orientalis L.) wood species were heat-treated at different temperatures. The effect of chemical changes on the FT-Raman and ATR-FTIR bands or ratios of heat-treated wood was related with the OH association of cellulose, functional groups, and the aromatic system of lignin. The effects of heat treatment on the carbohydrate and lignin peaks varied depending on the wood species. The spectral changes that occurred after heat treatment reflected the progress of the condensation reaction of lignin. Degradation of hemicelluloses led to a decrease in free hydroxyl groups. High temperature caused crystalline cellulose to increase due to the degradation of amorphous cellulose. Copyright © 2016 Elsevier B.V. All rights reserved.

Physico-chemical parameters and Ichthyofauna diversity of Arasalar estuary in southeast coast of India

NASA Astrophysics Data System (ADS)

Raju, C.; Sridharan, G.; Mariappan, P.; Chelladurai, G.

2017-03-01

The physico-chemical changes may have the tendency to accumulate in the various organs of estuarine organisms, especially fish which may in turn enter into the human metabolism through consumption causing serious hazards. Hence, the present study was carried out to dete rmine the physico-chemical characteristics of water and Ichthyofauna in Arasalar estuary in southeast coast of India for the period of 1 year during September 2012-August 2013. The environmental parameters such as, temperature, pH, salinity, DO, silicate, nitrate and phosphate were observed from Department of Zoology, Rajah Serfoji Goverment College, Thanjavur, Tamil Nadu, India. During the period of study, air temperature varied from 28.8 to 35 °C. The surface water temperature also varied from 25 to 31.5 °C. The monthly mean values of hydrogen ion concentration of water varied from 7.1 to 8.2. The salinity of water varied from 5.5 ‰ to 34. Dissolved oxygen in Arasalar estuary was varied from 3.5 to 7.2 mg/l. The total phosphorus varied from 0.29 to 2.15 µg/1. The nitrate varied from 0.47 to 3.75 µg/l. The silicate content varied from 28.25 to 98.74 µg/l. Totally 866 fishes were collected belonging to 4 orders and 5 families. Mystus gulio was found to be the dominant species (25.40 %) in the study area.

Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belianinov, Alex; Burch, Matthew J.; Hysmith, Holland E.

Transitioning to multi-material systems as either interfaced 2D materials or 3D heterostructures can lead to the next generation multi-functional device architectures. Combined direct physical and chemical nanoscale control of these systems offers a new way to tailor material and device functionality as functional structures reach their physical limit. Transition metal thiophosphate (TPS), Cu 1-xIn 1+x/3P 2S 6, that have ferroelectric polarization behavior as layered crystals at room temperature and above make them attractive candidates for direct material sculpting of both chemical and functional properties. The bulk material exhibits stable ferroelectric polarization corroborated by domain structures, rewritable polarization, and hysteresis loops.more » Our previous studies have demonstrated that ferroic order persists on the surface and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we elucidate the chemical changes induced through helium ion irradiation in the TPS family library with varying Cu/In ratio formulations using correlated AFM and ToF-SIMS imaging. We correlate nano- and micro- structures that scale, in area and volume, to the total dose of the helium ion beam, as well as the overall copper concentration in the sample. Furthermore, our ToF-SIMS results show that ion irradiation leads to oxygen penetration as a function of Cu concentration, and proceeds along the Cu domains to the stopping distance of the helium ions in the TPS material. These results opens up new opportunities to understand and implement ferroicly coupled van der Waal devices into an existing framework of 2D heterostructures by locally tuning material chemistry and functionality.« less

Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam

DOE PAGES

Belianinov, Alex; Burch, Matthew J.; Hysmith, Holland E.; ...

2017-11-30

Transitioning to multi-material systems as either interfaced 2D materials or 3D heterostructures can lead to the next generation multi-functional device architectures. Combined direct physical and chemical nanoscale control of these systems offers a new way to tailor material and device functionality as functional structures reach their physical limit. Transition metal thiophosphate (TPS), Cu 1-xIn 1+x/3P 2S 6, that have ferroelectric polarization behavior as layered crystals at room temperature and above make them attractive candidates for direct material sculpting of both chemical and functional properties. The bulk material exhibits stable ferroelectric polarization corroborated by domain structures, rewritable polarization, and hysteresis loops.more » Our previous studies have demonstrated that ferroic order persists on the surface and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we elucidate the chemical changes induced through helium ion irradiation in the TPS family library with varying Cu/In ratio formulations using correlated AFM and ToF-SIMS imaging. We correlate nano- and micro- structures that scale, in area and volume, to the total dose of the helium ion beam, as well as the overall copper concentration in the sample. Furthermore, our ToF-SIMS results show that ion irradiation leads to oxygen penetration as a function of Cu concentration, and proceeds along the Cu domains to the stopping distance of the helium ions in the TPS material. These results opens up new opportunities to understand and implement ferroicly coupled van der Waal devices into an existing framework of 2D heterostructures by locally tuning material chemistry and functionality.« less

[Model antigens and their significance for occupational dermatology].

PubMed

Schwartze, G; Lübbe, D; Wozniak, K D

1989-07-01

By means of epicutaneous tests we studied the contact hypersensitivity to DNP-amino acids in individuals sensitized to dinitrochlorobenzene (DNCB). We found a high incidence of positive skin responses to DNP-glycine, di-DNP-L-cystine, and DNP-L-alpha-alanine, but only in some cases DNP-beta-alanine induced skin reactivity. The results are discussed both in connection with the influence of varying molecular sizes and chemical structure on the immunological reactivity and the possibility to develop a beta-alanine containing protective ointment against protein-reactive haptens.

Chemical structure of bismuth compounds determines their gastric ulcer healing efficacy and anti-Helicobacter pylori activity.

PubMed

Sandha, G S; LeBlanc, R; Van Zanten, S J; Sitland, T D; Agocs, L; Burford, N; Best, L; Mahoney, D; Hoffman, P; Leddin, D J

1998-12-01

The recognition of the role of Helicobacter pylori in the pathogenesis of peptic ulcer disease has led to renewed interest in bismuth pharmacology since bismuth compounds have both anti-Helicobacter pylori and ulcer healing properties. The precise chemical structure of current bismuth compounds is not known. This has hindered the development of new and potentially more efficacious formulations. We have created two new compounds, 2-chloro-1,3-dithia-2-bismolane (CDTB) and 1,2-[bis(1,3-dithia-2-bismolane)thio]ethane (BTBT), with known structure. In a rat model of gastric ulceration, BTBT was comparable to, and CDTB was significantly less effective than colloidal bismuth subcitrate in healing cryoprobe-induced ulcers. However, both BTBT and CDTB inhibited H. pylori growth in vitro at concentrations <1/10 that of colloidal bismuth subcitrate. The effects on ulcer healing are not mediated by suppression of acid secretion, pepsin inhibition, or prostaglandin production. Since all treated animals received the same amount of elemental bismuth, it appears that the efficacy of bismuth compounds varies with compound structure and is not simply dependent on the delivery of bismuth ion. Because the structure of the novel compounds is known, our understanding of the relationship of bismuth compound structure and to biologic activity will increase. In the future it may be possible to design other novel bismuth compounds with more potent anti-H. pylori and ulcer healing effects.

An integrated approach using orthogonal analytical techniques to characterize heparan sulfate structure.

PubMed

Beccati, Daniela; Lech, Miroslaw; Ozug, Jennifer; Gunay, Nur Sibel; Wang, Jing; Sun, Elaine Y; Pradines, Joël R; Farutin, Victor; Shriver, Zachary; Kaundinya, Ganesh V; Capila, Ishan

2017-02-01

Heparan sulfate (HS), a glycosaminoglycan present on the surface of cells, has been postulated to have important roles in driving both normal and pathological physiologies. The chemical structure and sulfation pattern (domain structure) of HS is believed to determine its biological function, to vary across tissue types, and to be modified in the context of disease. Characterization of HS requires isolation and purification of cell surface HS as a complex mixture. This process may introduce additional chemical modification of the native residues. In this study, we describe an approach towards thorough characterization of bovine kidney heparan sulfate (BKHS) that utilizes a variety of orthogonal analytical techniques (e.g. NMR, IP-RPHPLC, LC-MS). These techniques are applied to characterize this mixture at various levels including composition, fragment level, and overall chain properties. The combination of these techniques in many instances provides orthogonal views into the fine structure of HS, and in other instances provides overlapping / confirmatory information from different perspectives. Specifically, this approach enables quantitative determination of natural and modified saccharide residues in the HS chains, and identifies unusual structures. Analysis of partially digested HS chains allows for a better understanding of the domain structures within this mixture, and yields specific insights into the non-reducing end and reducing end structures of the chains. This approach outlines a useful framework that can be applied to elucidate HS structure and thereby provides means to advance understanding of its biological role and potential involvement in disease progression. In addition, the techniques described here can be applied to characterization of heparin from different sources.

Modeling the effects of vegetation heterogeneity on wildland fire behavior

NASA Astrophysics Data System (ADS)

Atchley, A. L.; Linn, R.; Sieg, C.; Middleton, R. S.

2017-12-01

Vegetation structure and densities are known to drive fire-spread rate and burn severity. Many fire-spread models incorporate an average, homogenous fuel density in the model domain to drive fire behavior. However, vegetation communities are rarely homogenous and instead present significant heterogeneous structure and fuel densities in the fires path. This results in observed patches of varied burn severities and mosaics of disturbed conditions that affect ecological recovery and hydrologic response. Consequently, to understand the interactions of fire and ecosystem functions, representations of spatially heterogeneous conditions need to be incorporated into fire models. Mechanistic models of fire disturbance offer insight into how fuel load characterization and distribution result in varied fire behavior. Here we use a physically-based 3D combustion model—FIRETEC—that solves conservation of mass, momentum, energy, and chemical species to compare fire behavior on homogenous representations to a heterogeneous vegetation distribution. Results demonstrate the impact vegetation heterogeneity has on the spread rate, intensity, and extent of simulated wildfires thus providing valuable insight in predicted wildland fire evolution and enhanced ability to estimate wildland fire inputs into regional and global climate models.

Entropy density of an adiabatic relativistic Bose-Einstein condensate star

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khaidir, Ahmad Firdaus; Kassim, Hasan Abu; Yusof, Norhasliza

Inspired by recent works, we investigate how the thermodynamics parameters (entropy, temperature, number density, energy density, etc) of Bose-Einstein Condensate star scale with the structure of the star. Below the critical temperature in which the condensation starts to occur, we study how the entropy behaves with varying temperature till it reaches its own stability against gravitational collapse and singularity. Compared to photon gases (pressure is described by radiation) where the chemical potential, μ is zero, entropy of photon gases obeys the Stefan-Boltzmann Law for a small values of T while forming a spiral structure for a large values of Tmore » due to general relativity. The entropy density of Bose-Einstein Condensate is obtained following the similar sequence but limited under critical temperature condition. We adopt the scalar field equation of state in Thomas-Fermi limit to study the characteristics of relativistic Bose-Einstein condensate under varying temperature and entropy. Finally, we obtain the entropy density proportional to (σT{sup 3}-3T) which obeys the Stefan-Boltzmann Law in ultra-relativistic condition.« less

Electric field induced microstructures in thin films on physicochemically heterogeneous and patterned substrates.

PubMed

Srivastava, Samanvaya; Reddy, P Dinesh Sankar; Wang, Cindy; Bandyopadhyay, Dipankar; Sharma, Ashutosh

2010-05-07

We study by nonlinear simulations the electric field induced pattern formation in a thin viscous film resting on a topographically or chemically patterned substrate. The thin film microstructures can be aligned to the substrate patterns within a window of parameters where the spinodal length scale of the field induced instability is close to the substrate periodicity. We investigate systematically the change in the film morphology and order when (i) the substrate pattern periodicity is varied at a constant film thickness and (ii) the film thickness is varied at a constant substrate periodicity. Simulations show two distinct pathway of evolution when the substrate-topography changes from protrusions to cavities. The isolated substrate defects generate locally ordered ripplelike structures distinct from the structures on a periodically patterned substrate. In the latter case, film morphology is governed by a competition between the pattern periodicity and the length scale of instability. Relating the thin film morphologies to the underlying substrate pattern has implications for field induced patterning and robustness of inter-interface pattern transfer, e.g., coding-decoding of information printed on a substrate.

The effect of seasons on Brazilian red propolis and its botanical source: chemical composition and antibacterial activity.

PubMed

Bueno-Silva, Bruno; Marsola, Alexandre; Ikegaki, Masaharu; Alencar, Severino M; Rosalen, Pedro L

2017-06-01

The aim of this study was to evaluate the effect of seasons on the chemical composition and antibacterial activity of Brazilian red propolis (BRP) and its plant source. BRP was collected from Maceio, Alagoas state, north-east of Brazil, during one year. Chemical composition was determined by physicochemical analyses and HPLC while antimicrobial activity was assessed against Streptococcus mutans, Streptococcus sobrinus, Staphylococcus aureus and Actinomyces naeslundii by determining the minimal inhibitory and bactericidal concentrations (MIC and MBC, respectively). The comparative chemical profiles varied quantitatively according to the collection period. Formononetin was the most abundant compound in both propolis and resin, while isoliquiritigenin, (3S)-neovestitol, (3S)-vestitol are suggested to be responsible for antimicrobial activity of Brazilian red propolis. MIC varied from 15.6 to 125 μg/mL, whereas MBC varied from 31.2 to 500 μg/mL. Therefore, season in which propolis and its botanical source are collected indeed influences their chemical compositions, resulting in variations in their antibacterial activity.

Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanrahan, Michael P.; Fought, Ellie L.; Windus, Theresa L.

The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1H– 29Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1H– 29Si HETCOR and dipolar 2D 1H– 1H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Insteadmore » the 2D NMR spectra illustrate that there is large distribution of 1H and 29Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1H– 29Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH 3), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1H and 29Si chemical shifts. Furthermore, the approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.« less

Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy

DOE PAGES

Hanrahan, Michael P.; Fought, Ellie L.; Windus, Theresa L.; ...

2017-11-22

The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1H– 29Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1H– 29Si HETCOR and dipolar 2D 1H– 1H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Insteadmore » the 2D NMR spectra illustrate that there is large distribution of 1H and 29Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1H– 29Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH 3), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1H and 29Si chemical shifts. Furthermore, the approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.« less

Lyophilization closures for protein based drugs.

PubMed

DeGrazio, F; Flynn, K

1992-01-01

Rubber stopper formulations which are currently used as lyophilization stoppers vary widely in their capacities to absorb and release moisture. Release of moisture from the stopper over the shelf life of the product may result in drug degradation for extremely low cake weight products. The degree to which rubber formulations absorb water is dependent upon the components of these formulations. Independently, polymers and fillers absorb water during autoclave cycles to varying levels depending upon such factors as the solubility, structure, possibility of chemical reactions and impurity levels of these materials. Once combined into a stopper formulation, the raw materials can react to form species which further promote absorption. Data is presented comparing the absorption characteristics of low versus high absorbent rubber formulations. The release of moisture from these formulas when stoppered on vials containing dry product is also discussed.

Spectroscopic analysis of hot-water- and dilute-acid-extracted hardwood and softwood chips

NASA Astrophysics Data System (ADS)

Lehto, Joni; Louhelainen, Jarmo; Huttunen, Marko; Alén, Raimo

2017-09-01

Hot-water and dilute sulfuric acid pretreatments were performed prior to chemical pulping for silver/white birch (Betula pendula/B. pubescens) and Scots pine (Pinus sylvestris) chips to determine if varying pretreatment conditions on the original wood material were detectable via attenuated total reflectance (ATR) infrared spectroscopy. Pretreatment conditions varied with respect to temperature (130 °C and 150 °C) and treatment time (from 30 min to 120 min). The effects of the pretreatments on the composition of wood chips were determined by ATR infrared spectroscopy. The spectral data were compared to those determined by common wood chemistry analyses to evaluate the suitability of ATR spectroscopy method for rapid detection of changes in the wood chemical composition caused by different pretreatment conditions. In addition to determining wood species-dependent differences in the wood chemical composition, analytical results indicated that most essential lignin- and carbohydrates-related phenomena taking place during hot-water and acidic pretreatments could be described by applying this simple spectral method requiring only a small sample amount and sample preparation. Such information included, for example, the cleavage of essential lignin bonds (i.e., mainly β-O-4 linkages in guaiacyl and syringyl lignin) and formation of newly condensed lignin structures under different pretreatment conditions. Carbohydrate analyses indicated significant removal of hemicelluloses (especially hardwood xylan) and hemicelluloses-derived acetyl groups during the pretreatments, but they also confirmed the highly resistant nature of cellulose towards mild pretreatments.

Spectroscopic analysis of hot-water- and dilute-acid-extracted hardwood and softwood chips.

PubMed

Lehto, Joni; Louhelainen, Jarmo; Huttunen, Marko; Alén, Raimo

2017-09-05

Hot-water and dilute sulfuric acid pretreatments were performed prior to chemical pulping for silver/white birch (Betula pendula/B. pubescens) and Scots pine (Pinus sylvestris) chips to determine if varying pretreatment conditions on the original wood material were detectable via attenuated total reflectance (ATR) infrared spectroscopy. Pretreatment conditions varied with respect to temperature (130°C and 150°C) and treatment time (from 30min to 120min). The effects of the pretreatments on the composition of wood chips were determined by ATR infrared spectroscopy. The spectral data were compared to those determined by common wood chemistry analyses to evaluate the suitability of ATR spectroscopy method for rapid detection of changes in the wood chemical composition caused by different pretreatment conditions. In addition to determining wood species-dependent differences in the wood chemical composition, analytical results indicated that most essential lignin- and carbohydrates-related phenomena taking place during hot-water and acidic pretreatments could be described by applying this simple spectral method requiring only a small sample amount and sample preparation. Such information included, for example, the cleavage of essential lignin bonds (i.e., mainly β-O-4 linkages in guaiacyl and syringyl lignin) and formation of newly condensed lignin structures under different pretreatment conditions. Carbohydrate analyses indicated significant removal of hemicelluloses (especially hardwood xylan) and hemicelluloses-derived acetyl groups during the pretreatments, but they also confirmed the highly resistant nature of cellulose towards mild pretreatments. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamics of Alkanethiol Self-Assembled Monolayer Assembly on Pd Surfaces.

PubMed

Kumar, Gaurav; Van Cleve, Timothy; Park, Jiyun; van Duin, Adri; Medlin, J Will; Janik, Michael J

2018-06-05

We investigate the structure and binding energy of alkanethiolate self-assembled monolayers (SAMs) on Pd (111), Pd (100), and Pd (110) facets at different coverages. Dispersion-corrected density functional theory calculations are used to correlate the binding energy of alkanethiolates with alkyl chain length and coverage. The equilibrium coverage of thiolate layers strongly prefers 1/3 monolayer (ML) on the Pd (111) surface. The coverage of thiolates varies with chemical potential on Pd (100) and Pd (110), increasing from 1/3 to 1/2 ML on (100) and from 1/4 to 1/2 ML on (110) as the thiol chemical potential is increased. Higher coverages are driven by attractive dispersion interactions between the extended alkyl chains, such that transitions to higher coverages occur at lower thiol chemical potentials for longer chain thiolates. Stronger adsorption to the Pd (100) surface causes the equilibrium Wulff construction of Pd particles to take on a cubic shape upon saturation with thiols. The binding of H, O, and CO adsorbates is weakened as the thiolate coverage is increased, with saturation coverages causing unfavorable binding of O and CO on Pd (100) and weakened binding on other facets. Temperature-dependent CO diffuse reflectance infrared Fourier transform spectroscopy experiments are used to corroborate the weakened binding of CO in the presence of thiolate SAMs of varying surface density. Preliminary results of multiscale modeling efforts on the Pd-thiol system using a reactive force field, ReaxFF, are also discussed.

Cranberry Resistance to Dodder Parasitism: Induced Chemical Defenses and Behavior of a Parasitic Plant.

PubMed

Tjiurutue, Muvari Connie; Sandler, Hilary A; Kersch-Becker, Monica F; Theis, Nina; Adler, Lynn A

2016-02-01

Parasitic plants are common in many ecosystems, where they can structure community interactions and cause major economic damage. For example, parasitic dodder (Cuscuta spp.) can cause up to 80-100 % yield loss in heavily infested cranberry (Vaccinium macrocarpon) patches. Despite their ecological and economic importance, remarkably little is known about how parasitic plants affect, or are affected by, host chemistry. To examine chemically-mediated interactions between dodder and its cranberry host, we conducted a greenhouse experiment asking whether: (1) dodder performance varies with cranberry cultivar; (2) cultivars differ in levels of phytohormones, volatiles, or phenolics, and whether such variation correlates with dodder parasitism; (3) dodder parasitism induced changes in phytohormones, volatiles, or phenolics, and whether the level of inducible response varied among cultivars. We used five cranberry cultivars to assess host attractiveness to dodder and dodder performance. Dodder performance did not differ across cultivars, but there were marginally significant differences in host attractiveness to dodder, with fewer dodder attaching to Early Black than to any other cultivar. Dodder parasitism induced higher levels of salicylic acid (SA) across cultivars. Cultivars differed in overall levels of flavonols and volatile profiles, but not phenolic acids or proanthocyanidins, and dodder attachment induced changes in several flavonols and volatiles. While cultivars differed slightly in resistance to dodder attachment, we did not find evidence of chemical defenses that mediate these interactions. However, induction of several defenses indicates that parasitism alters traits that could influence subsequent interactions with other species, thus shaping community dynamics.

Nano-hybrid carboxymethyl-hexanoyl chitosan modified with (3-aminopropyl)triethoxysilane for camptothecin delivery.

PubMed

Hsiao, Meng-Hsuan; Tung, Tsan-Hua; Hsiao, Chi-Sheng; Liu, Dean-Mo

2012-06-20

Silane-modified amphiphilic chitosan was synthesized by anchoring a silane coupling agent, (3-aminopropyl)triethoxysilane, to a novel amphiphilic carboxymethyl-hexanoyl chitosan (CHC). The chemical structure of this new organic-inorganic hybrid molecule was characterized by FTIR and 13C-, 29Si-nuclear magnetic resonance, while the structural evolution was examined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS). Experimental results indicated a self-assembly behaviour of molecules into nanoparticles with a stable polygonal geometry, consisting of ordered silane layers of 6 nm in thickness. The self-assembly property was found to be influenced by chemical composition and concentration of silane incorporated, while the size can be varied by the amount of anchored silane. It was also demonstrated that such vesicle exhibited excellent cytocompatibility and cellular internalization capability in ARPE-19 cell line, and presented well-controlled encapsulation and release profiles for (S)-(+)-camptothecin. These unique properties render it as a potential drug delivery nanosystem. Copyright © 2012 Elsevier Ltd. All rights reserved.

Probing defects in chemically synthesized ZnO nanostrucures by positron annihilation and photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Chaudhuri, S. K.; Ghosh, Manoranjan; Das, D.; Raychaudhuri, A. K.

2010-09-01

The present article describes the size induced changes in the structural arrangement of intrinsic defects present in chemically synthesized ZnO nanoparticles of various sizes. Routine x-ray diffraction and transmission electron microscopy have been performed to determine the shapes and sizes of the nanocrystalline ZnO samples. Detailed studies using positron annihilation spectroscopy reveals the presence of zinc vacancy. Whereas analysis of photoluminescence results predict the signature of charged oxygen vacancies. The size induced changes in positron parameters as well as the photoluminescence properties, has shown contrasting or nonmonotonous trends as size varies from 4 to 85 nm. Small spherical particles below a critical size (˜23 nm) receive more positive surface charge due to the higher occupancy of the doubly charge oxygen vacancy as compared to the bigger nanostructures where singly charged oxygen vacancy predominates. This electronic alteration has been seen to trigger yet another interesting phenomenon, described as positron confinement inside nanoparticles. Finally, based on all the results, a model of the structural arrangement of the intrinsic defects in the present samples has been reconciled.

The structure and mechanical properties of parts elaborated by direct laser deposition 316L stainless steel powder obtained in various ways

NASA Astrophysics Data System (ADS)

Loginova, I. S.; Solonin, A. N.; Prosviryakov, A. S.; Adisa, S. B.; Khalil, A. M.; Bykovskiy, D. P.; Petrovskiy, V. N.

2017-12-01

In this work the morphology, the size and the chemical composition of the powders of steel 316L received by the two methods was studied: fusion dispersion by a gas stream and reduction of metal chlorides with the subsequent plasma atomization of the received powder particles. The powder particles received by the first method have a spherical shape (aspect ratio 1,0-1,2) with an average size of 77 μm and are characterized by the absence of internal porosity. Particles of the powder received by the second method also have a spherical shape and faultless structure, however, their chemical composition may vary in different particles. The average size of particles is 32 μm. Though the obtained powders had different properties, the experimental samples received by DLD technology demonstrated by equally high durability (Ultimate strength is 623±5 and of 623±18 MPa respectively) and plasticity (38 and 41% respectively). It is established that mechanical properties of DLD samples increase for 7-10% after treatment of the surface.

Mechanical Properties of Nanostructured Materials Determined Through Molecular Modeling Techniques

NASA Technical Reports Server (NTRS)

Clancy, Thomas C.; Gates, Thomas S.

2005-01-01

The potential for gains in material properties over conventional materials has motivated an effort to develop novel nanostructured materials for aerospace applications. These novel materials typically consist of a polymer matrix reinforced with particles on the nanometer length scale. In this study, molecular modeling is used to construct fully atomistic models of a carbon nanotube embedded in an epoxy polymer matrix. Functionalization of the nanotube which consists of the introduction of direct chemical bonding between the polymer matrix and the nanotube, hence providing a load transfer mechanism, is systematically varied. The relative effectiveness of functionalization in a nanostructured material may depend on a variety of factors related to the details of the chemical bonding and the polymer structure at the nanotube-polymer interface. The objective of this modeling is to determine what influence the details of functionalization of the carbon nanotube with the polymer matrix has on the resulting mechanical properties. By considering a range of degree of functionalization, the structure-property relationships of these materials is examined and mechanical properties of these models are calculated using standard techniques.

Fabrication of Nanocarbon Composites Using In Situ Chemical Vapor Deposition and Their Applications.

PubMed

He, Chunnian; Zhao, Naiqin; Shi, Chunsheng; Liu, Enzuo; Li, Jiajun

2015-09-23

Nanocarbon (carbon nanotubes (CNTs) and graphene (GN)) composites attract considerable research interest due to their fascinating applications in many fields. Here, recent developments in the field of in situ chemical vapor deposition (CVD) for the design and controlled preparation of advanced nanocarbon composites are highlighted, specifically, CNT-reinforced bulk structural composites, as well as CNT, GN, and CNT/GN functional composites, together with their practical and potential applications. In situ CVD is a very attractive approach for the fabrication of composites because of its engaging features, such as its simplicity, low-cost, versatility, and tunability. The morphologies, structures, dispersion, and interface of the resulting nanocarbon composites can be easily modulated by varying the experimental parameters (such as temperature, catalysts, carbon sources, templates or template catalysts, etc.), which enables a great potential for the in situ synthesis of high-quality nanocarbons with tailored size and dimension for constructing high-performance composites, which has not yet been achieved by conventional methods. In addition, new trends of the in situ CVD toward nanocarbon composites are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The rheo-Raman microscope: Simultaneous chemical, conformational, mechanical, and microstructural measures of soft materials

NASA Astrophysics Data System (ADS)

Kotula, Anthony P.; Meyer, Matthew W.; De Vito, Francesca; Plog, Jan; Hight Walker, Angela R.; Migler, Kalman B.

2016-10-01

The design and performance of an instrument capable of simultaneous Raman spectroscopy, rheology, and optical microscopy are described. The instrument couples a Raman spectrometer and optical microscope to a rotational rheometer through an optically transparent base, and the resulting simultaneous measurements are particularly advantageous in situations where flow properties vary due to either chemical or conformational changes in molecular structure, such as in crystallization, melting, gelation, or curing processes. Instrument performance is demonstrated on two material systems that show thermal transitions. First, we perform steady state rotational tests, Raman spectroscopy, and polarized reflection microscopy during a melting transition in a cosmetic emulsion. Second, we perform small amplitude oscillatory shear measurements along with Raman spectroscopy and polarized reflection microscopy during crystallization of a high density polyethylene. The instrument can be applied to study structure-property relationships in a variety of soft materials including thermoset resins, liquid crystalline materials, colloidal suspensions undergoing sol-gel processes, and biomacromolecules. Official contribution of the National Institute of Standards and Technology; not subject to copyright in the United States.

Structural and magnetic properties of nanocomposite iron-containing SiCxNy films

NASA Astrophysics Data System (ADS)

Pushkarev, R. V.; Fainer, N. I.; Maurya, K. K.

2017-02-01

New ferromagnetic films with composition SiCxNyFez were synthesized using chemical vapor deposition technique. Films were deposited using ferrocene, 1,1,1,3,3,3-hexamethyldisilazane (HMDS) and hydrogen gaseous mixture. Chemical and phase composition of the films were studied by FTIR, Raman spectroscopy and X-ray diffraction with grazing incidence (GI-XRD). FTIR spectra analysis confirmed the existence of Si-C and Si-N bonds. Graphite inclusions and amorphous carbon were determined by Raman spectra analysis. The surface of the SiCxNyFez films studied by SEM is covered by nanocrystallites of iron oxide Fe3O4 phase. The main purpose of GI-XRD analysis is to describe the layered structure of the films in detail. It was shown by GI-XRD study, that phase composition of the SiCxNyFez films varies from iron oxide Fe3O4 to iron silicide Fe3Si and silicon carbide SiC with the deposition temperature growing. It was established, that SiCxNyFez films are perspective for application in the spintronic field.

Surface chemical structure of poly(ethylene naphthalate) films during degradation in low-pressure high-frequency plasma treatments

NASA Astrophysics Data System (ADS)

Kamata, Noritsugu; Yuji, Toshifumi; Thungsuk, Nuttee; Arunrungrusmi, Somchai; Chansri, Pakpoom; Kinoshita, Hiroyuki; Mungkung, Narong

2018-06-01

The surface chemical structure of poly(ethylene naphthalate) (PEN) films treated with a low-pressure, high-frequency plasma was investigated by storing in a box at room temperature to protect the PEN film surface from dust. The functional groups on the PEN film surface changed over time. The functional groups of –C=O, –COH, and –COOH were abundant in the Ar + O2 mixture gas plasma-treated PEN samples as compared with those in untreated PEN samples. The changes occurred rapidly after 2 d following the plasma treatment, reaching steady states 8 d after the treatment. Hydrophobicity had an inverse relationship with the concentration of these functional groups on the surface. Thus, the effect of the low-pressure high-frequency plasma treatment on PEN varies as a function of storage time. This means that radical oxygen and oxygen molecules are clearly generated in the plasma, and this is one index to confirm that radical reaction has definitely occurred between the gas and the PEN film surface with a low-pressure high-frequency plasma.

Molecular differences between deuterated and protonated polystyrenes using reversed-phase high-performance liquid chromatography.

PubMed

Kayillo, Sindy; Gray, Michael J; Shalliker, R Andrew; Dennis, Gary R

2005-05-06

Isotopic substitution is a technique used to highlight particular bonds within a molecule for kinetic, spectroscopic and structure analysis. It is presumed that although some properties such as stretching frequencies will not be the same for substituted analogues, the chemical interactions will not vary appreciably as a function of labelling. Reversed-phase liquid chromatography has been used to demonstrate that there are significant differences between the chromatographic behaviour of a sequence of deuterated and protonated oligomeric polystyrenes. Two-dimensional reversed-phase liquid chromatography was used to show that even the diasteromers of the oligomers (n = 5) have retention mechanisms that are dependent on the subtle changes to the molecular conformation and electronic structure, which are a consequence of deuteration.

Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property

DOE PAGES

Lee, Woo-Hyung; Park, Eun Joo; Han, Junyoung; ...

2017-05-05

A new design concept for ion-conducting polymers in anion exchange membranes (AEMs) fuel cells is proposed based on structural studies and conformational analysis of polymers and their effect on the properties of AEMs. Thermally, chemically, and mechanically stable terphenyl-based polymers with pendant quaternary ammonium alkyl groups were synthesized to investigate the effect of varying the arrangement of the polymer backbone and cation-tethered alkyl chains. The results demonstrate that the microstructure and morphology of these polymeric membranes significantly influence ion conductivity and fuel cell performance. Finally, the results of this study provide new insights that will guide the molecular design ofmore » polymer electrolyte materials to improve fuel cell performance.« less

Molecular Design of Branched and Binary Molecules at Ordered Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genson, Kirsten Larson

2005-01-01

This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformationmore » which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to exert on the packing structure. The amphiphilic balance of the different molecular series exhibited control on the ordering behavior at the air-water interface and within bulk structures. The shell nature and tail type was determined to dictate the preferential ordering structure and molecular reorganization at interfaces with the core nature effect secondary.« less

Quantitative Chemical Imaging and Unsupervised Analysis Using Hyperspectral Coherent Anti-Stokes Raman Scattering Microscopy

PubMed Central

2013-01-01

In this work, we report a method to acquire and analyze hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy images of organic materials and biological samples resulting in an unbiased quantitative chemical analysis. The method employs singular value decomposition on the square root of the CARS intensity, providing an automatic determination of the components above noise, which are retained. Complex CARS susceptibility spectra, which are linear in the chemical composition, are retrieved from the CARS intensity spectra using the causality of the susceptibility by two methods, and their performance is evaluated by comparison with Raman spectra. We use non-negative matrix factorization applied to the imaginary part and the nonresonant real part of the susceptibility with an additional concentration constraint to obtain absolute susceptibility spectra of independently varying chemical components and their absolute concentration. We demonstrate the ability of the method to provide quantitative chemical analysis on known lipid mixtures. We then show the relevance of the method by imaging lipid-rich stem-cell-derived mouse adipocytes as well as differentiated embryonic stem cells with a low density of lipids. We retrieve and visualize the most significant chemical components with spectra given by water, lipid, and proteins segmenting the image into the cell surrounding, lipid droplets, cytosol, and the nucleus, and we reveal the chemical structure of the cells, with details visualized by the projection of the chemical contrast into a few relevant channels. PMID:24099603

Many Molecular Properties from One Kernel in Chemical Space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramakrishnan, Raghunathan; von Lilienfeld, O. Anatole

We introduce property-independent kernels for machine learning modeling of arbitrarily many molecular properties. The kernels encode molecular structures for training sets of varying size, as well as similarity measures sufficiently diffuse in chemical space to sample over all training molecules. Corresponding molecular reference properties provided, they enable the instantaneous generation of ML models which can systematically be improved through the addition of more data. This idea is exemplified for single kernel based modeling of internal energy, enthalpy, free energy, heat capacity, polarizability, electronic spread, zero-point vibrational energy, energies of frontier orbitals, HOMOLUMO gap, and the highest fundamental vibrational wavenumber. Modelsmore » of these properties are trained and tested using 112 kilo organic molecules of similar size. Resulting models are discussed as well as the kernels’ use for generating and using other property models.« less

Wanted: Scalable Tracers for Diffusion Measurements

PubMed Central

2015-01-01

Scalable tracers are potentially a useful tool to examine diffusion mechanisms and to predict diffusion coefficients, particularly for hindered diffusion in complex, heterogeneous, or crowded systems. Scalable tracers are defined as a series of tracers varying in size but with the same shape, structure, surface chemistry, deformability, and diffusion mechanism. Both chemical homology and constant dynamics are required. In particular, branching must not vary with size, and there must be no transition between ordinary diffusion and reptation. Measurements using scalable tracers yield the mean diffusion coefficient as a function of size alone; measurements using nonscalable tracers yield the variation due to differences in the other properties. Candidate scalable tracers are discussed for two-dimensional (2D) diffusion in membranes and three-dimensional diffusion in aqueous solutions. Correlations to predict the mean diffusion coefficient of globular biomolecules from molecular mass are reviewed briefly. Specific suggestions for the 3D case include the use of synthetic dendrimers or random hyperbranched polymers instead of dextran and the use of core–shell quantum dots. Another useful tool would be a series of scalable tracers varying in deformability alone, prepared by varying the density of crosslinking in a polymer to make say “reinforced Ficoll” or “reinforced hyperbranched polyglycerol.” PMID:25319586

Magnesium content within the skeletal architecture of the coral Montastraea faveolata: locations of brucite precipitation and implications to fine-scale data fluctuations

USGS Publications Warehouse

Buster, N.A.; Holmes, C.W.

2006-01-01

Small portions of coral cores were analyzed using a high-resolution laser ablation inductively coupled plasma mass spectrometer (LA ICP-MS) to determine the geochemical signatures within and among specific skeletal structures in the large framework coral, Montastraea faveolata. Vertical transects were sampled along three parallel skeletal structures: endothecal (septal flank), corallite wall, and exothecal (costal flank) areas. The results demonstrate that trace element levels varied among the three structures. Magnesium (Mg) varied among adjacent structures and was most abundant within the exothecal portion of the skeleton. Scanning electron microscopy (SEM) revealed the presence of hexagonal crystals forming thick discs, pairs or doublets of individual crystals, and rosettes in several samples. High Mg within these crystals was confirmed with energy dispersive spectroscopy (EDS), infrared spectrometry, and LA ICP-MS. The chemical composition is consistent with the mineral brucite [Mg(OH2)]. These crystals are located exclusively in the exothecal area of the skeleton, are often associated with green endolithic algae, and are commonly associated with increased Mg levels found in the adjacent corallite walls. Although scattered throughout the exothecal, the brucite crystals are concentrated within green bands where levels of Mg increase substantially relative to other portions of the skeleton. The presence and locations of high-Mg crystals may explain the fine-scale fluctuations in Mg data researchers have been questioning for years.

Toxicokinetic Triage for Environmental Chemicals

PubMed Central

Wambaugh, John F.; Wetmore, Barbara A.; Pearce, Robert; Strope, Cory; Goldsmith, Rocky; Sluka, James P.; Sedykh, Alexander; Tropsha, Alex; Bosgra, Sieto; Shah, Imran; Judson, Richard; Thomas, Russell S.; Woodrow Setzer, R.

2015-01-01

Toxicokinetic (TK) models link administered doses to plasma, blood, and tissue concentrations. High-throughput TK (HTTK) performs in vitro to in vivo extrapolation to predict TK from rapid in vitro measurements and chemical structure-based properties. A significant toxicological application of HTTK has been “reverse dosimetry,” in which bioactive concentrations from in vitro screening studies are converted into in vivo doses (mg/kg BW/day). These doses are predicted to produce steady-state plasma concentrations that are equivalent to in vitro bioactive concentrations. In this study, we evaluate the impact of the approximations and assumptions necessary for reverse dosimetry and develop methods to determine whether HTTK tools are appropriate or may lead to false conclusions for a particular chemical. Based on literature in vivo data for 87 chemicals, we identified specific properties (eg, in vitro HTTK data, physico-chemical descriptors, and predicted transporter affinities) that correlate with poor HTTK predictive ability. For 271 chemicals we developed a generic HT physiologically based TK (HTPBTK) model that predicts non-steady-state chemical concentration time-courses for a variety of exposure scenarios. We used this HTPBTK model to find that assumptions previously used for reverse dosimetry are usually appropriate, except most notably for highly bioaccumulative compounds. For the thousands of man-made chemicals in the environment that currently have no TK data, we propose a 4-element framework for chemical TK triage that can group chemicals into 7 different categories associated with varying levels of confidence in HTTK predictions. For 349 chemicals with literature HTTK data, we differentiated those chemicals for which HTTK approaches are likely to be sufficient, from those that may require additional data. PMID:26085347

Effects of Timber Harvest on River Food Webs: Physical, Chemical and Biological Responses

PubMed Central

Wootton, J. Timothy

2012-01-01

I compared physical, chemical and biological characteristics of nine rivers running through three timber harvest regimes to investigate the effects of land use on river ecosystems, to determine whether these corresponded to changes linked with downstream location, and to compare the response of different types of indicator variables. Physical variables changed with downstream location, but varied little with timber harvest. Most chemical variables increased strongly with timber harvest, but not with downstream location. Most biological variables did not vary systematically with either timber harvst or downstream location. Dissolved organic carbon did not vary with timber harvest or downstream location, but correlated positively with salmonid abundance. Nutrient manipulations revealed no general pattern of nutrient limitation with timber harvest or downstream location. The results suggest that chemical variables most reliably indicate timber harvest impact in these systems. The biological variables most relevant to human stakeholders were surprisingly insensitive to timber harvest, however, apparently because of decoupling from nutrient responses and unexpectedly weak responses by physical variables. PMID:22957030

Structure-solubility relationships in fluoride-containing phosphate based bioactive glasses

NASA Astrophysics Data System (ADS)

Shaharyar, Yaqoot

The dissolution of fluoride-containing bioactive glasses critically affects their biomedical applications. Most commercial fluoride-releasing bioactive glasses have been designed in the soda-lime-silica system. However, their relatively slow chemical dissolution and the adverse effect of fluoride on their bioactivity are stimulating the study of novel biodegradable materials with higher bioactivity, such as biodegradable phosphate-based bioactive glasses, which can be a viable alternative for applications where a fast release of active ions is sought. In order to design new biomaterials with controlled degradability and high bioactivity, it is essential to understand the connection between chemical composition, molecular structure, and solubility in physiological fluids.Accordingly, in this work we have combined the strengths of various experimental techniques with Molecular Dynamics (MD) simulations, to elucidate the impact of fluoride ions on the structure and chemical dissolution of bioactive phosphate glasses in the system: 10Na2O - (45-x) CaO - 45P2O5 - xCaF2, where x varies between 0 -- 10 mol.%. NMR and MD data reveal that the medium-range atomic-scale structure of thse glasses is dominated by Q2 phosphate units followed by Q1 units, and the MD simulations further show that fluoride tends to associate with network modifier cations to form alkali/alkaline-earth rich ionic aggregates. On a macroscopic scale, we find that incorporating fluoride in phosphate glasses does not affect the rate of apatite formation on the glass surface in simulated body fluid (SBF). However, fluoride has a marked favorable impact on the glass dissolution in deionized water. Similarly, fluoride incorporation in the glasses results in significant weight gain due to adsorption of water (in the form of OH ions). These macroscopic trends are discussed on the basis of the F effect on the atomistic structure of the glasses, such as the F-induced phosphate network re-polymerization, in a first attempt to establish composition-structure-property relationships for these biomaterials.

Establishing the solubility and local structure(s) of Amorphous Calcium Carbonate (ACC): Toward an understanding of invertebrate biomineralization

NASA Astrophysics Data System (ADS)

Mergelsberg, S. T.; Ulrich, R. N.; Michel, F. M.; Dove, P. M.

2017-12-01

Recent advances in high-resolution imaging show the widespreadd occurrence of multistep pathways to mineralization in biological and geological settings (De Yoreo et al., 2015, Science). For example, carbonate biomineralization often involves precipitation of amorphous calcium carbonate (ACC) as a reactive intermediate that subsequently transforms to crystalline products with diverse structures. Although current carbonate mineral proxies are based upon the composition of final crystalline products, the final signatures may be recording the properties of the initial amorphous phase. Thus, it is critical to establish the physical properties of ACC and understand the factors that influence its evolution to final products at conditions that approximate biological environments. This disconnect limits our ability to build a process-based understanding of when/how minor and trace elements are recorded in mineral composition proxies. In this experimental study, we quantified the chemical and physical properties of ACC and its evolution to final products. We first determined ACC solubility under controlled chemical conditions using a new type of flow-through reactor developed by our research group (Blue and Dove, 2015, GCA; Blue et al., 2017, GCA). The experimental design varied Mg concentration and total alkalinity while maintaining a mild pH that approximates biological environments. ACC solubility was measured at specific time points during the precipitation (from super- and undersaturated conditions) and during its subsequent evolution. Parallel experiments characterized the structure of the corresponding amorphous products using in situ pair distribution function (PDF) and small-angle x-ray scattering (SAXS) analyses. The measurements demonstrate at least two types of ACC can be produced by tuning Mg concentration and alkalinity. Each "phase" exhibits distinct short-range ordering that demonstrates structure-specific solubility. We also find temporal changes in the short-range order of each type of ACC that are dependent upon Mg content. Insights from this study hold promise for quantifying the chemical and structural properties of ACC and reconcile discrepancies in the literature.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux.

PubMed

Padgett, Mark C; Tick, Geoffrey R; Carroll, Kenneth C; Burke, William R

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions >0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. <0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux

NASA Astrophysics Data System (ADS)

Padgett, Mark C.; Tick, Geoffrey R.; Carroll, Kenneth C.; Burke, William R.

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions > 0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤ 0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. < 0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations.

Reduced sensitizing capacity of epoxy resin systems: a structure-activity relationship study.

PubMed

Niklasson, Ida B; Broo, Kerstin; Jonsson, Charlotte; Luthman, Kristina; Karlberg, Ann-Therese

2009-11-01

Epoxy resins can be prepared from numerous chemical compositions. Until recently, alternatives to epoxy resins based on diglycidyl ethers of bisphenol A (DGEBA) or bisphenol F (DGEBF) monomers have not received commercial interest, but are presently doing so, as epoxy resins with various properties are desired. Epoxy resin systems are known to cause allergic contact dermatitis because of contents of uncured monomers, reactive diluents, and hardeners. Reactive diluents, for example, glycidyl ethers, which also contain epoxide moieties, are added to reduce viscosity and improve polymerization. We have investigated the contact allergenic properties of a series of six analogues to phenyl glycidyl ether (PGE), all with similar basic structures but with varying carbon chain lengths and degrees of saturation. The chemical reactivity of the compounds in the test series toward the hexapeptide H-Pro-His-Cys-Lys-Arg-Met-OH was investigated. All epoxides were shown to bind covalently to both cysteine and proline residues. The percent depletion of nonreacted peptide was also studied resulting in 88% depletion when using PGE and 46% when using butyl glycidyl ether (5) at the same time point, thus revealing a large difference between the fastest and the slowest reacting epoxide. The skin sensitization potencies of the epoxides using the murine local lymph node assay (LLNA) were evaluated in relation to the observed physicochemical and reactivity properties. To enable determination of statistical significance between structurally closely related compounds, a nonpooled LLNA was performed. It was found that the compounds investigated ranged from strong to weak sensitizers, congruent with the reactivity data, indicating that even small changes in chemical structure result in significant differences in sensitizing capacity.

Does deposition freezing really exist? At least different as we thought

NASA Astrophysics Data System (ADS)

Abdelmonem, Ahmed

2017-04-01

The structural and chemical properties of the surface of an IN-particle (INP) play a major role in its IN ability. This role is not well explored in terms of water/INP-surface molecular-level interactions. Recent MD simulations on deposition freezing showed that water first deposits as liquid clusters and then crystallize isothermally from there [1]. We probe freezing of water on INPs of different structural and chemical properties under varying supersaturation conditions using non-linear optical spectroscopy, mainly second harmonic generation (SHG) and sum frequency generation (SFG) [2, 3]. This presentation will show very recent preliminary experimental results comparing deposition, condensation and immersion freezing (DF, CF and IF respectively) on an atmospheric relevant metal oxide surface (mica) using supercooled SHG measurements. It is found that the signal drops upon the formation of a thin film regardless of 1) the freezing path (DF or CF), 2) the formed phase (ice or liquid), indicating a similar molecular structuring. The observed structuring similarity between DF, CF and LC films is a kick-off experimental confirmation of those computational results. References 1. Lupi, L., N. Kastelowitz, and V. Molinero, Vapor deposition of water on graphitic surfaces: Formation of amorphous ice, bilayer ice, ice I, and liquid water. The Journal of Chemical Physics, 2014. 141(18): p. 18C508. 2. Abdelmonem, A., J. Lützenkirchen, and T. Leisner, Probing ice-nucleation processes on the molecular level using second harmonic generation spectroscopy. Atmospheric Measurement Techniques, 2015. 8(8): p. 3519-3526. 3. Abdelmonem, A., et al., Surface charge-induced orientation of interfacial water suppresses heterogeneous ice nucleation on α-alumina (0001). Angewandte Chemie (Submitted), 2017.

Post Processing and Biological Evaluation of the Titanium Scaffolds for Bone Tissue Engineering.

PubMed

Wysocki, Bartłomiej; Idaszek, Joanna; Szlązak, Karol; Strzelczyk, Karolina; Brynk, Tomasz; Kurzydłowski, Krzysztof J; Święszkowski, Wojciech

2016-03-15

Nowadays, post-surgical or post-accidental bone loss can be substituted by custom-made scaffolds fabricated by additive manufacturing (AM) methods from metallic powders. However, the partially melted powder particles must be removed in a post-process chemical treatment. The aim of this study was to investigate the effect of the chemical polishing with various acid baths on novel scaffolds' morphology, porosity and mechanical properties. In the first stage, Magics software (Materialise NV, Leuven, Belgium) was used to design a porous scaffolds with pore size equal to (A) 200 µm, (B) 500 µm and (C) 200 + 500 µm, and diamond cell structure. The scaffolds were fabricated from commercially pure titanium powder (CP Ti) using a SLM50 3D printing machine (Realizer GmbH, Borchen, Germany). The selective laser melting (SLM) process was optimized and the laser beam energy density in range of 91-151 J/mm³ was applied to receive 3D structures with fully dense struts. To remove not fully melted titanium particles the scaffolds were chemically polished using various HF and HF-HNO₃ acid solutions. Based on scaffolds mass loss and scanning electron (SEM) observations, baths which provided most uniform surface cleaning were proposed for each porosity. The pore and strut size after chemical treatments was calculated based on the micro-computed tomography (µ-CT) and SEM images. The mechanical tests showed that the treated scaffolds had Young's modulus close to that of compact bone. Additionally, the effect of pore size of chemically polished scaffolds on cell retention, proliferation and differentiation was studied using human mesenchymal stem cells. Small pores yielded higher cell retention within the scaffolds, which then affected their growth. This shows that in vitro cell performance can be controlled to certain extent by varying pore sizes.

Post Processing and Biological Evaluation of the Titanium Scaffolds for Bone Tissue Engineering

PubMed Central

Wysocki, Bartłomiej; Idaszek, Joanna; Szlązak, Karol; Strzelczyk, Karolina; Brynk, Tomasz; Kurzydłowski, Krzysztof J.; Święszkowski, Wojciech

2016-01-01

Nowadays, post-surgical or post-accidental bone loss can be substituted by custom-made scaffolds fabricated by additive manufacturing (AM) methods from metallic powders. However, the partially melted powder particles must be removed in a post-process chemical treatment. The aim of this study was to investigate the effect of the chemical polishing with various acid baths on novel scaffolds’ morphology, porosity and mechanical properties. In the first stage, Magics software (Materialise NV, Leuven, Belgium) was used to design a porous scaffolds with pore size equal to (A) 200 µm, (B) 500 µm and (C) 200 + 500 µm, and diamond cell structure. The scaffolds were fabricated from commercially pure titanium powder (CP Ti) using a SLM50 3D printing machine (Realizer GmbH, Borchen, Germany). The selective laser melting (SLM) process was optimized and the laser beam energy density in range of 91–151 J/mm3 was applied to receive 3D structures with fully dense struts. To remove not fully melted titanium particles the scaffolds were chemically polished using various HF and HF-HNO3 acid solutions. Based on scaffolds mass loss and scanning electron (SEM) observations, baths which provided most uniform surface cleaning were proposed for each porosity. The pore and strut size after chemical treatments was calculated based on the micro-computed tomography (µ-CT) and SEM images. The mechanical tests showed that the treated scaffolds had Young’s modulus close to that of compact bone. Additionally, the effect of pore size of chemically polished scaffolds on cell retention, proliferation and differentiation was studied using human mesenchymal stem cells. Small pores yielded higher cell retention within the scaffolds, which then affected their growth. This shows that in vitro cell performance can be controlled to certain extent by varying pore sizes. PMID:28773323

A Novel Water Delivery System for Administering Volatile Chemicals while Minimizing Chemical Waste in Rodent Toxicity Studies

EPA Science Inventory

Rodent toxicity studies typically use water bottles to administer test chemicals via drinking water. However, water bottles provide inconsistent exposure of volatile chemicals due to varying headspace, as well as lead to excessive waste of test material. In order to refine drin...

A novel water delivery system for administering volatile chemicals while minimizing chemical waste in rodent toxicity sutdies

EPA Science Inventory

Rodent toxicity studies typically use water bottles to administer test chemicals via drinking water. However, water bottles provide inconsistent exposure of volatile chemicals due to varying headspace, as well as lead to excessive waste of test material. In order to refine drinki...

Chemical defense and chemical variation in some tropical Pacific species of Halimeda (Halimedaceae; Chlorophyta)

NASA Astrophysics Data System (ADS)

Paul, Valerie J.; van Alstyne, Kathryn L.

1988-03-01

Over a dozen species of the genus Halimeda have been chemically investigated and found to produce the diterpenoid metabolites halimedatrial (1) and halimedatetraacetate (2) in varying concentrations. These meabolites have been proposed to play a role in chemical defense against herbivores based on their chemical structures and their demonstrated biological activities in laboratory and aquarium assays. We examined and compared the feeding deterrent effects of these two compounds tovard herbivorous fishes in field experiments on Guam reefs. Halimedatrial is a more effective feeding deterrent than halimedatetraacetate. It is the major secondary metabolite in young Halimeda macroloba and in the newly produced segments of growing plants. The organic extracts from young plants and new segments were significantly more deterrent than extracts from mature plant tissue. Some populations of Halimeda growing in reef-slope habitats, where herbivory is intense, also have high concentrations of halimedatrial. We compared extracts between reef slope and reef flat collections of Halimeda opuntia on Guam and Pohnpei (= Ponape), and H. discoidea and H. macroloba on Guam. We found that halimedtrial was the major metabolite in reef-slope collections of H. opuntia from Pohnpei and Pago Bay, Guam, and that halimedatetraacetate was the major metabolite a non-reef slope populations. In the cases examined, chemical defenses were greatest in (1) plant parts and (2) populations that were at greatest risk to herbivores.

Conjugated-Backbone Effect of Organic Small Molecules for n-Type Thermoelectric Materials with ZT over 0.2.

PubMed

Huang, Dazhen; Yao, Huiying; Cui, Yutao; Zou, Ye; Zhang, Fengjiao; Wang, Chao; Shen, Hongguang; Jin, Wenlong; Zhu, Jia; Diao, Ying; Xu, Wei; Di, Chong-An; Zhu, Daoben

2017-09-20

Conjugated backbones play a fundamental role in determining the electronic properties of organic semiconductors. On the basis of two solution-processable dihydropyrrolo[3,4-c]pyrrole-1,4-diylidenebis(thieno[3,2-b]thiophene) derivatives with aromatic and quinoid structures, we have carried out a systematic study of the relationship between the conjugated-backbone structure and the thermoelectric properties. In particular, a combination of UV-vis-NIR spectra, photoemission spectroscopy, and doping optimization are utilized to probe the interplay between energy levels, chemical doping, and thermoelectric performance. We found that a moderate change in the conjugated backbone leads to varied doping mechanisms and contributes to dramatic changes in the thermoelectric performance. Notably, the chemically doped A-DCV-DPPTT, a small molecule with aromatic structure, exhibits an electrical conductivity of 5.3 S cm -1 and a high power factor (PF 373 K ) up to 236 μW m -1 K -2 , which is 50 times higher than that of Q-DCM-DPPTT with a quinoid structure. More importantly, the low thermal conductivity enables A-DCV-DPPTT to possess a figure of merit (ZT) of 0.23 ± 0.03, which is the highest value reported to date for thermoelectric materials based on organic small molecules. These results demonstrate that the modulation of the conjugated backbone represents a powerful strategy for tuning the electronic structure and mobility of organic semiconductors toward a maximum thermoelectric performance.

Effects of haze pollution on microbial community changes and correlation with chemical components in atmospheric particulate matter.

PubMed

Sun, Yujiao; Xu, Shangwei; Zheng, Danyang; Li, Jie; Tian, Hezhong; Wang, Yong

2018-05-10

In this study, particulate matter (PM) with aerodynamic diameters of ≤2.5 and ≤10 μm (PM 2.5 and PM 10 , respectively), which was found at different concentrations in spring, was collected in Beijing. The chemical composition and bacterial community diversity of PM were determined, and the relationship between them was studied by 16S rRNA sequencing and mathematical statistics. Chemical composition analysis revealed greater relative percentages of total organic compounds (TOC) and secondary ions (NO 3 - , SO 4 2- , and NH 4 + ). The concentrations of Ca 2+ , Na + , Mg 2+ , K + and SO 4 2- increased in high-concentration PM, which was associated with the contribution of soil, dust and soot. Microbiological analysis revealed 1191 operational taxonomic units. Microbial community structure was stable at the phylum level. The most abundant phyla were Proteobacteria, Actinobacteria, Firmicutes, Bacteroidetes and Cyanobacteria. Community clustering analysis at the genus level showed that the difference in bacterial community structure between different PM concentrations (clean air vs. smog) was greater than that between different particle sizes. The dominant genera varied in different concentrations of PM. An unclassified genus of Cyanobacteria and Comamonadaceae were most abundant in low- and high-concentration PM, respectively. The microbial community structure was dynamic at the genus level due to different environmental factors. The dominant bacteria in high-concentration PM were widely distributed in soils, indicating that the soil contributed more to the increase in the PM. The individual microbes that were detected did not increase significantly as the PM concentration increased. The bacterial community structure was strongly correlated with K + , Ca 2+ , Na + , Mg 2+ , SO 4 2- and TOC in high-concentration PM and had a good correlation with NO 3 - , Cl - , NH 4 + and TIC in low-concentration PM. Soil and dust contributed to the increase in the concentration of the particles, and the relevant chemical components also produced differences in the bacterial community structure in different concentrations of PM. Copyright © 2018. Published by Elsevier B.V.

NMR spectroscopic study of organic phosphate esters coprecipitated with calcite

NASA Astrophysics Data System (ADS)

Phillips, Brian L.; Zhang, Zelong; Kubista, Laura; Frisia, Silvia; Borsato, Andrea

2016-06-01

Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31P{1H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31P NMR chemical shifts of the coprecipitates in the range of +1.8 to -2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C-O-P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31P/13C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13C-labeled carbonate. All coprecipitates showed significant 31P dephasing effects upon 13C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate-carbonate distances. Comparison of 31P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small signals occur with characteristics consistent with phosphate monoesters. The results of this study indicate that trace- to minor concentrations of dissolved organic molecules can be effectively taken up during calcite precipitation and incorporated in the structure, leaving a resilient record of materials present during crystallization.

Ozonation of wastewater: removal and transformation products of drugs of abuse.

PubMed

Rodayan, Angela; Segura, Pedro Alejandro; Yargeau, Viviane

2014-07-15

In this study amphetamine, methamphetamine, methylenedioxymethamphetamine (MDMA), cocaine (COC), benzoylecgonine (BE), ketamine (KET) and oxycodone (OXY) in wastewater at concentrations of 100 μgL(-1) were subjected to ozone to determine their removals as a function of ozone dose and to identify significant oxidation transformation products (OTPs) produced as a result of ozonation. A method based on high resolution mass spectrometry and differential analysis was used to facilitate and accelerate the identification and structural elucidation of the transformation products. The drug removal ranged from 3 to 50% depending on the complexity of the matrix and whether a mixture or individual drugs were ozonated. Both transient and persistent oxidation transformation products were identified for MDMA, COC and OXY and their chemical formulae were determined. Three possible structures of the persistent transformation product of MDMA (OTP-213) with chemical formula C10H16O4N, were determined based on MS(n) mass spectra and the most plausible structure (OTP-213a) was determined based on the chemistry of ozone. These results indicate that ozone is capable of removing drugs of abuse from wastewater to varying extents and that persistent transformation products are produced as a result of treatment. Copyright © 2013 Elsevier B.V. All rights reserved.

Structure, morphology and functionality of acetylated and oxidised barley starches.

PubMed

El Halal, Shanise Lisie Mello; Colussi, Rosana; Pinto, Vânia Zanella; Bartz, Josiane; Radunz, Marjana; Carreño, Neftali Lenin Villarreal; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

2015-02-01

Acetylation and oxidation are chemical modifications which alter the properties of starch. The degree of modification of acetylated and oxidized starches is dependent on the catalyst and active chlorine concentrations, respectively. The objective of this study was to evaluate the effect of acetylation and oxidation on the structural, morphological, physical-chemical, thermal and pasting properties of barley starch. Barley starches were acetylated at different catalyst levels (11%, 17%, and 23% of NaOH solution) and oxidized at different sodium hypochlorite concentrations (1.0%, 1.5%, and 2.0% of active chlorine). Fourier-transformed infrared spectroscopy (FTIR), X-ray diffractograms, thermal, morphological, and pasting properties, swelling power and solubility of starches were evaluated. The degree of substitution (DS) of the acetylated starches increased with the rise in catalyst concentration. The percentage of carbonyl (CO) and carboxyl (COOH) groups in oxidized starches also increased with the rise of active chlorine level. The presence of hydrophobic acetyl groups, carbonyl and carboxyl groups caused a partial disorganization and depolymerization of starch granules. The structural, morphological and functional changes in acetylated and oxidized starches varied according to reaction conditions. Acetylation makes barley starch more hydrophobic by the insertion of acetyl groups. Also the oxidation promotes low retrogradation and viscosity. All these characteristics are important for biodegradable film production. Copyright © 2014 Elsevier Ltd. All rights reserved.

A structural approach in the study of bones: fossil and burnt bones at nanosize scale

NASA Astrophysics Data System (ADS)

Piga, Giampaolo; Baró, Maria Dolors; Escobal, Irati Golvano; Gonçalves, David; Makhoul, Calil; Amarante, Ana; Malgosa, Assumpció; Enzo, Stefano; Garroni, Sebastiano

2016-12-01

We review the different factors affecting significantly mineral structure and composition of bones. Particularly, it is assessed that micro-nanostructural and chemical properties of skeleton bones change drastically during burning; the micro- and nanostructural changes attending those phases manifest themselves, amongst others, in observable alterations to the bones colour, morphology, microstructure, mechanical strength and crystallinity. Intense changes involving the structure and chemical composition of bones also occur during the fossilization process. Bioapatite material is contaminated by an heavy fluorination process which, on a long-time scale reduces sensibly the volume of the original unit cell, mainly the a-axis of the hexagonal P63/m space group. Moreover, the bioapatite suffers to a varying degree of extent by phase contamination from the nearby environment, to the point that rarely a fluorapatite single phase may be found in fossil bones here examined. TEM images supply precise and localized information, on apatite crystal shape and dimension, and on different processes that occur during thermal processes or fossilization of ancient bone, complementary to that given by X-ray diffraction and Attenuated Total Reflection Infrared spectroscopy. We are presenting a synthesis of XRD, ATR-IR and TEM results on the nanostructure of various modern, burned and palaeontological bones.

Structural properties and gas sensing behavior of sol-gel grown nanostructured zinc oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajyaguru, Bhargav; Gadani, Keval; Kansara, S. B.

2016-05-06

In this communication, we report the results of the studies on structural properties and gas sensing behavior of nanostructured ZnO grown using acetone precursor based modified sol-gel technique. Final product of ZnO was sintered at different temperatures to vary the crystallite size while their structural properties have been studied using X-ray diffraction (XRD) measurement performed at room temperature. XRD results suggest the single phasic nature of all the samples and crystallite size increases from 11.53 to 20.96 nm with increase in sintering temperature. Gas sensing behavior has been studied for acetone gas which indicates that lower sintered samples are moremore » capable to sense the acetone gas and related mechanism has been discussed in the light of crystallite size, crystal boundary density, defect mechanism and possible chemical reaction between gas traces and various oxygen species.« less

On the influence of tetrahedral covalent-hybridization on electronic band structure of topological insulators from first principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, X. M.; Xu, G. Z.; Liu, E. K.

Based on first-principles calculations, we investigate the influence of tetrahedral covalent-hybridization between main-group and transition-metal atoms on the topological band structures of binary HgTe and ternary half-Heusler compounds, respectively. Results show that, for the binary HgTe, when its zinc-blend structure is artificially changed to rock-salt one, the tetrahedral covalent-hybridization will be removed and correspondingly the topologically insulating band character lost. While for the ternary half-Heusler system, the strength of covalent-hybridization can be tuned by varying both chemical compositions and atomic arrangements, and the competition between tetrahedral and octahedral covalent-hybridization has been discussed in details. As a result, we found thatmore » a proper strength of tetrahedral covalent-hybridization is probably in favor to realizing the topologically insulating state with band inversion occurring at the Γ point of the Brillouin zone.« less

Crystallization-induced emission enhancement: A novel fluorescent Au-Ag bimetallic nanocluster with precise atomic structure

PubMed Central

Chen, Tao; Yang, Sha; Chai, Jinsong; Song, Yongbo; Fan, Jiqiang; Rao, Bo; Sheng, Hongting; Yu, Haizhu; Zhu, Manzhou

2017-01-01

We report the first noble metal nanocluster with a formula of Au4Ag13(DPPM)3(SR)9 exhibiting crystallization-induced emission enhancement (CIEE), where DPPM denotes bis(diphenylphosphino)methane and HSR denotes 2,5-dimethylbenzenethiol. The precise atomic structure is determined by x-ray crystallography. The crystalline state of Au4Ag13 shows strong luminescence at 695 nm, in striking contrast to the weak emission of the amorphous state and hardly any emission in solution phase. The structural analysis and the density functional theory calculations imply that the compact C–H⋯π interactions significantly restrict the intramolecular rotations and vibrations and thus considerably enhance the radiative transitions in the crystalline state. Because the noncovalent interactions can be easily modulated via varying the chemical environments, the CIEE phenomenon might represent a general strategy to amplify the fluorescence from weakly (or even non-) emissive nanoclusters. PMID:28835926

Physicochemical modifications accompanying UV laser induced surface structures on poly(ethylene terephthalate) and their effect on adhesion of mesenchymal cells.

PubMed

Rebollar, Esther; Pérez, Susana; Hernández, Margarita; Domingo, Concepción; Martín, Margarita; Ezquerra, Tiberio A; García-Ruiz, Josefa P; Castillejo, Marta

2014-09-07

This work reports on the formation of different types of structures on the surface of polymer films upon UV laser irradiation. Poly(ethylene terephthalate) was irradiated with nanosecond UV pulses at 193 and 266 nm. The polarization of the laser beam and the irradiation angle of incidence were varied, giving rise to laser induced surface structures with different shapes and periodicities. The irradiated surfaces were topographically characterized by atomic force microscopy and the chemical modifications induced by laser irradiation were inspected via micro-Raman and fluorescence spectroscopies. Contact angle measurements were performed with different liquids, and the results evaluated in terms of surface free energy components. Finally, in order to test the influence of surface properties for a potential application, the modified surfaces were used for mesenchymal stem cell culture assays and the effect of nanostructure and surface chemistry on cell adhesion was evaluated.

Structural and Dynamical Details of Biotin

NASA Astrophysics Data System (ADS)

Korter, Timothy; Dunmire, David; Romero, Danilo; Middleton, Chris; Jenkins, Tim; Hudson, Bruce; Hight Walker, Angela

2003-03-01

Biotin, one of the B vitamins, is a key cofactor of enzymes that transfer units of CO2. Chemically linked to a lysine residue via its carboxylic acid side chain, biotin exhibits incredible flexibility when performing its intraprotein transport role. Not only does Biotin play a critical role in gluconeogenesis, it also is commonly used throughout biotechnology research due to its strong binding affinity for attachment, tethering and labeling chemistries. Therefore, a detailed probe of the structure and dynamics of biotin is important both metabolically and to aid further research. Here, we used several vibrational techniques, THz, IR, Raman and Inelastic Neutron Scattering, to gain a comprehensive understanding of biotin's structure, flexibility and dynamics. Specifically our interests are in hydrogen bonding interactions, torsional vibrations, and conformational changes with varying environments, which frequently lie in the far-infrared region of the spectrum below 200 cm-1. Interpretation and comparison of our multi-technique data are guided by high-level ab initio calculations.

Sulfation effect on levan polysaccharide chains structure with molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Coskunkan, Binnaz; Turgut, Deniz; Rende, Deniz; Malta, Seyda; Baysal, Nihat; Ozisik, Rahmi; Toksoy-Oner, Ebru

Diversity in conformations and structural heterogeneity make polysaccharides the most challenging biopolymer type for experimental and theoretical characterization studies. Levan is a biopolymer chain that consists of fructose rings with β(2-6) linkages. It is a glycan that has great potential as a functional biopolymer in foods, feeds, cosmetics, pharmaceutical and chemical industries. Sulfated polysaccharides are group of macromolecules with sulfated groups in their hydroxyl parts with a range of important biological properties. Sulfate groups and their positions have a major effect on anticoagulant activity. It is reported that sulfate modified levan has anticoagulant activity such as heparin. In the current study, the effect of sulfation on the structure and dynamics of unmodified and sulfate modified levan are investigated via fully atomistic Molecular Dynamics simulations in aqueous media and varying salt concentrations at 310 K. This material is based upon work supported by the National Science Foundation under Grant No. CMMI-1538730.

Finding Chemical Structures Corresponding to a Set of Coordinates in Chemical Descriptor Space.

PubMed

Miyao, Tomoyuki; Funatsu, Kimito

2017-08-01

When chemical structures are searched based on descriptor values, or descriptors are interpreted based on values, it is important that corresponding chemical structures actually exist. In order to consider the existence of chemical structures located in a specific region in the chemical space, we propose to search them inside training data domains (TDDs), which are dense areas of a training dataset in the chemical space. We investigated TDDs' features using diverse and local datasets, assuming that GDB11 is the chemical universe. These two analyses showed that considering TDDs gives higher chance of finding chemical structures than a random search-based method, and that novel chemical structures actually exist inside TDDs. In addition to those findings, we tested the hypothesis that chemical structures were distributed on the limited areas of chemical space. This hypothesis was confirmed by the fact that distances among chemical structures in several descriptor spaces were much shorter than those among randomly generated coordinates in the training data range. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass Spectrometry Imaging and Identification of Peptides Associated with Cephalic Ganglia Regeneration in Schmidtea mediterranea*

PubMed Central

Ong, Ta-Hsuan; Romanova, Elena V.; Roberts-Galbraith, Rachel H.; Yang, Ning; Zimmerman, Tyler A.; Collins, James J.; Lee, Ji Eun; Kelleher, Neil L.; Newmark, Phillip A.; Sweedler, Jonathan V.

2016-01-01

Tissue regeneration is a complex process that involves a mosaic of molecules that vary spatially and temporally. Insights into the chemical signaling underlying this process can be achieved with a multiplex and untargeted chemical imaging method such as mass spectrometry imaging (MSI), which can enable de novo studies of nervous system regeneration. A combination of MSI and multivariate statistics was used to differentiate peptide dynamics in the freshwater planarian flatworm Schmidtea mediterranea at different time points during cephalic ganglia regeneration. A protocol was developed to make S. mediterranea tissues amenable for MSI. MS ion images of planarian tissue sections allow changes in peptides and unknown compounds to be followed as a function of cephalic ganglia regeneration. In conjunction with fluorescence imaging, our results suggest that even though the cephalic ganglia structure is visible after 6 days of regeneration, the original chemical composition of these regenerated structures is regained only after 12 days. Differences were observed in many peptides, such as those derived from secreted peptide 4 and EYE53-1. Peptidomic analysis further identified multiple peptides from various known prohormones, histone proteins, and DNA- and RNA-binding proteins as being associated with the regeneration process. Mass spectrometry data also facilitated the identification of a new prohormone, which we have named secreted peptide prohormone 20 (SPP-20), and is up-regulated during regeneration in planarians. PMID:26884331

Conformational Plasticity of the Influenza A M2 Transmembrane Helix in Lipid Bilayers Under Varying pH, Drug Binding and Membrane Thickness

PubMed Central

Hu, Fanghao; Luo, Wenbin; Cady, Sarah D.; Hong, Mei

2010-01-01

Membrane proteins change their conformations to respond to environmental cues, thus conformational plasticity is important for function. The influenza A M2 protein forms an acid-activated proton channel important for the virus lifecycle. Here we have used solid-state NMR spectroscopy to examine the conformational plasticity of membrane-bound transmembrane domain of M2 (M2TM). 13C and 15N chemical shifts indicate coupled conformational changes of several pore-facing residues due to changes in bilayer thickness, drug binding and pH. The structural changes are attributed to the formation of a well-defined helical kink at G34 in the drug-bound state and in thick lipid bilayers, non-ideal backbone conformation of the secondary-gate residue V27 in the presence of drug, and non-ideal conformation of the proton-sensing residue H37 at high pH. The chemical shifts constrained the (ϕ, ψ) torsion angles for three basis states, the equilibrium among which explains the multiple resonances per site in the NMR spectra under different combinations of bilayer thickness, drug binding and pH conditions. Thus, conformational plasticity is important for the proton conduction and inhibition of M2TM. The study illustrates the utility of NMR chemical shifts for probing the structural plasticity and folding of membrane proteins. PMID:20883664

Explaining intraspecific diversity in plant secondary metabolites in an ecological context.

PubMed

Moore, Ben D; Andrew, Rose L; Külheim, Carsten; Foley, William J

2014-02-01

Plant secondary metabolites (PSMs) are ubiquitous in plants and play many ecological roles. Each compound can vary in presence and/or quantity, and the composition of the mixture of chemicals can vary, such that chemodiversity can be partitioned within and among individuals. Plant ontogeny and environmental and genetic variation are recognized as sources of chemical variation, but recent advances in understanding the molecular basis of variation may allow the future deployment of isogenic mutants to test the specific adaptive function of variation in PSMs. An important consequence of high intraspecific variation is the capacity to evolve rapidly. It is becoming increasingly clear that trait variance linked to both macro- and micro-environmental variation can also evolve and may respond more strongly to selection than mean trait values. This research, which is in its infancy in plants, highlights what could be a missing piece of the picture of PSM evolution. PSM polymorphisms are probably maintained by multiple selective forces acting across many spatial and temporal scales, but convincing examples that recognize the diversity of plant population structures are rare. We describe how diversity can be inherently beneficial for plants and suggest fruitful avenues for future research to untangle the causes and consequences of intraspecific variation. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

Factors Affecting Exocellular Polysaccharide Production by Lactobacillus delbrueckii subsp. bulgaricus Grown in a Chemically Defined Medium†

PubMed Central

Petry, Sandrine; Furlan, Sylviane; Crepeau, Marie-Jeanne; Cerning, Jutta; Desmazeaud, Michel

2000-01-01

We developed a chemically defined medium (CDM) containing lactose or glucose as the carbon source that supports growth and exopolysaccharide (EPS) production of two strains of Lactobacillus delbrueckii subsp. bulgaricus. The factors found to affect EPS production in this medium were oxygen, pH, temperature, and medium constituents, such as orotic acid and the carbon source. EPS production was greatest during the stationary phase. Composition analysis of EPS isolated at different growth phases and produced under different fermentation conditions (varying carbon source or pH) revealed that the component sugars were the same. The EPS from strain L. delbrueckii subsp. bulgaricus CNRZ 1187 contained galactose and glucose, and that of strain L. delbrueckii subsp. bulgaricus CNRZ 416 contained galactose, glucose, and rhamnose. However, the relative proportions of the individual monosaccharides differed, suggesting that repeating unit structures can vary according to specific medium alterations. Under pH-controlled fermentation conditions, L. delbrueckii subsp. bulgaricus strains produced as much EPS in the CDM as in milk. Furthermore, the relative proportions of individual monosaccharides of EPS produced in pH-controlled CDM or in milk were very similar. The CDM we developed may be a useful model and an alternative to milk in studies of EPS production. PMID:10919802

Resolving the Strange Behavior of Extraterrestrial Potassium in the Upper Atmosphere

NASA Technical Reports Server (NTRS)

Plane, J. M. C.; Feng, W.; Dawkins, E.; Chipperfield, M. P.; Hoeffner, J.; Janches, D.; Marsh, D. R.

2014-01-01

It has been known since the 1960s that the layers of Na and K atoms, which occur between 80 and 105km in the Earth's atmosphere as a result of meteoric ablation, exhibit completely different seasonal behavior. In the extratropics Na varies annually, with a pronounced wintertime maximum and summertime minimum. However, K varies semiannually with a small summertime maximum and minima at the equinoxes. This contrasting behavior has never been satisfactorily explained. Here we use a combination of electronic structure and chemical kinetic rate theory to determine two key differences in the chemistries of K and Na. First, the neutralization of K+ ions is only favored at low temperatures during summer. Second, cycling between K and its major neutral reservoir KHCO3 is essentially temperature independent. A whole atmosphere model incorporating this new chemistry, together with a meteor input function, now correctly predicts the seasonal behavior of the K layer.

Tuning the Magnetic and Electronic Properties of Iron(x )Silicon(1-x) Thin Films for Spintronics

NASA Astrophysics Data System (ADS)

Karel, Julie Elizabeth

This dissertation investigated the magnetic and electronic properties of a potentially better alternative: off-stoichimetry, bcc-like FexSi 1-x thin films (0.43800 K) and theoretically predicted high spin polarization (100%). However, little work has been done on off-stoichiometry FexSi1-x thin films (0.43

Electrodeposition on nanofibrous polymer scaffolds: Rapid mineralization, tunable calcium phosphate composition and topography

PubMed Central

He, Chuanglong; Xiao, Guiyong; Jin, Xiaobing; Sun, Chenghui; Ma, Peter X.

2011-01-01

We developed a straightforward, fast, and versatile technique to fabricate mineralized nanofibrous polymer scaffolds for bone regeneration in this work. Nanofibrous poly(l-lactic acid) scaffolds were fabricated using both electrospinning and phase separation techniques. An electrodeposition process was designed to deposit calcium phosphate on the nanofibrous scaffolds. Such scaffolds contain a high quality mineral coating on the fiber surface with tunable surface topography and chemical composition by varying the processing parameters, which can mimic the composition and structure of natural bone extracellular matrix and provide a more biocompatible interface for bone regeneration. PMID:21673827

Phenolic Lipids Affect the Activity and Conformation of Acetylcholinesterase from Electrophorus electricus (Electric eel)

PubMed Central

Stasiuk, Maria; Janiszewska, Alicja; Kozubek, Arkadiusz

2014-01-01

Phenolic lipids were isolated from rye grains, cashew nutshell liquid (CNSL) from Anacardium occidentale, and fruit bodies of Merrulius tremellosus, and their effects on the electric eel acetylcholinesterase activity and conformation were studied. The observed effect distinctly depended on the chemical structure of the phenolic lipids that were available for interaction with the enzyme. All of the tested compounds reduced the activity of acetylcholinesterase. The degree of inhibition varied, showing a correlation with changes in the conformation of the enzyme tested by the intrinsic fluorescence of the Trp residues of the protein. PMID:24787269

Long-time variation in magnetic structure of Ce(Ir xRh 1– x) 3Si 2: A new interpretation of time variation

DOE PAGES

Motoya, Kiyoichiro; Hagihala, Masato; Univ. of Tokyo, Chiba; ...

2017-02-03

Here, to clarify the key factor for the slow magnetic transitions in CeIr 3Si 2 and other materials, magnetization and neutron scattering measurements have been carried out on the system Ce(Ir xRh 1–x) 3Si 2. In this system, a magnetic phase transition is accomplished through slow and fast processes. The fractions of these processes vary with the chemical composition x. A new interpretation of magnetic phase transitions, which includes the coexistence of two processes, is presented.

AFOSR/AFRPL Chemical Rocket Research Meeting, Abstracts and Agenda. Includes Abstracts of AFOSR Sponsored Research on Diagnostics of Reacting Flow, 18-21 March 1985, Lancaster, California

DTIC Science & Technology

1985-02-01

elf C. . 2Y~ wAqUlnjO~l hydrte? S mc Figure I. Some cyclic per,(hydroxy) carbono s5 1985 ROCKET RESEARCH MEETING *’ Abstract 14 Pg 1 Structure...Division/United Technologies Corporatiqn, Sa Jose, Ca (New Start) 1600 14 STRUCTUTU-DE=CMnITION RMATIOUSUIPS IN NSW E rTc MATERIALS. Thomas B. Brill and...its great synthetic. flexability. Hycroxy-terminated EGM prepolymers with vary- ing percentage of straight chain alkyl groups (12, 14 , .16, 18 a 20

An NMR Study of Microvoids in Polymers

NASA Technical Reports Server (NTRS)

Toy, James; Mattrix, Larry

1996-01-01

An understanding of polymer defect structures, like microvoids in polymeric matrices, is most crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally not be found naturally in polymer or in NMR probe materials. There are two NMR active Xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb and Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe-129-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts in Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of Xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A series of spectra were obtained interspersed with applications of vacuum and heating to drive out the adsorbed Xe and determine the role of Xe-Xe interactions in the observed chemical shift.

From micron to mountain-scale, using accessory phase petrochronology to quantify the rates of deformation in the Himalaya and beyond

NASA Astrophysics Data System (ADS)

Mottram, C. M.

2016-12-01

Mountains form where the Earth's plates collide; during this upheaval rocks are deformed by massive forces. The rates and timescales over which these deformational processes occur are determined from tiny accessory minerals that record geological time through radioactive decay. However, there remain major unresolved challenges in using chemical and microstructural markers to link the dates yielded from these accessory phases to specific deformation events and discerning the effects of deformation on the isotopic and elemental tracers in these phases. Here, the chemical signatures and deformation textures from micron-scale accessory phases are used to decode the record of mountain belt-scale deformational processes encrypted in the rocks. The Himalayan orogen is used as an ideal natural laboratory to understand the chemical processes that have modified the Earth's crust during orogenesis. Combined laser ablation split-stream U-Th-Pb and REE analysis of deformed monazite and titanite, along with Electron BackScatter Diffraction (EBSD) imaging and Pressure-Temperature (P-T) phase equilibria modelling are used to: (1) link accessory phase `age' to `metamorphic stage'; (2) to quantify the influence of deformation on monazite (re)crystallisation mechanisms and its subsequent effect on the crystallographic structure, ages and trace-element distribution in individual grains; and (3) understand how deformation is accommodated through different chemical and structural processes that operate at varying scales through time. This study highlights the importance of fully integrating the pressure-temperature-time-deformation history of multiple accessory phases to better interpret the deformational history of the cores of evolving mountain belts.

Soot agglomeration in isolated, free droplet combustion

NASA Technical Reports Server (NTRS)

Choi, M. Y.; Dryer, F. L.; Green, G. J.; Sangiovanni, J. J.

1993-01-01

Under the conditions of an isolated, free droplet experiment, hollow, carbonaceous structures, called soot spheres, were observed to form during the atmospheric pressure, low Reynolds number combustion of 1-methylnaphthalene. These structures which are agglomerates composed of smaller spheroidal units result from both thermophoretic effects induced by the envelope flame surrounding each drop and aerodynamic effects caused by changes in the relative gas/drop velocities. A chemically reacting flow model was used to analyze the process of sootshell formation during microgravity droplet combustion. The time-dependent temperature and gas property field surrounding the droplet was determined, and the soot cloud location for microgravity combustion of n-heptane droplets was predicted. Experiments showed that the sooting propensity of n-alkane fuel droplets can be varied through diluent substitution, oxygen-index variations, and ambient pressure reductions.

120 MeV Ni Ion beam induced modifications in poly (ethylene terephthalate) used in commercial bottled water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Vijay; Sonkawade, R. G.; Ali, Yasir

2012-06-05

We report the effects of heavy ion irradiation on the optical, structural, and chemical properties of polyethylene terephthalate (PET) film used in commercial bottled water. PET bottles were exposed with 120 MeV Ni ions at fluences varying from 3 x 10{sup 10} to 3 x 10{sup 12} ion/cm{sup 2}. The modifications so induced were analyzed by using UV-Vis, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy. Substantial decrease in optical band gap is observed with the increase in ion fluence. In the FTIR spectra, most of bands are decreased due the degradation of the molecular structure. XRD measurements showmore » the decrease in peak intensity, which reflects the loss of crystallinity after irradiation.« less

Synthesis, lipophilicity and antimicrobial activity evaluation of some new thiazolyl-oxadiazolines

PubMed Central

STOICA, CRISTINA IOANA; IONUȚ, IOANA; PÎRNĂU, ADRIAN; POP, CARMEN; ROTAR, ANCUȚA; VLASE, LAURIAN; ONIGA, SMARANDA; ONIGA, OVIDIU

2015-01-01

Background and aims Synthesis of new potential antimicrobial agents and evaluation of their lipophilicity. Methods Ten new thiazolyl-oxadiazoline derivatives were synthesized and their structures were validated by 1H-NMR and mass spectrometry. The lipophilicity of the compounds was evaluated using the principal component analysis (PCA) method. The necessary data for applying this method were obtained by reverse-phase thin-layer chromatography (RP-TLC). The antimicrobial activities were tested in vitro against four bacterial strains and one fungal strain. Results The lipophilicity varied with the structure but could not be correlated with the antimicrobial activity, since this was modest. Conclusions We have synthesized ten new heterocyclic compounds. After their physical and chemical characterization, we determined their lipophilicity and screened their antimicrobial activity. PMID:26733751

Graft copolymerization of acrylonitrile onto recycled newspapers cellulose pulp

NASA Astrophysics Data System (ADS)

Awang, N. A.; Salleh, W. N. W.; Hasbullah, H.; Yusof, N.; Aziz, F.; Jaafar, J.; Ismail, A. F.

2017-09-01

The extraction of recycled newspapers (RNP) cellulose pulp began by a series of chemical alkali extraction, 5 wt% NaOH at 125°C for 2 h. Subsequently, the bleaching of alkalized pulp was carried out by using 2 wt% NaClO2 solutions in the presence of 60 wt% of nitric acid, for 4 h at 100°C. The graft copolymerization of acrylonitrile onto the bleached cellulose pulp was initiated by using ceric ammonium nitrate. The grafting conditions were optimized by varying the ceric ammonium nitrate (CAN) initiator concentration, acrylonitrile (ACN) concentration and reaction time. The successfully of the grafting process were determined by calculating the grafting yield (%GY) and grafting efficiency (%GE). The morphological and chemical structure of resulting grafted and ungrafted recycled newspaper cellulose pulp were characterized by using scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy.

AFM investigation and optical band gap study of chemically deposited PbS thin films

NASA Astrophysics Data System (ADS)

Zaman, S.; Mansoor, M.; Abubakar; Asim, M. M.

2016-08-01

The interest into deposition of nanocrystalline PbS thin films, the potential of designing and tailoring both the topographical features and the band gap energy (Eg) by controlling growth parameters, has significant technological importance. Nanocrystalline thin films of lead sulfide were grown onto glass substrates by chemical bath deposition (CBD) method. The experiments were carried out by varying deposition temperature. We report on the modification of structural and optical properties as a function of deposition temperature. The morphological changes of the films were analyzed by using SEM and AFM. AFM was also used to calculate average roughness of the films. XRD spectra indicated preferred growth of cubic phase of PbS films in (200) direction with increasing deposition time. Optical properties have been studied by UV-Spectrophotometer. From the diffused reflectance spectra we have calculated the optical Eg shift from 0.649-0.636 eV with increasing deposition time.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ann N.; Keller, Lindsay P.; Messenger, Scott, E-mail: lan-anh.n.nguyen@nasa.gov

We report the chemical and structural analysis of nine presolar silicate grains and one presolar oxide grain from the ungrouped chondrite Acfer 094 and the CR chondrite Queen Alexandra Range 99177. Oxygen isotopic analyses indicate that five of these grains condensed in the outflows of asymptotic giant branch (AGB) stars, four have supernova (SN) origins, and one grain likely has a nova origin. Transmission electron microscopy studies show that most of the grains are amorphous with widely varying non-stoichiometric chemical compositions. Three crystalline AGB grains were identified: a clinoenstatite-containing grain assemblage, a Fe-rich olivine grain, and a nanocrystalline enstatite grainmore » encased in an amorphous silicate shell. An amorphous stoichiometric enstatite (MgSiO{sub 3}) SN grain likely condensed as a crystal and was later rendered amorphous. We do not observe a systematic difference in the chemistries and mineralogies of presolar silicates from different stellar sources, suggesting that the grains formed under a similar range of conditions.« less

Mullite Whiskers and Mullite-whisker Felt

NASA Technical Reports Server (NTRS)

Talmy, Inna G.; Haught, Deborah A.

1993-01-01

The Naval Surface Warfare Center has developed processes for the preparation of mullite (3(Al2O3)(dot)2(SiO2)) whiskers and mullite-whisker felt. Three patents on the technology were issued in 1990. The processes are based on chemical reactions between AlF3, Al2O3, and SiO2. The felt is formed in-situ during the processing of shaped powdered precursors. It consists of randomly oriented whiskers which are mutually intergrown forming a rigid structure. The microstructure and properties of the felt and size of the whiskers can be modified by varying the amount of Al2O3 in the starting mixture. Loose mullite whiskers can be used as a reinforcement for polymer-, metal-, and ceramic-matrix composites. The felt can be used as preforms for fabricating composite materials as well as for thermal insulation and high temperature, chemically stable filters for liquids (melts) and gases.

Chemical acceleration of a neutral granulated blast-furnace slag activated by sodium carbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovtun, Maxim, E-mail: max.kovtun@up.ac.za; Kearsley, Elsabe P., E-mail: elsabe.kearsley@up.ac.za; Shekhovtsova, Julia, E-mail: j.shekhovtsova@gmail.com

2015-06-15

This paper presents results of a study on chemical acceleration of a neutral granulated blast-furnace slag activated using sodium carbonate. As strength development of alkali-activated slag cements containing neutral GBFS and sodium carbonate as activator at room temperature is known to be slow, three accelerators were investigated: sodium hydroxide, ordinary Portland cement and a combination of silica fume and slaked lime. In all cements, the main hydration product is C–(A)–S–H, but its structure varies between tobermorite and riversideite depending on the accelerator used. Calcite and gaylussite are present in all systems and they were formed due to either cation exchangemore » reaction between the slag and the activator, or carbonation. With accelerators, compressive strength up to 15 MPa can be achieved within 24 h in comparison to 2.5 MPa after 48 h for a mix without an accelerator.« less

The impact of heat blanketing envelopes on neutron stars cooling

NASA Astrophysics Data System (ADS)

Beznogov, M. V.; Yakovlev, D. G.; Fortin, M.; Haensel, P.; Zdunik, J. L.

2017-11-01

The goal of this work is to investigate the effects of chemical composition of heat blanketing envelopes of neutron stars on their thermal states and thermal evolution. To this purpose, we employ newly constructed models of the envelopes composed of binary ion mixtures (H-He, He-C, C-Fe) varying the mass of lighter ions (H, He or C) in the envelope. The results are compared with those calculated using the standard “onion-like” envelope. For illustration, we apply these results to estimate the internal temperature of the Vela pulsar and to study cooling of neutron stars. We show that uncertainties in the chemical composition of the envelopes can lead up to ~ 2.5 times uncertainty of the internal temperature of the star which significantly complicates theoretical reconstruction of the internal structure of cooling neutron stars from observations of their thermal surface emission.

Breath-Figure Self-Assembly, a Versatile Method of Manufacturing Membranes and Porous Structures: Physical, Chemical and Technological Aspects

PubMed Central

2017-01-01

The review is devoted to the physical, chemical, and technological aspects of the breath-figure self-assembly process. The main stages of the process and impact of the polymer architecture and physical parameters of breath-figure self-assembly on the eventual pattern are covered. The review is focused on the hierarchy of spatial and temporal scales inherent to breath-figure self-assembly. Multi-scale patterns arising from the process are addressed. The characteristic spatial lateral scales of patterns vary from nanometers to dozens of micrometers. The temporal scale of the process spans from microseconds to seconds. The qualitative analysis performed in the paper demonstrates that the process is mainly governed by interfacial phenomena, whereas the impact of inertia and gravity are negligible. Characterization and applications of polymer films manufactured with breath-figure self-assembly are discussed. PMID:28813026

Influence of the normalized ion flux on the constitution of alumina films deposited by plasma-assisted chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurapov, Denis; Reiss, Jennifer; Trinh, David H.

2007-07-15

Alumina thin films were deposited onto tempered hot working steel substrates from an AlCl{sub 3}-O{sub 2}-Ar-H{sub 2} gas mixture by plasma-assisted chemical vapor deposition. The normalized ion flux was varied during deposition through changes in precursor content while keeping the cathode voltage and the total pressure constant. As the precursor content in the total gas mixture was increased from 0.8% to 5.8%, the deposition rate increased 12-fold, while the normalized ion flux decreased by approximately 90%. The constitution, morphology, impurity incorporation, and the elastic properties of the alumina thin films were found to depend on the normalized ion flux. Thesemore » changes in structure, composition, and properties induced by normalized ion flux may be understood by considering mechanisms related to surface and bulk diffusion.« less

Annealing effects on capacitance-voltage characteristics of a-Si/SiN(x) multilayer prepared using hot-wire chemical vapour deposition.

PubMed

Panchal, A K; Rai, D K; Solanki, C S

2011-04-01

Post-deposition annealing of a-Si/SiN(x) multilayer films at different temperature shows varying shift in high frequency (1 MHz) capacitance-voltage (HFCV) characteristics. Various a-Si/SiN(x) multilayer films were deposited using hot wire chemical vapor deposition (HWCVD) and annealed in the temperature range of 800 to 900 degrees C to precipitate Si quantum dots (Si-QD) in a-Si layers. HFCV measurements of the as-deposited and annealed films in metal-insulator-semiconductor (MIS) structures show hysterisis in C-V curves. The hysteresis in the as-deposited films and annealed films is attributed to charge trapping in Si-dangling bonds in a-Si layer and in Si-QD respectively. The charge trapping density in Si-QD increases with temperature while the interface defects density (D(it)) remains constant.

A theoretical study of molecular structure, optical properties and bond activation of energetic compound FOX-7 under intense electric fields

NASA Astrophysics Data System (ADS)

Tao, Zhiqiang; Wang, Xin; Wei, Yuan; Lv, Li; Wu, Deyin; Yang, Mingli

2017-02-01

Molecular structure, vibrational and electronic absorption spectra, chemical reactivity of energetic compound FOX-7, one of the most widely used explosives, were studied computationally in presence of an electrostatic field of 0.01-0.05 a.u. The Csbnd N bond, which usually triggers the decomposition of FOX-7, is shortened/elongated under a parallel/antiparallel field. The Csbnd N bond activation energy varies with the external electric field, decreasing remarkably with the field strength in regardless of the field direction. This is attributed to two aspects: the bond weakening by the field parallel to the Csbnd N bond and the stabilization effect on the transition-state structure by the field antiparallel to the bond. The variations in the structure and property of FOX-7 under the electric fields were further analyzed with its distributional polarizability, which is dependent on the charge transfer characteristics through the Csbnd N bond.

Acetylene terminated matrix resins

NASA Technical Reports Server (NTRS)

Goldfarb, I. J.; Lee, Y. C.; Arnold, F. E.; Helminiak, T. E.

1985-01-01

The synthesis of resins with terminal acetylene groups has provided a promising technology to yield high performance structural materials. Because these resins cure through an addition reaction, no volatile by-products are produced during the processing. The cured products have high thermal stability and good properties retention after exposure to humidity. Resins with a wide variety of different chemical structures between the terminal acetylene groups are synthesized and their mechanical properties studied. The ability of the acetylene cured polymers to give good mechanical properties is demonstrated by the resins with quinoxaline structures. Processibility of these resins can be manipulated by varying the chain length between the acetylene groups or by blending in different amounts of reactive deluents. Processing conditions similar to the state-of-the-art epoxy can be attained by using backbone structures like ether-sulfone or bis-phenol-A. The wide range of mechanical properties and processing conditions attainable by this class of resins should allow them to be used in a wide variety of applications.

Sample limited characterization of a novel disulfide-rich venom peptide toxin from terebrid marine snail Terebra variegata.

PubMed

Anand, Prachi; Grigoryan, Alexandre; Bhuiyan, Mohammed H; Ueberheide, Beatrix; Russell, Victoria; Quinoñez, Jose; Moy, Patrick; Chait, Brian T; Poget, Sébastien F; Holford, Mandë

2014-01-01

Disulfide-rich peptide toxins found in the secretions of venomous organisms such as snakes, spiders, scorpions, leeches, and marine snails are highly efficient and effective tools for novel therapeutic drug development. Venom peptide toxins have been used extensively to characterize ion channels in the nervous system and platelet aggregation in haemostatic systems. A significant hurdle in characterizing disulfide-rich peptide toxins from venomous animals is obtaining significant quantities needed for sequence and structural analyses. Presented here is a strategy for the structural characterization of venom peptide toxins from sample limited (4 ng) specimens via direct mass spectrometry sequencing, chemical synthesis and NMR structure elucidation. Using this integrated approach, venom peptide Tv1 from Terebra variegata was discovered. Tv1 displays a unique fold not witnessed in prior snail neuropeptides. The novel structural features found for Tv1 suggest that the terebrid pool of peptide toxins may target different neuronal agents with varying specificities compared to previously characterized snail neuropeptides.

Strategies for Multi-Modal Analysis

NASA Astrophysics Data System (ADS)

Hexemer, Alexander; Wang, Cheng; Pandolfi, Ronald; Kumar, Dinesh; Venkatakrishnan, Singanallur; Sethian, James; Camera Team

This section on soft materials will be dedicated to discuss the extraction of the chemical distribution and spatial arrangement of constituent elements and functional groups at multiple length scales and, thus, the examination of collective dynamics, transport, and electronic ordering phenomena. Traditional measures of structure in soft materials have relied heavily on scattering and imaging based techniques due to their capacity to measure nanoscale dimensions and their capacity to monitor structure under conditions of dynamic stress loading. Special attentions are planned to focus on the application of resonant x-ray scattering, contrast-varied neutron scattering, analytical transmission electron microscopy, and their combinations. This session aims to bring experts in both scattering and electron microscope fields to discuss recent advances in selectively characterizing structural architectures of complex soft materials, which have often multi-components with a wide range of length scales and multiple functionalities, and thus hopes to foster novel ideas to decipher a higher level of structural complexity in soft materials in future. CAMERA, Early Career Award.

Phthalates and metabolic syndrome in U.S. Adolescents (NHANES 2003-2010)

EPA Science Inventory

Children’s health outcomes may result from interactions among chemical and non-chemical stressors. We use NHANES data to investigate: Association between phthalate metabolite concentrations and MetS in adolescents If associations vary by family income (a non-chemical stressor)

Advanced nondestructive techniques applied for the detection of discontinuities in aluminum foams

NASA Astrophysics Data System (ADS)

Katchadjian, Pablo; García, Alejandro; Brizuela, Jose; Camacho, Jorge; Chiné, Bruno; Mussi, Valerio; Britto, Ivan

2018-04-01

Metal foams are finding an increasing range of applications by their lightweight structure and physical, chemical and mechanical properties. Foams can be used to fill closed moulds for manufacturing structural foam parts of complex shape [1]; foam filled structures are expected to provide good mechanical properties and energy absorption capabilities. The complexity of the foaming process and the number of parameters to simultaneously control, demand a preliminary and hugely wide experimental activity to manufacture foamed components with a good quality. That is why there are many efforts to improve the structure of foams, in order to obtain a product with good properties. The problem is that even for seemingly identical foaming conditions, the effective foaming can vary significantly from one foaming trial to another. The variation of the foams often is related by structural imperfections, joining region (foam-foam or foam-wall mold) or difficulties in achieving a complete filling of the mould. That is, in a closed mold, the result of the mold filling and its structure or defects are not known a priori and can eventually vary significantly. These defects can cause a drastic deterioration of the mechanical properties [2] and lead to a low performance in its application. This work proposes the use of advanced nondestructive techniques for evaluating the foam distribution after filling the mold to improve the manufacturing process. To achieved this purpose ultrasonic technique (UT) and cone beam computed tomography (CT) were applied on plate and structures of different thicknesses filled with foam of different porosity. UT was carried out on transmission mode with low frequency air-coupled transducers [3], in focused and unfocused configurations.

Composition and conductance distributions of single GeSi quantum rings studied by conductive atomic force microscopy combined with selective chemical etching.

PubMed

Lv, Y; Cui, J; Jiang, Z M; Yang, X J

2013-02-15

Atomic force microscopy imaging combined with selective chemical etching is employed to quantitatively investigate three-dimensional (3D) composition distributions of single GeSi quantum rings (QRs). In addition, the 3D quantitative composition distributions and the corresponding conductance distributions are simultaneously obtained on the same single GeSi QRs by conductive atomic force microscopy combined with selective chemical etching, allowing us to investigate the correlations between the conductance and composition distributions of single QRs. The results show that the QRs' central holes have higher Ge content, but exhibit lower conductance, indicating that the QRs' conductance distribution is not consistent with their composition distribution. By comparing the topography, composition and conductance profiles of the same single QRs before and after different etching processes, it is found that the conductance distributions of GeSi QRs do not vary with the change of composition distribution. Instead, the QRs' conductance distributions are found to be consistent with their topographic shapes, which can be supposed to be due to the shape determined electronic structures.

Potential and kinetic energetic analysis of phonon modes in varied molecular solids

NASA Astrophysics Data System (ADS)

Kraczek, Brent

2015-03-01

We calculate partitioned kinetic and potential energies of the phonon modes in molecular solids to illuminate the dynamical behavior of the constituent molecules. This enables analysis of the relationship between the characteristics of sets of phonon modes, molecular structure and chemical reactivity by partitioning the kinetic energy into the translational, rotational and vibrational motions of groups of atoms (including molecules), and the potential energy into the energy contained within interatomic interactions. We consider three solids of differing size and rigidity: naphthalene (C1 0 H6), nitromethane (CH3NO2)andα-HMX(C4H8N8O8). Naphthalene and nitromethane mostly act in the semi-rigid manner often expected in molecular solids. HMX exhibits behavior that is significantly less-rigid. While there are definite correlations between the kinetic and potential energetic analyses, there are also differences, particularly in the excitation of chemical bonds by low-frequency lattice modes. This suggests that in many cases computational and experimental methods dependent on atomic displacements may not identify phonon modes active in chemical reactivity.

Spatially Localized Chemical Patterns around an A + B → Oscillator Front.

PubMed

Budroni, M A; Lemaigre, L; Escala, D M; Muñuzuri, A P; De Wit, A

2016-02-18

When two gels, each loaded with a different set of reactants A and B of an oscillatory reaction, are brought into contact, reaction-diffusion patterns such as waves or Turing patterns can develop in the reactive contact zone. The initial condition which separates the reactants at the beginning leads to a localization in space of the different dynamical regimes accessible to the chemical oscillator. We study here both numerically and experimentally the composite traveling structures resulting from the interaction between chemical fronts and localized waves in the case in which the reactants of such an A + B → oscillator system are those of the canonical Belousov-Zhabotinsky (BZ) oscillating reaction. A transition between different dynamics is obtained by varying the initial concentration of the organic substrate of the BZ reactants, which is one of the parameters controlling the local excitability. We show that the dynamical regime (excitable or oscillatory) characterizing the BZ oscillator in the initial contact area is the key feature which determines the spatiotemporal evolution of the system. The experimental results are in qualitative agreement with the theoretical predictions.

Effective communication of information about chemical hazards.

PubMed

Lee, T R

1986-05-01

Given that the best available means have been used to assess the risks arising from a chemical process or product, it is a crucial aspect of management to inform the employees and the public. This task of communicating may fall to industry, government, regulating authority, professional association or an environmental protection group. It requires some understanding of the public's perceptions of the risks involved and an ethical duty to try to modify attitudes judged to be either over-anxious or complacent. There is as yet no structured knowledge on communication about chemical hazards as such. Also, circumstances vary enormously. Hence, this paper deploys the general analytic framework constructed within social psychology and reviews the extensive experimental research (and some field studies) with the aim of providing understanding and some guidance. It considers the basic modelling of attitude change as induced by printed or verbal communications. The variables influencing the effectiveness of communications are divided into: the source (e.g. his/her credibility, power or attractiveness); the message (e.g. emotional versus logical; one-sided versus both-sided arguments); and modality or media effects (e.g. spoken versus written; the mass media; campaigns).

Designing functionality in perovskite thin films using ion implantation techniques: Assessment and insights from first-principles calculations

DOE PAGES

Sharma, Vinit K.; Herklotz, Andreas; Ward, Thomas Zac; ...

2017-09-11

Ion implantation has been widely used in the semiconductor industry for decades to selectively control electron/hole doping for device applications. Recently, experimental studies on ion implantation into more structurally and electronically complex materials have been undertaken in which defect generation has been used to control a variety of functional phenomena. Of particular interest, are recent findings demonstrating that low doses of low energy helium ions into single crystal films can be used to tailor the structural properties. These initial experimental studies have shown that crystal symmetry can be continuously controlled by applying increasingly large doses of He ions into amore » crystal. The observed changes in lattice structure were then observed to correlate with functional changes, such as metal-insulator transition temperature2 and optical bandgap3. In these preliminary experimental studies, changes to lattice expansion was proposed to be the direct result of chemical pressure originating predominantly from the implanted He applying chemical pressure at interstitial sites. However, the influence of possible secondary knock-on damage arising from the He atoms transferring energy to the lattice through nuclear-nuclear collision with the crystal lattice remains largely unaddressed. In this work, we focus on a SrRuO3 model system to provide a comprehensive examination of the impact of common defects on structural and electronic properties, obtain calculated defect formation energies, and define defect migration barriers. Our model indicates that, while interstitial He can modify the crystal properties, a dose significantly larger than those reported in experimental studies would be required. The true origin of the observed structural changes is likely the result of a combination of secondary defects created during He implantation. Of particular importance, we observe that different defect types can generate greatly varied local electronic structures and that the formation energies and migration energy barriers vary by defect type. Thus, we may have identified a new method of selectively inducing controlled defect complexes into single crystal materials. Development of this approach would have a broad impact on both our ability to probe specific defect contributions in fundamental studies and allow a new level of control over functional properties driven by specific defect complexes.« less

Low-pressure chemical vapor deposition of low in situ phosphorus doped silicon thin films

NASA Astrophysics Data System (ADS)

Sarret, M.; Liba, A.; Bonnaud, O.

1991-09-01

In situ low phosphorus doped silicon films are deposited onto glass substrates by low-pressure chemical vapor deposition method. The deposition parameters, temperature, total pressure, and pure silane gas flow are, respectively, fixed at 550 °C, 0.08 Torr, and 50 sccm. The varying deposition parameter is phosphine/silane mole ratio; when this ratio varies from 2×10-6 to 4×10-4, the phosphorus concentration and the resistivity after annealing, respectively, vary from 2×1018 to 3×1020 atoms cm-3 and from 1.5 Ω cm to 2.5×10-3 Ω cm.

ACCURACY AND COST CONSIDERATIONS IN CHOOSING A CHEMICAL MECHANISM FOR OPERATIONAL USE IN AQ MODELS

EPA Science Inventory

There are several contemporary chemical kinetic mechanisms available for use in tropospheric air quality simulation models, with varying degrees of condensation of the chemical reaction pathways. Likewise, there are several different numerical solution methods available to use w...

Phthalates and metabolic syndrome in US Adolescents ...

EPA Pesticide Factsheets

Children’s health outcomes may result from interactions among chemical and non-chemical stressors. We use NHANES data to investigate: Association between phthalate metabolite concentrations and MetS in adolescents If associations vary by family income (a non-chemical stressor) Poster for 2017 CEHN Conference

Sum over Histories Representation for Kinetic Sensitivity Analysis: How Chemical Pathways Change When Reaction Rate Coefficients Are Varied

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Shirong; Davis, Michael J.; Skodje, Rex T.

2015-11-12

The sensitivity of kinetic observables is analyzed using a newly developed sum over histories representation of chemical kinetics. In the sum over histories representation, the concentrations of the chemical species are decomposed into the sum of probabilities for chemical pathways that follow molecules from reactants to products or intermediates. Unlike static flux methods for reaction path analysis, the sum over histories approach includes the explicit time dependence of the pathway probabilities. Using the sum over histories representation, the sensitivity of an observable with respect to a kinetic parameter such as a rate coefficient is then analyzed in terms of howmore » that parameter affects the chemical pathway probabilities. The method is illustrated for species concentration target functions in H-2 combustion where the rate coefficients are allowed to vary over their associated uncertainty ranges. It is found that large sensitivities are often associated with rate limiting steps along important chemical pathways or by reactions that control the branching of reactive flux« less

The effect of the solution flow rate on the properties of zinc oxide (ZnO) thin films deposited by ultrasonic spray

NASA Astrophysics Data System (ADS)

Attaf, A.; Benkhetta, Y.; Saidi, H.; Bouhdjar, A.; Bendjedidi, H.; Nouadji, M.; Lehraki, N.

2015-03-01

In this work, we used a system based on ultrasonic spray pyrolysis technique. By witch, we have deposited thin films of zinc oxide (ZnO) with the variation of solution flow rate from 50 ml / h to 150 ml / h, and set other parameters such as the concentration of the solution, the deposition time, substrate temperature and the nozzel -substrate distance. In order to study the influence of the solution flow rate on the properties of the films produced, we have several characterization techniques such as X-ray diffraction to determine the films structure, the scanning electron microscopy SEM for the morphology of the surfaces, EDS spectroscopy for the chemical composition, UV-Visible-Nir spectroscopy for determination the optical proprieties of thin films.The experimental results show that: the films have hexagonal structure at the type (wurtzite), the average size of grains varies from 20.11 to 32.45 nm, the transmittance of the films equals 80% in visible rang and the band gap is varied between 3.274 and 3.282 eV, when the solution flow rate increases from 50 to 150 ml/h.

Library of electrocatalytic sites in nano-structured domains: electrocatalysis of hydrogen peroxide.

PubMed

Pandey, Prem C; Singh, Bhupendra

2008-12-01

Electrochemical detection of hydrogen peroxide at eight types of ormosil-modified electrodes, referred as hexacyanoferrate-system; Prussian blue systems (PB-1, PB-2, and PB-3), palladium (Pd-) system, graphite (Gr-) system, gold nanoparticle (AuNPs) system and palladium-gold nanoparticle (Pd-AuNPs) system were studied. The results on electrochemical detection suggested that hydrogen peroxide does not undergo homogeneous electrochemical mediation; however, the presence of redox mediator within nano-structured domains facilitates the electro-analysis of the same via redox electrocatalysis. Four approaches causing manipulation in nano-structured domains are described: (a) increase in the molecular size of the components generating nano-structured domains; (b) modulation via chemical reactivity; (c) modulation by non-reactive moieties and known nanoparticles; and (d) modulation by mixed approaches (a-c), all leading to decrease in a nano-structured domains. The results demonstrated that an increase in the size of nano-structured domains or decrease in micro-porous geometry increases the efficiency of electrocatalysis. The basic reaction protocol adopted in generating nano-structured domains, followed by manipulation protocols, supported the introduction of a library for creating electrocatalytic sites with varying electrocatalytic efficiency within the same basic nano-structured platform.

Developing an approach for teaching and learning about Lewis structures

NASA Astrophysics Data System (ADS)

Kaufmann, Ilana; Hamza, Karim M.; Rundgren, Carl-Johan; Eriksson, Lars

2017-08-01

This study explores first-year university students' reasoning as they learn to draw Lewis structures. We also present a theoretical account of the formal procedure commonly taught for drawing these structures. Students' discussions during problem-solving activities were video recorded and detailed analyses of the discussions were made through the use of practical epistemology analysis (PEA). Our results show that the formal procedure was central for drawing Lewis structures, but its use varied depending on situational aspects. Commonly, the use of individual steps of the formal procedure was contingent on experiences of chemical structures, and other information such as the characteristics of the problem given. The analysis revealed a number of patterns in how students constructed, checked and modified the structure in relation to the formal procedure and the situational aspects. We suggest that explicitly teaching the formal procedure as a process of constructing, checking and modifying might be helpful for students learning to draw Lewis structures. By doing so, the students may learn to check the accuracy of the generated structure not only in relation to the octet rule and formal charge, but also to other experiences that are not explicitly included in the formal procedure.

On mantle chemical and thermal heterogeneities and anisotropy as mapped by inversion of global surface wave data

NASA Astrophysics Data System (ADS)

Khan, A.; Boschi, L.; Connolly, J. A. D.

2009-09-01

We invert global observations of fundamental and higher-order Love and Rayleigh surface wave dispersion data jointly at selected locations for 1-D radial profiles of Earth's mantle composition, thermal state, and anisotropic structure using a stochastic sampling algorithm. Considering mantle compositions as equilibrium assemblages of basalt and harzburgite, we employ a self-consistent thermodynamic method to compute their phase equilibria and bulk physical properties (P, S wave velocity and density). Combining these with locally varying anisotropy profiles, we determine anisotropic P and S wave velocities to calculate dispersion curves for comparison with observations. Models fitting data within uncertainties provide us with a range of profiles of composition, temperature, and anisotropy. This methodology presents an important complement to conventional seismic tomography methods. Our results indicate radial and lateral gradients in basalt fraction, with basalt depletion in the upper and enrichment of the upper part of the lower mantle, in agreement with results from geodynamical calculations, melting processes at mid-ocean ridges, and subduction of chemically stratified lithosphere. Compared with preliminary reference Earth model (PREM) and seismic tomography models, our velocity models are generally faster in the upper transition zone (TZ) and slower in the lower TZ, implying a steeper velocity gradient. While less dense than PREM, density gradients in the TZ are also steeper. Mantle geotherms are generally adiabatic in the TZ, whereas in the upper part of the lower mantle, stronger lateral variations are observed. The retrieved anisotropy structure agrees with previous studies indicating positive as well as laterally varying upper mantle anisotropy, while there is little evidence for anisotropy in and below the TZ.

Nepheline structural and chemical dependence on melt composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marcial, José; Crum, Jarrod; Neill, Owen

Nepheline crystallizes upon slow-cooling in some melts concentrated in Na2O and Al2O3, which can result in a residual glass phase of low chemical durability. Nepheline can incorporate many components often found in high-level waste radioactive borosilicate glass, including glass network ions (e.g., Si, Al, Fe), alkali metals (e.g., Cs, K, Na, and possibly Li), alkaline-earth metals (e.g., Ba, Sr, Ca, Mg), and transition metals (e.g., Mn, and possibly Cr, Zn, Ni). When crystallized from melts of different compositions, nepheline chemistry varies as a function of starting glass composition. Five simulated high level nuclear waste borosilicate glasses shown to crystallize largemore » fractions of nepheline on slow cooling, were selected for study. These melts constituted a range of Al2O3, B2O3, CaO, Na2O, K2O, Fe2O3, and SiO2 compositions. Compositional analyses of nepheline crystals in glass by electron probe micro-analysis (EPMA) indicate that boron is unlikely to be present in any significant concentration, if at all, in nepheline. Also, several models are presented for calculating the fraction of vacancies in the nepheline structure.« less

Biogeochemical control points in a water-limited critical zone

NASA Astrophysics Data System (ADS)

Chorover, J.; Brooks, P. D.; Gallery, R. E.; McIntosh, J. C.; Olshansky, Y.; Rasmussen, C.

2017-12-01

The routing of water and carbon through complex terrain is postulated to control structure evolution in the sub-humid critical zone of the southwestern US. By combining measurements of land-atmosphere exchange, ecohydrologic partitioning, and subsurface biogeochemistry, we seek to quantify how a heterogeneous (in time and space) distribution of "reactants" impacts both short-term (sub-)catchment response (e.g., pore and surface water chemical dynamics) and long-term landscape evolution (e.g., soil geochemistry/morphology and regolith weathering depth) in watersheds underlain by rhyolite and schist. Instrumented pedons in convergent, planar, and divergent landscape positions show distinct depth-dependent responses to precipitation events. Wetting front propagation, dissolved carbon flux and associated biogeochemical responses (e.g., pulses of CO2 production, O2 depletion, solute release) vary with topography, revealing the influence of lateral subsidies of water and carbon. The impacts of these episodes on the evolution of porous media heterogeneity is being investigated by statistical analysis of pore water chemistry, chemical/spectroscopic studies of solid phase organo-mineral products, sensor-derived water characteristic curves, and quantification of co-located microbial community activity/composition. Our results highlight the interacting effects of critical zone structure and convergent hydrologic flows in the evolution of biogeochemical control points.

From Chemistry to Behavior. Molecular Structure and Bioactivity of Repellents against Ixodes ricinus Ticks

PubMed Central

Fabbro, Simone Del; Nazzi, Francesco

2013-01-01

Tick-borne zoonoses are considered as emerging diseases. Tick repellents represent an effective tool for reducing the risk of tick bite and pathogens transmission. Previous work demonstrated the repellent activity of the phenylpropanoid eugenol against Ixodes ricinus; here we investigate the relationship between molecular structure and repellency in a group of substances related to that compound. We report the biological activity of 18 compounds varying for the presence/number of several moieties, including hydroxyl and methoxy groups and carbon side-chain. Each compound was tested at different doses with a bioassay designed to measure repellency against individual tick nymphs. Both vapor pressure and chemical features of the tested compounds appeared to be related to repellency. In particular, the hydroxyl and methoxy groups as well as the side-chain on the benzene ring seem to play a role. These results are discussed in light of available data on chemical perception in ticks. In the course of the study new repellent compounds were identified; the biological activity of some of them (at least as effective as the “gold standard” repellent DEET) appears to be very promising from a practical point of view. PMID:23805329

NMR based solvent exchange experiments to understand the conformational preference of intrinsically disordered proteins using FG-nucleoporin peptide as a model

PubMed Central

Heisel, Kurt A.; Krishnan, V. V.

2014-01-01

The conformational preference of a peptide with three phenylalanine-glycine (FG) repeats from the intrinsically disordered domain of nucleoporin 159 (nup159) from the yeast nucleopore complex (NPC) is studied. Conformational states of this FG-peptide in dimethyl sulfoxide (DMSO), a non-native solvent are first studied. A solvent exchange scheme is designed and performed to understand how the conformational preferences of the peptide are altered as the solvent shifts from DMSO to water. An ensemble of structures of a 19-residue peptide is determined based on 13Cα, 1Hα, and 1HN chemical shifts and with inter-proton distances. An experimental model is then presented where chemical shifts and amide-proton temperature dependence is probed at changing DMSO to water ratios. These co-solvent experiments provide evidence of a conformational change as the fraction of water increases by the stark change in the behavior of amide protons under varied temperature. This investigation provides a NMR based experimental method in the field of intrinsically disordered proteins to realize conformational transitions from a non-native set of structures (in DMSO) to a native set of disordered conformers (in water). PMID:24037535

Nuclear magnetic resonance studies of the solvation structures of a high-performance nonaqueous redox flow electrolyte

NASA Astrophysics Data System (ADS)

Deng, Xuchu; Hu, Mary; Wei, Xiaoliang; Wang, Wei; Mueller, Karl T.; Chen, Zhong; Hu, Jian Zhi

2016-03-01

Understanding the solvation structures of electrolytes is important for developing nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivatived ferrocene compound, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C, 1H and 17O NMR investigations were carried out using electrolyte solutions consisting of Fc1N112-TFSI as the solute and the mixed alkyl carbonate as the solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergo linewidth broadening, indicating interactions between solute and solvent molecules. Quantum chemistry calculations of both molecular structures and chemical shifts (13C, 1H and 17O) are performed for interpreting experimental results and for understanding the detailed solvation structures. The results indicate that Fc1N112-TFSI is dissociated at varying degrees in mixed solvent depending on concentrations. At dilute solute concentrations, most Fc1N112+ and TFSI- are fully disassociated with their own solvation shells formed by solvent molecules. At saturated concentration, Fc1N112+-TFSI- contact ion pairs are formed and the solvent molecules are preferentially interacting with the Fc rings rather than interacting with the ionic pendant arm of Fc1N112-TFSI.

Iodide uptake by negatively charged clay interlayers?

PubMed

Miller, Andrew; Kruichak, Jessica; Mills, Melissa; Wang, Yifeng

2015-09-01

Understanding iodide interactions with clay minerals is critical to quantifying risk associated with nuclear waste disposal. Current thought assumes that iodide does not interact directly with clay minerals due to electrical repulsion between the iodide and the negatively charged clay layers. However, a growing body of work indicates a weak interaction between iodide and clays. The goal of this contribution is to report a conceptual model for iodide interaction with clays by considering clay mineral structures and emergent behaviors of chemical species in confined spaces. To approach the problem, a suite of clay minerals was used with varying degrees of isomorphic substitution, chemical composition, and mineral structure. Iodide uptake experiments were completed with each of these minerals in a range of swamping electrolyte identities (NaCl, NaBr, KCl) and concentrations. Iodide uptake behaviors form distinct trends with cation exchange capacity and mineral structure. These trends change substantially with electrolyte composition and concentration, but do not appear to be affected by solution pH. The experimental results suggest that iodide may directly interact with clays by forming ion-pairs (e.g., NaI(aq)) which may concentrate within the interlayer space as well as the thin areas surrounding the clay particle where water behavior is more structured relative to bulk water. Ion pairing and iodide concentration in these zones is probably driven by the reduced dielectric constant of water in confined space and by the relatively high polarizability of the iodide species. Copyright © 2015 Elsevier Ltd. All rights reserved.

Somatic and gastrointestinal in vivo biotransformation rates of hydrophobic chemicals in fish.

PubMed

Lo, Justin C; Campbell, David A; Kennedy, Christopher J; Gobas, Frank A P C

2015-10-01

To improve current bioaccumulation assessment methods, a methodology is developed, applied, and investigated for measuring in vivo biotransformation rates of hydrophobic organic substances in the body (soma) and gastrointestinal tract of the fish. The method resembles the Organisation for Economic Co-operation and Development (OECD) 305 dietary bioaccumulation test but includes reference chemicals to determine both somatic and gastrointestinal biotransformation rates of test chemicals. Somatic biotransformation rate constants for the test chemicals ranged between 0 d(-1) and 0.38 (standard error [SE] 0.03)/d(-1) . Gastrointestinal biotransformation rate constants varied from 0 d(-1) to 46 (SE 7) d(-1) . Gastrointestinal biotransformation contributed more to the overall biotransformation in fish than somatic biotransformation for all test substances but 1. Results suggest that biomagnification tests can reveal the full extent of biotransformation in fish. The common presumption that the liver is the main site of biotransformation may not apply to many substances exposed through the diet. The results suggest that the application of quantitative structure-activity relationships (QSARs) for somatic biotransformation rates and hepatic in vitro models to assess the effect of biotransformation on bioaccumulation can underestimate biotransformation rates and overestimate the biomagnification potential of chemicals that are biotransformed in the gastrointestinal tract. With some modifications, the OECD 305 test can generate somatic and gastrointestinal biotransformation data to develop biotransformation QSARs and test in vitro-in vivo biotransformation extrapolation methods. © 2015 SETAC.

Fabrication of Superhydrophobic Surfaces with Controllable Electrical Conductivity and Water Adhesion.

PubMed

Ye, Lijun; Guan, Jipeng; Li, Zhixiang; Zhao, Jingxin; Ye, Cuicui; You, Jichun; Li, Yongjin

2017-02-14

A facile and versatile strategy for fabricating superhydrophobic surfaces with controllable electrical conductivity and water adhesion is reported. "Vine-on-fence"-structured and cerebral cortex-like superhydrophobic surfaces are constructed by filtering a suspension of multiwalled carbon nanotubes (MWCNTs), using polyoxymethylene nonwovens as the filter paper. The nonwovens with micro- and nanoporous two-tier structures act as the skeleton, introducing a microscale structure. The MWCNTs act as nanoscale structures, creating hierarchical surface roughness. The surface topography and the electrical conductivity of the superhydrophobic surfaces are controlled by varying the MWCNT loading. The vine-on-fence-structured surfaces exhibit "sticky" superhydrophobicity with high water adhesion. The cerebral cortex-like surfaces exhibit self-cleaning properties with low water adhesion. The as-prepared superhydrophobic surfaces are chemically resistant to acidic and alkaline environments of pH 2-12. They therefore have potential in applications such as droplet-based microreactors and thin-film microextraction. These findings aid our understanding of the role that surface topography plays in the design and fabrication of superhydrophobic surfaces with different water-adhesion properties.

Multifunctional 3D printing of heterogeneous hydrogel structures

NASA Astrophysics Data System (ADS)

Nadernezhad, Ali; Khani, Navid; Skvortsov, Gözde Akdeniz; Toprakhisar, Burak; Bakirci, Ezgi; Menceloglu, Yusuf; Unal, Serkan; Koc, Bahattin

2016-09-01

Multimaterial additive manufacturing or three-dimensional (3D) printing of hydrogel structures provides the opportunity to engineer geometrically dependent functionalities. However, current fabrication methods are mostly limited to one type of material or only provide one type of functionality. In this paper, we report a novel method of multimaterial deposition of hydrogel structures based on an aspiration-on-demand protocol, in which the constitutive multimaterial segments of extruded filaments were first assembled in liquid state by sequential aspiration of inks into a glass capillary, followed by in situ gel formation. We printed different patterned objects with varying chemical, electrical, mechanical, and biological properties by tuning process and material related parameters, to demonstrate the abilities of this method in producing heterogeneous and multi-functional hydrogel structures. Our results show the potential of proposed method in producing heterogeneous objects with spatially controlled functionalities while preserving structural integrity at the switching interface between different segments. We anticipate that this method would introduce new opportunities in multimaterial additive manufacturing of hydrogels for diverse applications such as biosensors, flexible electronics, tissue engineering and organ printing.

Multifunctional 3D printing of heterogeneous hydrogel structures

PubMed Central

Nadernezhad, Ali; Khani, Navid; Skvortsov, Gözde Akdeniz; Toprakhisar, Burak; Bakirci, Ezgi; Menceloglu, Yusuf; Unal, Serkan; Koc, Bahattin

2016-01-01

Multimaterial additive manufacturing or three-dimensional (3D) printing of hydrogel structures provides the opportunity to engineer geometrically dependent functionalities. However, current fabrication methods are mostly limited to one type of material or only provide one type of functionality. In this paper, we report a novel method of multimaterial deposition of hydrogel structures based on an aspiration-on-demand protocol, in which the constitutive multimaterial segments of extruded filaments were first assembled in liquid state by sequential aspiration of inks into a glass capillary, followed by in situ gel formation. We printed different patterned objects with varying chemical, electrical, mechanical, and biological properties by tuning process and material related parameters, to demonstrate the abilities of this method in producing heterogeneous and multi-functional hydrogel structures. Our results show the potential of proposed method in producing heterogeneous objects with spatially controlled functionalities while preserving structural integrity at the switching interface between different segments. We anticipate that this method would introduce new opportunities in multimaterial additive manufacturing of hydrogels for diverse applications such as biosensors, flexible electronics, tissue engineering and organ printing. PMID:27630079

Progress toward clonable inorganic nanoparticles

NASA Astrophysics Data System (ADS)

Ni, Thomas W.; Staicu, Lucian C.; Nemeth, Richard S.; Schwartz, Cindi L.; Crawford, David; Seligman, Jeffrey D.; Hunter, William J.; Pilon-Smits, Elizabeth A. H.; Ackerson, Christopher J.

2015-10-01

Pseudomonas moraviensis stanleyae was recently isolated from the roots of the selenium (Se) hyperaccumulator plant Stanleya pinnata. This bacterium tolerates normally lethal concentrations of SeO32- in liquid culture, where it also produces Se nanoparticles. Structure and cellular ultrastructure of the Se nanoparticles as determined by cellular electron tomography shows the nanoparticles as intracellular, of narrow dispersity, symmetrically irregular and without any observable membrane or structured protein shell. Protein mass spectrometry of a fractionated soluble cytosolic material with selenite reducing capability identified nitrite reductase and glutathione reductase homologues as NADPH dependent candidate enzymes for the reduction of selenite to zerovalent Se nanoparticles. In vitro experiments with commercially sourced glutathione reductase revealed that the enzyme can reduce SeO32- (selenite) to Se nanoparticles in an NADPH-dependent process. The disappearance of the enzyme as determined by protein assay during nanoparticle formation suggests that glutathione reductase is associated with or possibly entombed in the nanoparticles whose formation it catalyzes. Chemically dissolving the nanoparticles releases the enzyme. The size of the nanoparticles varies with SeO32- concentration, varying in size form 5 nm diameter when formed at 1.0 μM [SeO32-] to 50 nm maximum diameter when formed at 100 μM [SeO32-]. In aggregate, we suggest that glutathione reductase possesses the key attributes of a clonable nanoparticle system: ion reduction, nanoparticle retention and size control of the nanoparticle at the enzyme site.Pseudomonas moraviensis stanleyae was recently isolated from the roots of the selenium (Se) hyperaccumulator plant Stanleya pinnata. This bacterium tolerates normally lethal concentrations of SeO32- in liquid culture, where it also produces Se nanoparticles. Structure and cellular ultrastructure of the Se nanoparticles as determined by cellular electron tomography shows the nanoparticles as intracellular, of narrow dispersity, symmetrically irregular and without any observable membrane or structured protein shell. Protein mass spectrometry of a fractionated soluble cytosolic material with selenite reducing capability identified nitrite reductase and glutathione reductase homologues as NADPH dependent candidate enzymes for the reduction of selenite to zerovalent Se nanoparticles. In vitro experiments with commercially sourced glutathione reductase revealed that the enzyme can reduce SeO32- (selenite) to Se nanoparticles in an NADPH-dependent process. The disappearance of the enzyme as determined by protein assay during nanoparticle formation suggests that glutathione reductase is associated with or possibly entombed in the nanoparticles whose formation it catalyzes. Chemically dissolving the nanoparticles releases the enzyme. The size of the nanoparticles varies with SeO32- concentration, varying in size form 5 nm diameter when formed at 1.0 μM [SeO32-] to 50 nm maximum diameter when formed at 100 μM [SeO32-]. In aggregate, we suggest that glutathione reductase possesses the key attributes of a clonable nanoparticle system: ion reduction, nanoparticle retention and size control of the nanoparticle at the enzyme site. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04097c

Solution NMR characterization of chemokine CXCL8/IL-8 monomer and dimer binding to glycosaminoglycans: structural plasticity mediates differential binding interactions

PubMed Central

Joseph, Prem Raj B.; Mosier, Philip D.; Desai, Umesh R.; Rajarathnam, Krishna

2015-01-01

Chemokine CXCL8/interleukin-8 (IL-8) plays a crucial role in directing neutrophils and oligodendrocytes to combat infection/injury and tumour cells in metastasis development. CXCL8 exists as monomers and dimers and interaction of both forms with glycosaminoglycans (GAGs) mediate these diverse cellular processes. However, very little is known regarding the structural basis underlying CXCL8–GAG interactions. There are conflicting reports on the affinities, geometry and whether the monomer or dimer is the high-affinity GAG ligand. To resolve these issues, we characterized the binding of a series of heparin-derived oligosaccharides [heparin disaccharide (dp2), heparin tetrasaccharide (dp4), heparin octasaccharide (dp8) and heparin 14-mer (dp14)] to the wild-type (WT) dimer and a designed monomer using solution NMR spectroscopy. The pattern and extent of binding-induced chemical shift perturbation (CSP) varied between dimer and monomer and between longer and shorter oligosaccharides. NMR-based structural models show that different interaction modes coexist and that the nature of interactions varied between monomer and dimer and oligosaccharide length. MD simulations indicate that the binding interface is structurally plastic and provided residue-specific details of the dynamic nature of the binding interface. Binding studies carried out under conditions at which WT CXCL8 exists as monomers and dimers provide unambiguous evidence that the dimer is the high-affinity GAG ligand. Together, our data indicate that a set of core residues function as the major recognition/binding site, a set of peripheral residues define the various binding geometries and that the structural plasticity of the binding interface allows multiplicity of binding interactions. We conclude that structural plasticity most probably regulates in vivo CXCL8 monomer/dimer–GAG interactions and function. PMID:26371375

Protein structure refinement using a quantum mechanics-based chemical shielding predictor.

PubMed

Bratholm, Lars A; Jensen, Jan H

2017-03-01

The accurate prediction of protein chemical shifts using a quantum mechanics (QM)-based method has been the subject of intense research for more than 20 years but so far empirical methods for chemical shift prediction have proven more accurate. In this paper we show that a QM-based predictor of a protein backbone and CB chemical shifts (ProCS15, PeerJ , 2016, 3, e1344) is of comparable accuracy to empirical chemical shift predictors after chemical shift-based structural refinement that removes small structural errors. We present a method by which quantum chemistry based predictions of isotropic chemical shielding values (ProCS15) can be used to refine protein structures using Markov Chain Monte Carlo (MCMC) simulations, relating the chemical shielding values to the experimental chemical shifts probabilistically. Two kinds of MCMC structural refinement simulations were performed using force field geometry optimized X-ray structures as starting points: simulated annealing of the starting structure and constant temperature MCMC simulation followed by simulated annealing of a representative ensemble structure. Annealing of the CHARMM structure changes the CA-RMSD by an average of 0.4 Å but lowers the chemical shift RMSD by 1.0 and 0.7 ppm for CA and N. Conformational averaging has a relatively small effect (0.1-0.2 ppm) on the overall agreement with carbon chemical shifts but lowers the error for nitrogen chemical shifts by 0.4 ppm. If an amino acid specific offset is included the ProCS15 predicted chemical shifts have RMSD values relative to experiments that are comparable to popular empirical chemical shift predictors. The annealed representative ensemble structures differ in CA-RMSD relative to the initial structures by an average of 2.0 Å, with >2.0 Å difference for six proteins. In four of the cases, the largest structural differences arise in structurally flexible regions of the protein as determined by NMR, and in the remaining two cases, the large structural change may be due to force field deficiencies. The overall accuracy of the empirical methods are slightly improved by annealing the CHARMM structure with ProCS15, which may suggest that the minor structural changes introduced by ProCS15-based annealing improves the accuracy of the protein structures. Having established that QM-based chemical shift prediction can deliver the same accuracy as empirical shift predictors we hope this can help increase the accuracy of related approaches such as QM/MM or linear scaling approaches or interpreting protein structural dynamics from QM-derived chemical shift.

Structure, Dynamics, and Deuterium Fractionation of Massive Pre-stellar Cores

NASA Astrophysics Data System (ADS)

Goodson, Matthew D.; Kong, Shuo; Tan, Jonathan C.; Heitsch, Fabian; Caselli, Paola

2016-12-01

High levels of deuterium fraction in N2H+ are observed in some pre-stellar cores. Single-zone chemical models find that the timescale required to reach observed values ({D}{frac}{{{N}}2{{{H}}}+}\\equiv {{{N}}}2{{{D}}}+/{{{N}}}2{{{H}}}+≳ 0.1) is longer than the free-fall time, possibly 10 times longer. Here, we explore the deuteration of turbulent, magnetized cores with 3D magnetohydrodynamics simulations. We use an approximate chemical model to follow the growth in abundances of N2H+ and N2D+. We then examine the dynamics of the core using each tracer for comparison to observations. We find that the velocity dispersion of the core as traced by N2D+ appears slightly sub-virial compared to predictions of the Turbulent Core Model of McKee & Tan, except at late times just before the onset of protostar formation. By varying the initial mass surface density, the magnetic energy, the chemical age, and the ortho-to-para ratio of H2, we also determine the physical and temporal properties required for high deuteration. We find that low initial ortho-to-para ratios (≲ 0.01) and/or multiple free-fall times (≳ 3) of prior chemical evolution are necessary to reach the observed values of deuterium fraction in pre-stellar cores.

Micro-poromechanics model of fluid-saturated chemically active fibrous media.

PubMed

Misra, Anil; Parthasarathy, Ranganathan; Singh, Viraj; Spencer, Paulette

2015-02-01

We have developed a micromechanics based model for chemically active saturated fibrous media that incorporates fiber network microstructure, chemical potential driven fluid flow, and micro-poromechanics. The stress-strain relationship of the dry fibrous media is first obtained by considering the fiber behavior. The constitutive relationships applicable to saturated media are then derived in the poromechanics framework using Hill's volume averaging. The advantage of this approach is that the resultant continuum model accounts for the discrete nature of the individual fibers while retaining a form suitable for porous materials. As a result, the model is able to predict the influence of micro-scale phenomena, such as the fiber pre-strain caused by osmotic effects and evolution of fiber network structure with loading, on the overall behavior and in particular, on the poromechanics parameters. Additionally, the model can describe fluid-flow related rate-dependent behavior under confined and unconfined conditions and varying chemical environments. The significance of the approach is demonstrated by simulating unconfined drained monotonic uniaxial compression under different surrounding fluid bath molarity, and fluid-flow related creep and relaxation at different loading-levels and different surrounding fluid bath molarity. The model predictions conform to the experimental observations for saturated soft fibrous materials. The method can potentially be extended to other porous materials such as bone, clays, foams and concrete.

Extremely far from equilibrium: the multiscale dynamics of streamers

NASA Astrophysics Data System (ADS)

Ebert, Ute

2012-10-01

Streamers can emerge when high voltages are applied to gases. At their tips, the electric field is strongly enhanced, and electron energies locally reach distributions very far from equilibrium, with long tails at high energies. These exotic electron energies create radiation and chemical excitations at very low energy input, as the gas stays cold while the ionization front passes. Applications are multiple: highly efficient O* radical production in air for disinfection, combustion gas cleaning, plasma assisted combustion, plasma bullets in medicine etc. In that sense, streamers can be considered as very efficient converters of pulsed electric into chemical energy, in particular, if the electric circuits are optimized for the application. Streamers are also ubiquitous in nature, e.g., in the streamer corona of lightning leaders, in sprite discharges high above the clouds; and streamers also seem to contribute to generating gamma-ray flashes and even to electron-positron beams in active thunderstorms. Unravelling the intrinsic mechanisms of streamers is challenging: they can move with up to one tenth of the speed of light, and they have an intricate nonlinear structure with a hierarchy of scales. I will review how theory and experiment deal with these structures, and I will discuss the basic differences between positive and negative streamers, electron acceleration at streamer tips and the consecutive radiation and chemical reactions, the propagation mechanism of positive streamers in different gases, streamer velocities and diameters varying over at least two orders of magnitude, streamer branching and interaction, and their three-dimensional tree structure. Both theory and experiment work with a patchwork of methods, and geophysics can provide movies that cannot be taken in the lab. I will sketch the state and outline open questions.

Model tool to describe chemical structures in XML format utilizing structural fragments and chemical ontology.

PubMed

Sankar, Punnaivanam; Alain, Krief; Aghila, Gnanasekaran

2010-05-24

We have developed a model structure-editing tool, ChemEd, programmed in JAVA, which allows drawing chemical structures on a graphical user interface (GUI) by selecting appropriate structural fragments defined in a fragment library. The terms representing the structural fragments are organized in fragment ontology to provide a conceptual support. ChemEd describes the chemical structure in an XML document (ChemFul) with rich semantics explicitly encoding the details of the chemical bonding, the hybridization status, and the electron environment around each atom. The document can be further processed through suitable algorithms and with the support of external chemical ontologies to generate understandable reports about the functional groups present in the structure and their specific environment.

Toxicokinetic Triage for Environmental Chemicals.

PubMed

Wambaugh, John F; Wetmore, Barbara A; Pearce, Robert; Strope, Cory; Goldsmith, Rocky; Sluka, James P; Sedykh, Alexander; Tropsha, Alex; Bosgra, Sieto; Shah, Imran; Judson, Richard; Thomas, Russell S; Setzer, R Woodrow

2015-09-01

Toxicokinetic (TK) models link administered doses to plasma, blood, and tissue concentrations. High-throughput TK (HTTK) performs in vitro to in vivo extrapolation to predict TK from rapid in vitro measurements and chemical structure-based properties. A significant toxicological application of HTTK has been "reverse dosimetry," in which bioactive concentrations from in vitro screening studies are converted into in vivo doses (mg/kg BW/day). These doses are predicted to produce steady-state plasma concentrations that are equivalent to in vitro bioactive concentrations. In this study, we evaluate the impact of the approximations and assumptions necessary for reverse dosimetry and develop methods to determine whether HTTK tools are appropriate or may lead to false conclusions for a particular chemical. Based on literature in vivo data for 87 chemicals, we identified specific properties (eg, in vitro HTTK data, physico-chemical descriptors, and predicted transporter affinities) that correlate with poor HTTK predictive ability. For 271 chemicals we developed a generic HT physiologically based TK (HTPBTK) model that predicts non-steady-state chemical concentration time-courses for a variety of exposure scenarios. We used this HTPBTK model to find that assumptions previously used for reverse dosimetry are usually appropriate, except most notably for highly bioaccumulative compounds. For the thousands of man-made chemicals in the environment that currently have no TK data, we propose a 4-element framework for chemical TK triage that can group chemicals into 7 different categories associated with varying levels of confidence in HTTK predictions. For 349 chemicals with literature HTTK data, we differentiated those chemicals for which HTTK approaches are likely to be sufficient, from those that may require additional data. Published by Oxford University Press on behalf of Society of Toxicology 2015. This work is written by US Government employees and is in the public domain in the US.

Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

PubMed

Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

2017-05-16

Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

Analytical electron microscope study of eight ataxites

NASA Technical Reports Server (NTRS)

Novotny, P. M.; Goldstein, J. I.; Williams, D. B.

1982-01-01

Optical and electron optical (SEM, TEM, AEM) techniques were employed to investigate the fine structure of eight ataxite-iron meteorites. Structural studies indicated that the ataxites can be divided into two groups: a Widmanstaetten decomposition group and a martensite decomposition group. The Widmanstaetten decomposition group has a Type I plessite microstructure and the central taenite regions contain highly dislocated lath martensite. The steep M shaped Ni gradients in the taenite are consistent with the fast cooling rates, of not less than 500 C/my, observed for this group. The martensite decomposition group has a Type III plessite microstructure and contains all the chemical group IVB ataxites. The maximum taenite Ni contents vary from 47.5 to 52.7 wt % and are consistent with slow cooling to low temperatures of not greater than 350 C at cooling rates of not greater than 25 C/my.

Synthesis of platinum nanowheels using a bicellar template.

PubMed

Song, Yujiang; Dorin, Rachel M; Garcia, Robert M; Jiang, Ying-Bing; Wang, Haorong; Li, Peng; Qiu, Yan; van Swol, Frank; Miller, James E; Shelnutt, John A

2008-09-24

Disk-like surfactant bicelles provide a unique meso-structured reaction environment for templating the wet-chemical reduction of platinum(II) salt by ascorbic acid to produce platinum nanowheels. The Pt wheels are 496 +/-55 nm in diameter and possess thickened centers and radial dendritic nanosheets (about 2-nm in thickness) culminating in flared dendritic rims. The structural features of the platinum wheels arise from confined growth of platinum within the bilayer that is also limited at edges of the bicelles. The size of CTAB/FC7 bicelles is observed to evolve with the addition of Pt(II) complex and ascorbic acid. Synthetic control is demonstrated by varying the reaction parameters including metal salt concentration, temperature, and total surfactant concentration. This study opens up opportunities for the use of other inhomogeneous soft templates for synthesizing metals, metal alloys, and possibly semiconductors with complex nanostructures.

Development of epoxide compound from kapok oil for enhanced oil recovery

NASA Astrophysics Data System (ADS)

Anam, M. K.; Supranto; Murachman, B.; Purwono, S.

2017-06-01

Epoxide compound is made by reacting Kapok Oil with acetic acid and hydrogen peroxide with in situ method. The epoxidation reaction was varied at temperatures of 60 °C, 70 °C and 80 °C, while the time of reaction time was varied at 15 minutes, 30 minutes, 60 minutes and 90 minutes. The reaction rate coefficient for the epoxide was obtained as {\\boldsymbol{k}}{\\boldsymbol{=}}{{124}}{\\boldsymbol{,}}{{82}} {{\\exp }} {\\boldsymbol{\\bigg(}}\\frac{{\\boldsymbol-}{{24}}{\\boldsymbol{,}}{{14}}}{{\\boldsymbol{R}}{\\boldsymbol{T}}}{\\boldsymbol{\\bigg)}}. The addition of the epoxide compound 0.5 w/w in the formulation of SLS was able to reduce the IFT value up to 9.95 x 10-2 m N/m. The addition of co-surfactant (1-octanol) was varied between 0.1 and 0.4 of the total mass of the main formulation (SLS + epoxide + water formation). The smallest interfacial tension value is obtained on the addition of co-surfactants as much as 0.2 w/w, with the IFT value is 2.43 x 10-3 m N/m. The effectiveness of the chemicals was tested through micro displacement using artificial porous medium. The experimental results show that some chemicals developed in the laboratory can be used as EOR chemicals. The oil displacement experiments show that as much as 20 to 80 of remaining oil can be recovered by flooding it with the chemicals. The results also show that the oil recovery depends on type of chemicals and chemical concentration.

Chemical composition of rocks and soils at Taurus-Littrow

NASA Technical Reports Server (NTRS)

Rose, H. J., Jr.; Cuttitta, F.; Berman, S.; Brown, F. W.; Carron, M. K.; Christian, R. P.; Dwornik, E. J.; Greenland, L. P.

1974-01-01

Seventeen soils and seven rock samples were analyzed for major elements, minor elements, and trace elements. Unlike the soils at previous Apollo sites, which showed little difference in composition at each collection area, the soils at Taurus-Littrow vary widely. Three soil types are evident, representative of (1) the light mantle at the South Massif, (2) the dark mantle in the valley, and (3) the surface material at the North Massif. The dark-mantle soils are chemically similar to those at Tranquillitatis. Basalt samples from the dark mantle are chemically similar although they range from fine to coarse grained. It is suggested that they originated from the same source but crystallized at varying depths from the surface.

THE USE OF STRUCTURE-ACTIVITY RELATIONSHIPS IN INTEGRATING THE CHEMISTRY AND TOXICOLOGY OF ENDOCRINE DISRUPTING CHEMICALS

EPA Science Inventory

Structure activity relationships (SARs) are based on the principle that structurally similar chemicals should have similar biological activity. SARs relate specifically-defined toxicological activity of chemicals to their molecular structure and physico-chemical properties. To de...

Magnesium K-edge XANES spectroscopy of geological standards.

PubMed

Yoshimura, Toshihiro; Tamenori, Yusuke; Iwasaki, Nozomu; Hasegawa, Hiroshi; Suzuki, Atsushi; Kawahata, Hodaka

2013-09-01

Magnesium K-edge X-ray absorption near-edge structure (XANES) spectra have been investigated to develop a systematic understanding of a suite of Mg-bearing geological materials such as silicate and carbonate minerals, sediments, rocks and chemical reagents. For the model compounds the Mg XANES was found to vary widely between compounds and to provide a fingerprint for the form of Mg involved in geologic materials. The energy positions and resonance features obtained from these spectra can be used to specify the dominant molecular host site of Mg, thus shedding light on Mg partitioning and isotope fractionation in geologic materials and providing a valuable complement to existing knowledge of Mg geochemistry.

Plant Oil-Derived Epoxy Polymers toward Sustainable Biobased Thermosets.

PubMed

Wang, Zhongkai; Yuan, Liang; Ganewatta, Mitra S; Lamm, Meghan E; Rahman, Md Anisur; Wang, Jifu; Liu, Shengquan; Tang, Chuanbing

2017-06-01

Epoxy polymers (EPs) derived from soybean oil with varied chemical structures are synthesized. These polymers are then cured with anhydrides to yield soybean-oil-derived epoxy thermosets. The curing kinetic, thermal, and mechanical properties are well characterized. Due to the high epoxide functionality per epoxy polymer chain, these thermosets exhibit tensile strength over an order of magnitude higher than a control formulation with epoxidized soybean oil. More importantly, thermosetting materials ranging from soft elastomers to tough thermosets can be obtained simply by using different EPs and/or by controlling feed ratios of EPs to anhydrides. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning topological phases in the XMnSb2 system via chemical substitution from first principles

NASA Astrophysics Data System (ADS)

Griffin, Sinead M.; Neaton, Jeffrey B.

New Dirac materials are sought for their interesting fundamental physics and for their potential technological applications. Protected symmetries offer a route to potential zero mass Dirac and Weyl fermions, and can lead unique transport properties and spectroscopic signatures. In this work, we use first-principles calculations to study the XMnSb2 family of materials and show how varying X changes the nature of bulk protected topological features in their electronic structure. We further discuss new design rules for predicting new topological materials suggested by our calculations. SG is supported by the Early Postdoc Mobility Fellowship of the SNF.

Structure and dynamics of Earth's lower mantle.

PubMed

Garnero, Edward J; McNamara, Allen K

2008-05-02

Processes within the lowest several hundred kilometers of Earth's rocky mantle play a critical role in the evolution of the planet. Understanding Earth's lower mantle requires putting recent seismic and mineral physics discoveries into a self-consistent, geodynamically feasible context. Two nearly antipodal large low-shear-velocity provinces in the deep mantle likely represent chemically distinct and denser material. High-resolution seismological studies have revealed laterally varying seismic velocity discontinuities in the deepest few hundred kilometers, consistent with a phase transition from perovskite to post-perovskite. In the deepest tens of kilometers of the mantle, isolated pockets of ultralow seismic velocities may denote Earth's deepest magma chamber.

Substitution and diffusion of Cr 2+ and Cr 3+ in synthetic forsterite and natural olivine at 1200–1500 °C and 1 bar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jollands, M. C.; O'Neill, H. St. C.; Van Orman, J.

The diffusion and substitution mechanisms of Cr in forsterite were studied as a function of crystallographic orientation and the chemical potentials of all four components in the system MgO-SiO2-Cr-O. Oxygen fugacity (fO2) was varied over 15.4 log units at 1400 °C and was fixed at the iron-wüstite equilibrium for a temperature series (1200–1500 °C). The valence state changes of Cr along some diffusion profiles was also investigated using X-ray absorption near edge structure spectroscopy.

Role of the chemical substitution on the luminescence properties of solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} (0 ≤ x ≤1)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taoufyq, A.; Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir; CEA, DEN, Département d'Etudes des Réacteurs, Service de Physique Expérimentale, Laboratoire Dosimétrie Capteurs Instrumentation, 13108 Saint-Paul-lez-Durance

2015-10-15

Highlights: • Luminescence can be modified by chemical substitution in solid solutions Ca{sub 1−x}Cd{sub x}WO{sub 4}. • The various emission spectra (charge transfer) were obtained under X-ray excitation. • Scheelite or wolframite solid solutions presented two types of emission spectra. • A luminescence component depended on cadmium substitution in each solid solution. • A component was only characteristic of oxyanion symmetry in each solid solution. - Abstract: We have investigated the chemical substitution effects on the luminescence properties under X-ray excitation of the solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} with 0 ≤ x ≤ 1. Two types of wide spectralmore » bands, associated with scheelite-type or wolframite-type solid solutions, have been observed at room temperature. We decomposed each spectral band into several spectral components characterized by energies and intensities varying with composition x. One Gaussian component was characterized by an energy decreasing regularly with the composition x, while the other Gaussian component was only related to the tetrahedral or octahedral configurations of tungstate groups WO{sub 4}{sup 2−} or WO{sub 6}{sup 6−}. The luminescence intensities exhibited minimum values in the composition range x < 0.5 corresponding to scheelite-type structures, then, they regularly increased for cadmium compositions x > 0.5 corresponding to wolframite-type structures.« less

Effects of annealing on the optical, structural, and chemical properties of TiO2 and MgF2 thin films prepared by plasma ion-assisted deposition.

PubMed

Woo, Seouk-Hoon; Hwangbo, Chang Kwon

2006-03-01

Effects of thermal annealing at 400 degrees C on the optical, structural, and chemical properties of TiO2 single-layer, MgF2 single-layer, and TiO2/MgF2 narrow-bandpass filters deposited by conventional electron-beam evaporation (CE) and plasma ion-assisted deposition (PIAD) were investigated. In the case of TiO2 films, the results show that the annealing of both CE and PIAD TiO2 films increases the refractive index slightly and the extinction coefficient and surface roughness greatly. Annealing decreases the thickness of CE TiO2 films drastically, whereas it does not vary that of PIAD TiO2 films. For PIAD MgF2 films, annealing increases the refractive index and decreases the extinction coefficient drastically. An x-ray photoelectron spectroscopy analysis suggests that an increase in the refractive index and a decrease in the extinction coefficient for PIAD MgF2 films after annealing may be related to the enhanced concentration of MgO in the annealed PIAD MgF2 films and the changes in the chemical bonding states of Mg 2p, F 1s, and O is. It is found that (TiO2/MgF2) multilayer filters, consisting of PIAD TiO2 and CE MgF2 films, are as deposited without microcracks and are also thermally stable after annealing.

Measuring and predicting sooting tendencies of oxygenates, alkanes, alkenes, cycloalkanes, and aromatics on a unified scale

DOE PAGES

Das, Dhrubajyoti D.; St. John, Peter C.; McEnally, Charles S.; ...

2017-12-27

Databases of sooting indices, based on measuring some aspect of sooting behavior in a standardized combustion environment, are useful in providing information on the comparative sooting tendencies of different fuels or pure compounds. However, newer biofuels have varied chemical structures including both aromatic and oxygenated functional groups, which expands the chemical space of relevant compounds. In this work, we propose a unified sooting tendency database for pure compounds, including both regular and oxygenated hydrocarbons, which is based on combining two disparate databases of yield-based sooting tendency measurements in the literature. Unification of the different databases was made possible by leveragingmore » the greater dynamic range of the color ratio pyrometry soot diagnostic. This unified database contains a substantial number of pure compounds (≥ 400 total) from multiple categories of hydrocarbons important in modern fuels and establishes the sooting tendencies of aromatic and oxygenated hydrocarbons on the same numeric scale for the first time. Then, using this unified sooting tendency database, we have developed a predictive model for sooting behavior applicable to a broad range of hydrocarbons and oxygenated hydrocarbons. The model decomposes each compound into single-carbon fragments and assigns a sooting tendency contribution to each fragment based on regression against the unified database. The model’s predictive accuracy (as demonstrated by leave-one-out cross-validation) is comparable to a previously developed, more detailed predictive model. The fitted model provides insight into the effects of chemical structure on soot formation, and cases where its predictions fail reveal the presence of more complicated kinetic sooting mechanisms. Our work will therefore enable the rational design of low-sooting fuel blends from a wide range of feedstocks and chemical functionalities.« less

Molecular Studies of Complex Soil Organic Matter Interactions with Metal Ions and Mineral Surfaces using Classical Molecular Dynamics and Quantum Chemistry Methods

NASA Astrophysics Data System (ADS)

Andersen, A.; Govind, N.; Laskin, A.

2017-12-01

Mineral surfaces have been implicated as potential protectors of soil organic matter (SOM) against decomposition and ultimate mineralization to small molecules which can provide nutrients for plants and soil microbes and can also contribute to the Earth's elemental cycles. SOM is a complex mixture of organic molecules of biological origin at varying degrees of decomposition and can, itself, self-assemble in such a way as to expose some biomolecule types to biotic and abiotic attack while protecting other biomolecule types. The organization of SOM and SOM with mineral surfaces and solvated metal ions is driven by an interplay of van der Waals and electrostatic interactions leading to partitioning of hydrophilic (e.g. sugars) and hydrophobic (e.g., lipids) SOM components that can be bridged with amphiphilic molecules (e.g., proteins). Classical molecular dynamics simulations can shed light on assemblies of organic molecules alone or complexation with mineral surfaces. The role of chemical reactions is also an important consideration in potential chemical changes of the organic species such as oxidation/reduction, degradation, chemisorption to mineral surfaces, and complexation with solvated metal ions to form organometallic systems. For the study of chemical reactivity, quantum chemistry methods can be employed and combined with structural insight provided by classical MD simulations. Moreover, quantum chemistry can also simulate spectroscopic signatures based on chemical structure and is a valuable tool in interpreting spectra from, notably, x-ray absorption spectroscopy (XAS). In this presentation, we will discuss our classical MD and quantum chemistry findings on a model SOM system interacting with mineral surfaces and solvated metal ions.

Lethal Dietary Toxicities of Environmental Contaminants and Pesticides to Coturnix

USGS Publications Warehouse

Hill, E.F.; Camardese, M.B.

1986-01-01

Five-day subacute dietary toxicity tests of 193 potential environmental contaminants, pesticides, organic solvents, and various adjuvants are presented for young coturnix (Japanese quail, Coturnix japonica Temminck and Schlegel). The report provides the most comprehensive data base available for avian subacute dietary toxicity tests and is primarily intended for use in ranking toxicities by a standard method that has a reasonable degree of environmental relevance. Findings are presented in two parts: Part I is a critique of selected drugs that includes discussion of subacute toxicity in relation to chemical class and structure, pesticide formulation, and age of animals; Part II is a summary of toxicologic findings for each test substance and provides a statistically basis for comparing toxicities. Data presented include the median lethal concentration (LC50), slope of the probit regression curve (dose-response curve), response chronology, and food consumption. We observed that: 1) fewer than 15% of the compounds were classed 'very' or 'highly' toxic (i.e, LC50 < 200 ppm) and all of these were either chlorinated hydrocarbons, organophosphates, or organometallics; 2) subacute toxicity may vary widely among structurally similar chemicals and between different formulations of the same chemical; therefore, conclusions about lethal hazard must be made cautiously until the actual formulation of inset has been tested: 3) inclusion of a general standard in each battery of tests is useful for detection of atypical trials and monitoring population changes but should not be used indiscriminantly for adjusting LC50's for intertest differences unless the chemicals of concern and the standard elicit their toxicities through the same action; 4) although other species have been tested effectively under the subacute protocol, coturnix were ideal for the stated purpose of this research because they are inexpensive, well-adapted to the laboratory environment, and yield good intertest reproducibility of response.

Flame thickness and conditional scalar dissipation rate in a premixed temporal turbulent reacting jet

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaudhuri, Swetaprovo; Kolla, Hemanth; Dave, Himanshu L.

The flame structure corresponding to lean hydrogen–air premixed flames in intense sheared turbulence in the thin reaction zone regime is quantified from flame thickness and conditional scalar dissipation rate statistics, obtained from recent direct numerical simulation data of premixed temporally-evolving turbulent slot jet flames. It is found that, on average, these sheared turbulent flames are thinner than their corresponding planar laminar flames. Extensive analysis is performed to identify the reason for this counter-intuitive thinning effect. The factors controlling the flame thickness are analyzed through two different routes i.e., the kinematic route, and the transport and chemical kinetics route. The kinematicmore » route is examined by comparing the statistics of the normal strain rate due to fluid motion with the statistics of the normal strain rate due to varying flame displacement speed or self-propagation. It is found that while the fluid normal straining is positive and tends to separate iso-scalar surfaces, the dominating normal strain rate due to self-propagation is negative and tends to bring the iso-scalar surfaces closer resulting in overall thinning of the flame. The transport and chemical kinetics route is examined by studying the non-unity Lewis number effect on the premixed flames. The effects from the kinematic route are found to couple with the transport and chemical kinetics route. In addition, the intermittency of the conditional scalar dissipation rate is also examined. It is found to exhibit a unique non-monotonicity of the exponent of the stretched exponential function, conventionally used to describe probability density function tails of such variables. As a result, the non-monotonicity is attributed to the detailed chemical structure of hydrogen-air flames in which heat release occurs close to the unburnt reactants at near free-stream temperatures.« less

Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth''s Atmosphere

NASA Technical Reports Server (NTRS)

Salby, Murry

1998-01-01

A 3-dimensional model was developed to support mechanistic studies. The model solves the global primitive equations in isentropic coordinates, which directly characterize diabatic processes forcing the Brewer-Dobson circulation of the middle atmosphere. It's numerical formulation is based on Hough harmonics, which partition horizontal motion into its rotational and divergent components. These computational features, along with others, enable 3D integrations to be performed practically on RISC computer architecture, on which they can be iterated to support mechanistic studies. The model conserves potential vorticity quite accurately under adiabatic conditions. Forced by observed tropospheric structure, in which integrations are anchored, the model generates a diabatic circulation that is consistent with satellite observations of tracer behavior and diabatic cooling rates. The model includes a basic but fairly complete treatment of gas-phase photochemistry that represents some 20 chemical species and 50 governing reactions with diurnally-varying shortwave absorption. The model thus provides a reliable framework to study transport and underlying diabatic processes, which can then be compared against chemical and dynamical structure observed and in GCM integrations. Integrations with the Langley GCM were performed to diagnose feedback between simulated convection and the tropical circulation. These were studied in relation to tropospheric properties controlling moisture convergence and environmental conditions supporting deep convection, for comparison against mechanistic integrations of wave CISK that successfully reproduce the Madden-Julian Oscillation (MJO) of the tropical circulation. These comparisons were aimed at identifying and ultimately improving aspects of the convective simulation, with the objective of recovering a successful simulation of the MJO in the Langley GCM, behavior that should be important to budgets of upper-tropospheric water vapor and chemical species.

Flame thickness and conditional scalar dissipation rate in a premixed temporal turbulent reacting jet

DOE PAGES

Chaudhuri, Swetaprovo; Kolla, Hemanth; Dave, Himanshu L.; ...

2017-07-07

The flame structure corresponding to lean hydrogen–air premixed flames in intense sheared turbulence in the thin reaction zone regime is quantified from flame thickness and conditional scalar dissipation rate statistics, obtained from recent direct numerical simulation data of premixed temporally-evolving turbulent slot jet flames. It is found that, on average, these sheared turbulent flames are thinner than their corresponding planar laminar flames. Extensive analysis is performed to identify the reason for this counter-intuitive thinning effect. The factors controlling the flame thickness are analyzed through two different routes i.e., the kinematic route, and the transport and chemical kinetics route. The kinematicmore » route is examined by comparing the statistics of the normal strain rate due to fluid motion with the statistics of the normal strain rate due to varying flame displacement speed or self-propagation. It is found that while the fluid normal straining is positive and tends to separate iso-scalar surfaces, the dominating normal strain rate due to self-propagation is negative and tends to bring the iso-scalar surfaces closer resulting in overall thinning of the flame. The transport and chemical kinetics route is examined by studying the non-unity Lewis number effect on the premixed flames. The effects from the kinematic route are found to couple with the transport and chemical kinetics route. In addition, the intermittency of the conditional scalar dissipation rate is also examined. It is found to exhibit a unique non-monotonicity of the exponent of the stretched exponential function, conventionally used to describe probability density function tails of such variables. As a result, the non-monotonicity is attributed to the detailed chemical structure of hydrogen-air flames in which heat release occurs close to the unburnt reactants at near free-stream temperatures.« less

Measuring and predicting sooting tendencies of oxygenates, alkanes, alkenes, cycloalkanes, and aromatics on a unified scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Dhrubajyoti D.; St. John, Peter C.; McEnally, Charles S.

Databases of sooting indices, based on measuring some aspect of sooting behavior in a standardized combustion environment, are useful in providing information on the comparative sooting tendencies of different fuels or pure compounds. However, newer biofuels have varied chemical structures including both aromatic and oxygenated functional groups, which expands the chemical space of relevant compounds. In this work, we propose a unified sooting tendency database for pure compounds, including both regular and oxygenated hydrocarbons, which is based on combining two disparate databases of yield-based sooting tendency measurements in the literature. Unification of the different databases was made possible by leveragingmore » the greater dynamic range of the color ratio pyrometry soot diagnostic. This unified database contains a substantial number of pure compounds (≥ 400 total) from multiple categories of hydrocarbons important in modern fuels and establishes the sooting tendencies of aromatic and oxygenated hydrocarbons on the same numeric scale for the first time. Then, using this unified sooting tendency database, we have developed a predictive model for sooting behavior applicable to a broad range of hydrocarbons and oxygenated hydrocarbons. The model decomposes each compound into single-carbon fragments and assigns a sooting tendency contribution to each fragment based on regression against the unified database. The model’s predictive accuracy (as demonstrated by leave-one-out cross-validation) is comparable to a previously developed, more detailed predictive model. The fitted model provides insight into the effects of chemical structure on soot formation, and cases where its predictions fail reveal the presence of more complicated kinetic sooting mechanisms. Our work will therefore enable the rational design of low-sooting fuel blends from a wide range of feedstocks and chemical functionalities.« less

Systematic evaluation and optimization of modification reactions of oligonucleotides with amines and carboxylic acids for the synthesis of DNA-encoded chemical libraries.

PubMed

Franzini, Raphael M; Samain, Florent; Abd Elrahman, Maaly; Mikutis, Gediminas; Nauer, Angela; Zimmermann, Mauro; Scheuermann, Jörg; Hall, Jonathan; Neri, Dario

2014-08-20

DNA-encoded chemical libraries are collections of small molecules, attached to DNA fragments serving as identification barcodes, which can be screened against multiple protein targets, thus facilitating the drug discovery process. The preparation of large DNA-encoded chemical libraries crucially depends on the availability of robust synthetic methods, which enable the efficient conjugation to oligonucleotides of structurally diverse building blocks, sharing a common reactive group. Reactions of DNA derivatives with amines and/or carboxylic acids are particularly attractive for the synthesis of encoded libraries, in view of the very large number of building blocks that are commercially available. However, systematic studies on these reactions in the presence of DNA have not been reported so far. We first investigated conditions for the coupling of primary amines to oligonucleotides, using either a nucleophilic attack on chloroacetamide derivatives or a reductive amination on aldehyde-modified DNA. While both methods could be used for the production of secondary amines, the reductive amination approach was generally associated with higher yields and better purity. In a second endeavor, we optimized conditions for the coupling of a diverse set of 501 carboxylic acids to DNA derivatives, carrying primary and secondary amine functions. The coupling efficiency was generally higher for primary amines, compared to secondary amine substituents, but varied considerably depending on the structure of the acids and on the synthetic methods used. Optimal reaction conditions could be found for certain sets of compounds (with conversions >80%), but multiple reaction schemes are needed when assembling large libraries with highly diverse building blocks. The reactions and experimental conditions presented in this article should facilitate the synthesis of future DNA-encoded chemical libraries, while outlining the synthetic challenges that remain to be overcome.

Micromechanical Structures Fabrication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajic, S

2001-05-08

Work in materials other than silicon for MEMS applications has typically been restricted to metals and metal oxides instead of more ''exotic'' semiconductors. However, group III-V and II-VI semiconductors form a very important and versatile collection of material and electronic parameters available to the MEMS and MOEMS designer. With these materials, not only are the traditional mechanical material variables (thermal conductivity, thermal expansion, Young's modulus, etc.) available, but also chemical constituents can be varied in ternary and quaternary materials. This flexibility can be extremely important for both friction and chemical compatibility issues for MEMS. In addition, the ability to continuallymore » vary the bandgap energy can be particularly useful for many electronics and infrared detection applications. However, there are two major obstacles associated with alternate semiconductor material MEMS. The first issue is the actual fabrication of non-silicon micro-devices and the second impediment is communicating with these novel devices. We have implemented an essentially material independent fabrication method that is amenable to most group III-V and II-VI semiconductors. This technique uses a combination of non-traditional direct write precision fabrication processes such as diamond turning, ion milling, laser ablation, etc. This type of deterministic fabrication approach lends itself to an almost trivial assembly process. We also implemented a mechanical, electrical, and optical self-aligning hybridization technique for these alternate-material MEMS substrates.« less

From amorphous to nanocrystalline: the effect of nanograins in amorphous matrix on the thermal conductivity of hot-wire chemical-vapor deposited silicon films

DOE PAGES

Kearney, B. T.; Jugdersuren, B.; Queen, D. R.; ...

2017-12-28

Here, we have measured the thermal conductivity of amorphous and nanocrystalline silicon films with varying crystalline content from 85K to room temperature. The films were prepared by the hot-wire chemical-vapor deposition, where the crystalline volume fraction is determined by the hydrogen (H2) dilution ratio to the processing silane gas (SiH4), R=H2/SiH4. We varied R from 1 to 10, where the films transform from amorphous for R < 3 to mostly nanocrystalline for larger R. Structural analyses show that the nanograins, averaging from 2 to 9nm in sizes with increasing R, are dispersed in the amorphous matrix. The crystalline volume fractionmore » increases from 0 to 65% as R increases from 1 to 10. The thermal conductivities of the two amorphous silicon films are similar and consistent with the most previous reports with thicknesses no larger than a few um deposited by a variety of techniques. The thermal conductivities of the three nanocrystalline silicon films are also similar, but are about 50-70% higher than those of their amorphous counterparts. The heat conduction in nanocrystalline silicon films can be understood as the combined contribution in both amorphous and nanocrystalline phases, where increased conduction through improved nanocrystalline percolation path outweighs increased interface scattering between silicon nanocrystals and the amorphous matrix.« less

From amorphous to nanocrystalline: the effect of nanograins in amorphous matrix on the thermal conductivity of hot-wire chemical-vapor deposited silicon films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kearney, B. T.; Jugdersuren, B.; Queen, D. R.

Here, we have measured the thermal conductivity of amorphous and nanocrystalline silicon films with varying crystalline content from 85K to room temperature. The films were prepared by the hot-wire chemical-vapor deposition, where the crystalline volume fraction is determined by the hydrogen (H2) dilution ratio to the processing silane gas (SiH4), R=H2/SiH4. We varied R from 1 to 10, where the films transform from amorphous for R < 3 to mostly nanocrystalline for larger R. Structural analyses show that the nanograins, averaging from 2 to 9nm in sizes with increasing R, are dispersed in the amorphous matrix. The crystalline volume fractionmore » increases from 0 to 65% as R increases from 1 to 10. The thermal conductivities of the two amorphous silicon films are similar and consistent with the most previous reports with thicknesses no larger than a few um deposited by a variety of techniques. The thermal conductivities of the three nanocrystalline silicon films are also similar, but are about 50-70% higher than those of their amorphous counterparts. The heat conduction in nanocrystalline silicon films can be understood as the combined contribution in both amorphous and nanocrystalline phases, where increased conduction through improved nanocrystalline percolation path outweighs increased interface scattering between silicon nanocrystals and the amorphous matrix.« less

Control of the shape and size of iron oxide (α-Fe2O3) nanoparticles synthesized through the chemical precipitation method

NASA Astrophysics Data System (ADS)

Lassoued, Abdelmajid; Dkhil, Brahim; Gadri, Abdellatif; Ammar, Salah

Hematite (α-Fe2O3) nanoparticles were synthesized via a simple chemical precipitation method. The impact of varying the concentration of precursor on the crystalline phase, size and morphology of α-Fe2O3 products was explored. The characteristic of the synthesized hematite nanoparticles were evaluated by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Fourier Transform Infra-Red (FT-IR) spectroscopy, Raman spectroscopy, Differential Thermal Analysis (DTA), Thermo Gravimetric Analysis (TGA), Ultraviolet-Visible (UV-Vis) analysis and Photoluminescence (PL). XRD data revealed a rhombohedral (hexagonal) structure with the space group R-3c in all samples. Uniform spherical like morphology was confirmed by TEM and SEM. The result revealed that the particle sizes were varied between 21 and 82 nm and that the increase in precursor concentration (FeCl3, 6H2O) is accompanied by an increase in the particle size of 21 nm for pure α-Fe2O3 synthesized with [Fe3+] = 0.05 M at 82 nm for pure α-Fe2O3 synthesized with [Fe3+] = 0.4 M. FT-IR confirms the phase purity of the nanoparticles synthesized. The Raman spectroscopy was used not only to prove that we have synthesized pure hematite but also to identify their phonon modes. The thermal behavior of compound was studied by using TGA/DTA results: The TGA showed three mass losses, whereas DTA resulted in three endothermic peaks. Besides, the optical investigation revealed that samples have an optical gap of about 2.1 eV and that this value varies as a function of the precursor concentration.

Endocrine-Disrupting Compounds in Aquatic Ecosystems.

EPA Science Inventory

Endocrine disrupting chemicals (EDCs) are a ubiquitous issue of concern in our aquatic systems. Commonly detected EDCs include natural and synthetic hormones, surfactants, plasticizers, disinfectants, herbicides and metals. The potency of these chemicals varies substantially, as ...

Protein structure refinement using a quantum mechanics-based chemical shielding predictor† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04344e Click here for additional data file.

PubMed Central

2017-01-01

The accurate prediction of protein chemical shifts using a quantum mechanics (QM)-based method has been the subject of intense research for more than 20 years but so far empirical methods for chemical shift prediction have proven more accurate. In this paper we show that a QM-based predictor of a protein backbone and CB chemical shifts (ProCS15, PeerJ, 2016, 3, e1344) is of comparable accuracy to empirical chemical shift predictors after chemical shift-based structural refinement that removes small structural errors. We present a method by which quantum chemistry based predictions of isotropic chemical shielding values (ProCS15) can be used to refine protein structures using Markov Chain Monte Carlo (MCMC) simulations, relating the chemical shielding values to the experimental chemical shifts probabilistically. Two kinds of MCMC structural refinement simulations were performed using force field geometry optimized X-ray structures as starting points: simulated annealing of the starting structure and constant temperature MCMC simulation followed by simulated annealing of a representative ensemble structure. Annealing of the CHARMM structure changes the CA-RMSD by an average of 0.4 Å but lowers the chemical shift RMSD by 1.0 and 0.7 ppm for CA and N. Conformational averaging has a relatively small effect (0.1–0.2 ppm) on the overall agreement with carbon chemical shifts but lowers the error for nitrogen chemical shifts by 0.4 ppm. If an amino acid specific offset is included the ProCS15 predicted chemical shifts have RMSD values relative to experiments that are comparable to popular empirical chemical shift predictors. The annealed representative ensemble structures differ in CA-RMSD relative to the initial structures by an average of 2.0 Å, with >2.0 Å difference for six proteins. In four of the cases, the largest structural differences arise in structurally flexible regions of the protein as determined by NMR, and in the remaining two cases, the large structural change may be due to force field deficiencies. The overall accuracy of the empirical methods are slightly improved by annealing the CHARMM structure with ProCS15, which may suggest that the minor structural changes introduced by ProCS15-based annealing improves the accuracy of the protein structures. Having established that QM-based chemical shift prediction can deliver the same accuracy as empirical shift predictors we hope this can help increase the accuracy of related approaches such as QM/MM or linear scaling approaches or interpreting protein structural dynamics from QM-derived chemical shift. PMID:28451325

A novel technique to measure interface trap density in a GaAs MOS capacitor using time-varying magnetic fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhury, Aditya N. Roy, E-mail: aditya@physics.iisc.ernet.in; Venkataraman, V.

Interface trap density (D{sub it}) in a GaAs metal-oxide-semiconductor (MOS) capacitor can be measured electrically by measuring its impedance, i.e. by exciting it with a small signal voltage source and measuring the resulting current through the circuit. We propose a new method of measuring D{sub it} where the MOS capacitor is subjected to a (time-varying) magnetic field instead, which produces an effect equivalent to a (time-varying) voltage drop across the sample. This happens because the electron chemical potential of GaAs changes with a change in an externally applied magnetic field (unlike that of the gate metal); this is not themore » voltage induced by Faraday’s law of electromagnetic induction. So, by measuring the current through the MOS, D{sub it} can be found similarly. Energy band diagrams and equivalent circuits of a MOS capacitor are drawn in the presence of a magnetic field, and analyzed. The way in which a magnetic field affects a MOS structure is shown to be fundamentally different compared to an electrical voltage source.« less

The role of soil communities in improving ecosystem services in organic farming

NASA Astrophysics Data System (ADS)

Zandbergen, Jelmer; Koorneef, Guusje; Veen, Cees; Schrama, Jan; van der Putten, Wim

2017-04-01

Worldwide soil fertility decreases and it is generally believed that organic matter (OM) addition to agricultural soils can improve soil properties leading to beneficial ecosystem services. However, it remains unknown under which conditions and how fast biotic, physical and chemical soil properties respond to varying quality and quantity of OM inputs. Therefore, the aims of this research project are (1) to unravel biotic, physical and chemical responses of soils to varying quantity and quality of OM addition; and (2) to understand how we can accelerate the response of soils in order to improve beneficial soil ecosystem services faster. The first step in our research project is to determine how small-scale spatio-temporal patterns in soil biotic, physical and chemical properties relate to crop production and quality. To do this we combine field measurements on soil properties with remote and proximate sensing measures on crop development and yield in a long-term farming systems experiment in the Netherlands (Vredepeel). We hypothesize that spatio-temporal variation in crop development and yield are strongly related to spatio-temporal variation in soil parameters. In the second step of our project we will use this information to identify biological interactions underlying improving soil functions in response to OM addition over time. We will specifically focus on the role of soil communities in driving nutrient cycling, disease suppression and the formation of soil structure, all crucial elements of key soil services in agricultural soils. The knowledge that will be generated in our project can be used to detect specific organic matter qualities that support the underlying ecological processes to accelerate the transition towards improved soil functioning thereby governing enhanced crop yields.

Chemical reactions induced by oscillating external fields in weak thermal environments

NASA Astrophysics Data System (ADS)

Craven, Galen T.; Bartsch, Thomas; Hernandez, Rigoberto

2015-02-01

Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates predicted by stability analysis and rates obtained through numerical calculation of the reactive flux. We also show that the optimal dividing surface and the resulting reaction rate for a reactive system driven by weak thermal noise can be approximated well using the transition state geometry of the underlying deterministic system. This agreement persists as long as the thermal driving strength is less than the order of that of the periodic driving. The power of this result is its simplicity. The surprising accuracy of the time-dependent noise-free geometry for obtaining transition state theory rates in chemical reactions driven by periodic fields reveals the dynamics without requiring the cost of brute-force calculations.

The structure, surface topography and mechanical properties of Si-C-N films fabricated by RF and DC magnetron sputtering

NASA Astrophysics Data System (ADS)

Shi, Zhifeng; Wang, Yingjun; Du, Chang; Huang, Nan; Wang, Lin; Ning, Chengyun

2011-12-01

Silicon carbon nitride thin films were deposited on Co-Cr alloy under varying deposition conditions such as sputtering power and the partial pressure ratio of N2 to Ar by radio frequency and direct current magnetron sputtering techniques. The chemical bonding configurations, surface topography and hardness were characterized by means of X-ray photoelectron spectroscopy, atomic force microscopy and nano-indentation technique. The sputtering power exhibited important influence on the film composition, chemical bonding configurations and surface topography, the electro-negativity had primary effects on chemical bonding configurations at low sputtering power. A progressive densification of the film microstructure occurring with the carbon fraction was increased. The films prepared by RF magnetron sputtering, the relative content of the Si-N bond in the films increased with the sputtering power increased, and Si-C and Si-Si were easily detachable, and C-O, N-N and N-O on the film volatile by ion bombardment which takes place very frequently during the film formation process. With the increase of sputtering power, the films became smoother and with finer particle growth. The hardness varied between 6 GPa and 11.23 GPa depending on the partial pressure ratio of N2 to Ar. The tribological characterization of Co-Cr alloy with Si-C-N coating sliding against UHMWPE counter-surface in fetal bovine serum, shows that the wear resistance of the Si-C-N coated Co-Cr alloy/UHMWPE sliding pair show much favourable improvement over that of uncoated Co-Cr alloy/UHMWPE sliding pair. This study is important for the development of advanced coatings with tailored mechanical and tribological properties.

The HIFI spectral survey of AFGL 2591 (CHESS). III. Chemical structure of the protostellar envelope

NASA Astrophysics Data System (ADS)

Kaźmierczak-Barthel, M.; Semenov, D. A.; van der Tak, F. F. S.; Chavarría, L.; van der Wiel, M. H. D.

2015-02-01

Aims: The aim of this work is to understand the richness of chemical species observed in the isolated high-mass envelope of AFGL 2591, a prototypical object for studying massive star formation. Methods: Based on HIFI and JCMT data, the molecular abundances of species found in the protostellar envelope of AFGL 2591 were derived with a Monte Carlo radiative transfer code (Ratran), assuming a mixture of constant and 1D stepwise radial profiles for abundance distributions. The reconstructed 1D abundances were compared with the results of the time-dependent gas-grain chemical modeling, using the best-fit 1D power-law density structure. The chemical simulations were performed considering ages of 1-5 × 104 years, cosmic ray ionization rates of 5-500 × 10-17 s-1, uniformly-sized 0.1-1 μm dust grains, a dust/gas ratio of 1%, and several sets of initial molecular abundances with C/O < 1 and >1. The most important model parameters varied one by one in the simulations are age, cosmic ray ionization rate, external UV intensity, and grain size. Results: Constant abundance models give good fits to the data for CO, CN, CS, HCO+, H2CO, N2H+, CCH, NO, OCS, OH, H2CS, O, C, C+, and CH. Models with an abundance jump at 100 K give good fits to the data for NH3, SO, SO2, H2S, H2O, HCl, and CH3OH. For HCN and HNC, the best models have an abundance jump at 230 K. The time-dependent chemical model can accurately explain abundance profiles of 15 out of these 24 species. The jump-like radial profiles for key species like HCO+, NH3, and H2O are consistent with the outcome of the time-dependent chemical modeling. The best-fit model has a chemical age of ~10-50 kyr, a solar C/O ratio of 0.44, and a cosmic-ray ionization rate of ~5 × 10-17 s-1. The grain properties and the intensity of the external UV field do not strongly affect the chemical structure of the AFGL 2591 envelope, whereas its chemical age, the cosmic-ray ionization rate, and the initial abundances play an important role. Conclusions: We demonstrate that simple constant or jump-like abundance profiles constrained with 1D Ratran line radiative transfer simulations are in agreement with time-dependent chemical modeling for most key C-, O-, N-, and S-bearing molecules. The main exceptions are species with very few observed transitions (C, O, C+, and CH) or with a poorly established chemical network (HCl, H2S) or whose chemistry is strongly affected by surface processes (CH3OH). Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Investigating melting induced mantle heterogeneities in plate driven mantle convection models

NASA Astrophysics Data System (ADS)

Price, M.; Davies, H.; Panton, J.

2017-12-01

Observations from geochemistry and seismology continue to suggest a range of complex heterogeneity in Earth's mantle. In the deep mantle, two large low velocity provinces (LLVPs) have been regularly observed in seismic studies, with their longevity, composition and density compared to the surrounding mantle debated. The cause of these observed LLVPs is equally uncertain, with previous studies advocating either thermal or thermo-chemical causes. There is also evidence that these structures could provide chemically distinct reservoirs within the mantle, with recent studies also suggesting there may be additional reservoirs in the mantle, such as bridgmanite-enriched ancient mantle structures (BEAMS). One way to test these hypotheses is using computational models of the mantle, with models that capture the full 3D system being both complex and computationally expensive. Here we present results from our global mantle model TERRA. Using our model, we can track compositional variations in the convecting mantle that are generated by self-consistent, evolving melting zones. Alongside the melting, we track trace elements and other volatiles which can be partitioned during melting events, and expelled and recycled at the surface. Utilising plate reconstruction models as a boundary condition, the models generate the tectonic features observed at Earth's surface, while also organising the lower mantle into recognisable degree-two structures. This results in our models generating basaltic `oceanic' crusts which are then brought into the mantle at tectonic boundaries, providing additional chemical heterogeneity in the mantle volume. Finally, by utilising thermodynamic lookup tables to convert the final outputs from the model to seismic structures, together with resolution filters for global tomography models, we are able to make direct comparisons between our results and observations. By varying the parameters of the model, we investigate a range of current hypotheses for heterogeneity in the mantle. Our work attempts to reconcile the many proposed current ideas for the deep mantle, giving additional insight from modelling on the latest observations from other Deep Earth disciplines.

CHEMICAL STRUCTURE INDEXING OF TOXICITY DATA ON ...

EPA Pesticide Factsheets

Standardized chemical structure annotation of public toxicity databases and information resources is playing an increasingly important role in the 'flattening' and integration of diverse sets of biological activity data on the Internet. This review discusses public initiatives that are accelerating the pace of this transformation, with particular reference to toxicology-related chemical information. Chemical content annotators, structure locator services, large structure/data aggregator web sites, structure browsers, International Union of Pure and Applied Chemistry (IUPAC) International Chemical Identifier (InChI) codes, toxicity data models and public chemical/biological activity profiling initiatives are all playing a role in overcoming barriers to the integration of toxicity data, and are bringing researchers closer to the reality of a mineable chemical Semantic Web. An example of this integration of data is provided by the collaboration among researchers involved with the Distributed Structure-Searchable Toxicity (DSSTox) project, the Carcinogenic Potency Project, projects at the National Cancer Institute and the PubChem database. Standardizing chemical structure annotation of public toxicity databases

Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Ohsumi, Kazumasa; Mikouchi, Takashi; Hagiya, Kenji; Le, Loan

2008-01-01

The main long-term goal of this research is to understand the physical conditions in the early solar nebula through the detailed characterization of a key class of mineral present in all primitive materials: Fe-Ni sulfides [1&2]. Fe-Ni sulfides can take dozens of structures, depending on the temperature of formation, as well as other physico-chemical factors which are imperfectly understood. Add to this the additional varying factor of Ni content, and we have a potentially sensitive cosmothermometer [3]. Unfortunately, this tool requires exact knowledge of the crystal structure of each grain being considered, and there have been few (none?) studies of the detailed structures of sulfides in chondritic materials. We report here on coordinated compositional and crystallographic investigation of Fe-Ni sulfides in diverse carbonaceous chondrites, initially Acfer 094 (the most primitive CM2 [4]) Tagish Lake (a unique type C2 [5]), a C1 lithology in Kaidun [6], Bali (oxidized CV3 [7]), and Efremovka (reduced CV3 [7]).

Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide.

PubMed

Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J; Schlom, Darrell G; Alem, Nasim; Gopalan, Venkatraman

2016-08-31

Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

PubMed Central

Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

2016-01-01

Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden–Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure. PMID:27578622

Direct Electrospray Printing of Gradient Refractive Index Chalcogenide Glass Films.

PubMed

Novak, Spencer; Lin, Pao Tai; Li, Cheng; Lumdee, Chatdanai; Hu, Juejun; Agarwal, Anuradha; Kik, Pieter G; Deng, Weiwei; Richardson, Kathleen

2017-08-16

A spatially varying effective refractive index gradient using chalcogenide glass layers is printed on a silicon wafer using an optimized electrospray (ES) deposition process. Using solution-derived glass precursors, IR-transparent Ge 23 Sb 7 S 70 and As 40 S 60 glass films of programmed thickness are fabricated to yield a bilayer structure, resulting in an effective gradient refractive index (GRIN) film. Optical and compositional analysis tools confirm the optical and physical nature of the gradient in the resulting high-optical-quality films, demonstrating the power of direct printing of multimaterial structures compatible with planar photonic fabrication protocols. The potential application of such tailorable materials and structures as they relate to the enhancement of sensitivity in chalcogenide glass based planar chemical sensor device design is presented. This method, applicable to a broad cross section of glass compositions, shows promise in directly depositing GRIN films with tunable refractive index profiles for bulk and planar optical components and devices.

Structural features of dilute acid, steam exploded, and alkali pretreated mustard stalk and their impact on enzymatic hydrolysis.

PubMed

Kapoor, Manali; Raj, Tirath; Vijayaraj, M; Chopra, Anju; Gupta, Ravi P; Tuli, Deepak K; Kumar, Ravindra

2015-06-25

To overcome the recalcitrant nature of biomass several pretreatment methodologies have been explored to make it amenable to enzymatic hydrolysis. These methodologies alter cell wall structure primarily by removing/altering hemicelluloses and lignin. In this work, alkali, dilute acid, steam explosion pretreatment are systematically studied for mustard stalk. To assess the structural variability after pretreatment, chemical analysis, surface area, crystallinity index, accessibility of cellulose, FT-IR and thermal analysis are conducted. Although the extent of enzymatic hydrolysis varies upon the methodologies used, nevertheless, cellulose conversion increases from <10% to 81% after pretreatment. Glucose yield at 2 and 72h are well correlated with surface area and maximum adsorption capacity. However, no such relationship is observed for xylose yield. Mass balance of the process is also studied. Dilute acid pretreatment is the best methodology in terms of maximum sugar yield at lower enzyme loading. Copyright © 2015 Elsevier Ltd. All rights reserved.

Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide

NASA Astrophysics Data System (ADS)

Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

2016-08-01

Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

Temperature-Dependent Magnetic Response of Antiferromagnetic Doping in Cobalt Ferrite Nanostructures.

PubMed

Nairan, Adeela; Khan, Maaz; Khan, Usman; Iqbal, Munawar; Riaz, Saira; Naseem, Shahzad

2016-04-18

In this work Mn x Co 1- x Fe₂O₄ nanoparticles (NPs) were synthesized using a chemical co-precipitation method. Phase purity and structural analyses of synthesized NPs were performed by X-ray diffractometer (XRD). Transmission electron microscopy (TEM) reveals the presence of highly crystalline and narrowly-dispersed NPs with average diameter of 14 nm. The Fourier transform infrared (FTIR) spectrum was measured in the range of 400-4000 cm -1 which confirmed the formation of vibrational frequency bands associated with the entire spinel structure. Temperature-dependent magnetic properties in anti-ferromagnet (AFM) and ferromagnet (FM) structure were investigated with the aid of a physical property measurement system (PPMS). It was observed that magnetic interactions between the AFM (Mn) and FM (CoFe₂O₄) material arise below the Neel temperature of the dopant. Furthermore, hysteresis response was clearly pronounced for the enhancement in magnetic parameters by varying temperature towards absolute zero. It is shown that magnetic properties have been tuned as a function of temperature and an externally-applied field.

A multilayered supramolecular self-assembled structure from soybean oil by in situ polymerization and its applications.

PubMed

Kavitha, Varadharajan; Gnanamani, Arumugam

2013-05-01

The present study emphasizes in situ transformation of soybean oil to self-assembled supramolecular multilayered biopolymer material. The said polymer material was characterized and the entrapment efficacy of both hydrophilic and hydrophobic moieties was studied. In brief, soybean oil at varying concentration was mixed with mineral medium and incubated under agitation (200 rpm) at 37 degrees C for 240 h. Physical observations were made till 240 h and the transformed biopolymer was separated and subjected to physical, chemical and functional characterization. The maximum size of the polymer material was measured as 2 cm in diameter and the cross sectional view displayed the multilayered onion rings like structures. SEM analysis illustrated the presence of multilayered honeycomb channeled structures. Thermal analysis demonstrated the thermal stability (200 degrees C) and high heat enthalpy (1999 J/g). Further, this multilayered assembly was able to entrap both hydrophilic and hydrophobic components simultaneously, suggesting the potential industrial application of this material.

Effect of aluminum contents on sputter deposited CrAlN thin films

NASA Astrophysics Data System (ADS)

Vyas, A.; Zhou, Z. F.; Shen, Y. G.

2018-02-01

Pure CrN and CrAlN films with varied Al concentrations were prepared onto Si(100) substrates by an unbalanced reactive dc-magnetron sputtering system. The crystal structure, chemical states, and microstructure of the films were characterized by X-ray diffraction, X-ray photoelectron microscopy, transmission electron microscopy whereas mechanical properties were determined by nano-indentation measurements. XRD results showed a prominent (200) reflection in both CrN and CrAlN films. Results demonstrate that CrAlN films formed a solid solution and doping of Al atoms replace the Cr atoms affecting the lattice parameter and crystallization of the films. All Al doped films were of B1 NaCl-type structure, demonstrating that CrAlN films primarily crystallized in cubic structure. Microstructural investigation by TEM for a CrAlN film containing Al content of 24.1 at.%, revealed that there exists an amorphous/nanocrystalline domains (grains of about ∼ 11 nm) and hardness increases 22% when compared with pure CrN film.

Boron-doped few-walled carbon nanotubes: novel synthesis and properties

NASA Astrophysics Data System (ADS)

Preston, Colin; Song, Da; Taillon, Josh; Cumings, John; Hu, Liangbing

2016-11-01

Few-walled carbon nanotubes offer a unique marriage of graphitic quality and robustness to ink-processing; however, doping procedures that may alter the band structure of these few-walled nanotubes are still lacking. This report introduces a novel solution-injected chemical vapor deposition growth process to fabricate the first boron-doped few-walled carbon nanotubes (B-FWNTs) reported in literature, which may have extensive applications in battery devices. A comprehensive characterization of the as-grown B-FWNTs confirms successful boron substitution in the graphitic lattice, and reveals varying growth parameters impact the structural properties of B-FWNT yield. An investigation into the optimal growth purification parameters and ink-making procedures was also conducted. This study introduces the first process technique to successfully grow intrinsically p-doped FWNTs, and provides the first investigation into the impact factors of the growth parameters, purification steps, and ink-making processes on the structural properties of the B-FWNTs and the electrical properties of the resulting spray-coated thin-film electrodes.

Computational Study of Field Initiated Surface Reactions for Synthesis of Diamond and Silicon

NASA Technical Reports Server (NTRS)

Musgrave, Charles Bruce

1999-01-01

This project involves using quantum chemistry to simulate surface chemical reactions in the presence of an electric field for nanofabrication of diamond and silicon. A field delivered by a scanning tunneling microscope (STM) to a nanometer scale region of a surface affects chemical reaction potential energy surfaces (PES) to direct atomic scale surface modification to fabricate sub-nanometer structures. Our original hypothesis is that the applied voltage polarizes the charge distribution of the valence electrons and that these distorted molecular orbitals can be manipulated with the STM so as to change the relative stabilities of the electronic configurations over the reaction coordinates and thus the topology of the PES and reaction kinetics. Our objective is to investigate the effect of applied bias on surface reactions and the extent to which STM delivered fields can be used to direct surface chemical reactions on an atomic scale on diamond and silicon. To analyze the fundamentals of field induced chemistry and to investigate the application of this technique for the fabrication of nanostructures, we have employed methods capable of accurately describing molecular electronic structure. The methods we employ are density functional theory (DFT) quantum chemical (QC) methods. To determine the effect of applied bias on surface reactions we have calculated the QC PESs in various applied external fields for various reaction steps for depositing or etching diamond and silicon. We have chosen reactions which are thought to play a role in etching and the chemical vapor deposition growth of Si and diamond. The PESs of the elementary reaction steps involved are then calculated under the applied fields, which we vary in magnitude and configuration. We pay special attention to the change in the reaction barriers, and transition state locations, and search for low energy reaction channels which were inaccessible without the applied bias.

Effect of RF power and annealing on chemical bonding and morphology of a-CN{sub x} thin films as humidity sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aziz, N. F. H; Hussain, N. S. Mohamed; Awang, R.

2013-11-27

Amorphous carbon nitride (a-CN{sub x}) thin films were deposited using radio frequency plasma enhanced chemical vapor deposition (rf-PECVD) technique. A set of a-CN{sub x} thin films were prepared using pure methane (CH{sub 4}) gas diluted with nitrogen (N{sub 2}) gas. The rf power was varied at 50, 60, 70, 80, 90 and 100 W. These films were then annealed at 400 °C in a quartz tube furnace in argon (Ar) gas. The effects of rf power and thermal annealing on the chemical bonding and morphology of these samples were studied. Surface profilometer was used to measure film thickness. Fourier transformmore » infra-red spectroscopy (FTIR) and Field emission scanning electron microscopy (FESEM) measurements were used to determine their chemical bonding and morphology respectively. The deposition rate of the films increased constantly with increasing rf power up to 80W, before decreasing with further increase in rf power. Fourier transform infra-red spectroscopy (FTIR) studies showed a systematic change in the spectra and revealed three main peaks included C-N, C=N, C=C and C≡N triple bond. C=N and C≡N bonds decreased with increased C-N bonds after thermal annealing process. The FESEM images showed that the structure is porous for as-deposited and covered by granule-like grain structure after thermal annealing process was done. The resistance of the a-CN{sub x} thin film changed from 23.765 kΩ to 5.845 kΩ in the relative humidity range of 5 to 92 % and the film shows a good response and repeatability as a humidity sensing materials. This work showed that rf power and thermal annealing has significant effects on the chemical bonding and surface morphology of the a-CN{sub x} films and but yield films which are potential candidate as humidity sensor device.« less

LEACHABILITY STUDIES OF TRACE METALS FROM DREDGED SEDIMENT

EPA Science Inventory

Long term leaching and migration of chemicals from improperly disposed sediments may result in environmental concerns. Results of laboratory studies show that leachate losses may be minimized by using chemical amendment and/or varying operational practices.

EPA Analysis of FracFocus 1 Data

EPA Pesticide Factsheets

The EPA conducted an analysis to better understand the chemicals and water used to hydraulically fracture oil and gas production wells in the United States and how chemical and water use vary in different locations across the country.

Estimated Performance of Radial-Flow Exit Nozzles for Air in Chemical Equilibrium

NASA Technical Reports Server (NTRS)

Englert, Gerald W.; Kochendorfer, Fred D.

1959-01-01

The thrust, boundary-layer, and heat-transfer characteristics were computed for nozzles having radial flow in the divergent part. The working medium was air in chemical equilibrium, and the boundary layer was assumed to be all turbulent. Stagnation pressure was varied from 1 to 32 atmospheres, stagnation temperature from 1000 to 6000 R, and wall temperature from 1000 to 3000 R. Design pressure ratio was varied from 5 to 320, and operating pressure ratio was varied from 0.25 to 8 times the design pressure ratio. Results were generalized independent of divergence angle and were also generalized independent of stagnation pressure in the temperature range of 1000 to 3000 R. A means of determining the aerodynamically optimum wall angle is provided.

Influence of hydraulic regimes on bacterial community structure and composition in an experimental drinking water distribution system.

PubMed

Douterelo, I; Sharpe, R L; Boxall, J B

2013-02-01

Microbial biofilms formed on the inner-pipe surfaces of drinking water distribution systems (DWDS) can alter drinking water quality, particularly if they are mechanically detached from the pipe wall to the bulk water, such as due to changes in hydraulic conditions. Results are presented here from applying 454 pyrosequencing of the 16S ribosomal RNA (rRNA) gene to investigate the influence of different hydrological regimes on bacterial community structure and to study the potential mobilisation of material from the pipe walls to the network using a full scale, temperature-controlled experimental pipeline facility accurately representative of live DWDS. Analysis of pyrosequencing and water physico-chemical data showed that habitat type (water vs. biofilm) and hydraulic conditions influenced bacterial community structure and composition in our experimental DWDS. Bacterial community composition clearly differed between biofilms and bulk water samples. Gammaproteobacteria and Betaproteobacteria were the most abundant phyla in biofilms while Alphaproteobacteria was predominant in bulk water samples. This suggests that bacteria inhabiting biofilms, predominantly species belonging to genera Pseudomonas, Zooglea and Janthinobacterium, have an enhanced ability to express extracellular polymeric substances to adhere to surfaces and to favour co-aggregation between cells than those found in the bulk water. Highest species richness and diversity were detected in 28 days old biofilms with this being accentuated at highly varied flow conditions. Flushing altered the pipe-wall bacterial community structure but did not completely remove bacteria from the pipe walls, particularly under highly varied flow conditions, suggesting that under these conditions more compact biofilms were generated. This research brings new knowledge regarding the influence of different hydraulic regimes on the composition and structure of bacterial communities within DWDS and the implication that this might have on drinking water quality. Copyright © 2012 Elsevier Ltd. All rights reserved.

A comprehensive review on the colorless carotenoids phytoene and phytofluene.

PubMed

Meléndez-Martínez, Antonio J; Mapelli-Brahm, Paula; Benítez-González, Ana; Stinco, Carla M

2015-04-15

Carotenoids and their derivatives are versatile isoprenoids involved in many varied actions, hence their importance in the agri-food industry, nutrition, health and other fields. All carotenoids are derived from the colorless carotenes phytoene and phytofluene, which are oddities among carotenoids due to their distinct chemical structure. They occur together with lycopene in tomato and other lycopene-containing foods. Furthermore, they are also present in frequently consumed products like oranges and carrots, among others. The intake of phytoene plus phytofluene has been shown to be higher than that of lycopene and other carotenoids in Luxembourg. This is likely to be common in other countries. However, they are not included in food carotenoid databases, hence they have not been linked to health benefits in epidemiological studies. Interestingly, there are evidences in vitro, animal models and humans indicating that they may provide health benefits. In this sense, the study of these colorless carotenes in the context of food science, nutrition and health should be further encouraged. In this work, we review much of the existing knowledge concerning their chemical characteristics, physico-chemical properties, analysis, distribution in foods, bioavailability and likely biological activities. Copyright © 2015 Elsevier Inc. All rights reserved.

First-principles calculations of 17O nuclear magnetic resonance chemical shielding in Pb(Zr(1/2)Ti(1/2))O3 and Pb(Mg(1/3)Nb(2/3))O3: linear dependence on transition-metal/oxygen bond lengths.

PubMed

Pechkis, Daniel L; Walter, Eric J; Krakauer, Henry

2011-09-21

First-principles density functional theory oxygen chemical shift tensors were calculated for A(B,B')O(3) perovskite alloys Pb(Zr(1/2)Ti(1/2))O(3) (PZT) and Pb(Mg(1/3)Nb(2/3))O(3) (PMN). Quantum chemistry methods for embedded clusters and the gauge including projector augmented waves (GIPAW) method [C. J. Pickard and F. Mauri, Phys. Rev. B 63, 245101 (2001)] for periodic boundary conditions were used. Results from both methods are in good agreement for PZT and prototypical perovskites. PMN results were obtained using only GIPAW. Both isotropic δ(iso) and axial δ(ax) chemical shifts were found to vary approximately linearly as a function of the nearest-distance transition-metal/oxygen bond length, r(s). Using these results, we argue against Ti clustering in PZT, as conjectured from recent (17)O NMR magic-angle-spinning measurements. Our findings indicate that (17)O NMR measurements, coupled with first-principles calculations, can be an important probe of local structure in complex perovskite solid solutions.

First-principles calculations of 17O nuclear magnetic resonance chemical shielding in Pb(Zr1/2Ti1/2)O3 and Pb(Mg1/3Nb2/3)O3: Linear dependence on transition-metal/oxygen bond lengths

NASA Astrophysics Data System (ADS)

Pechkis, Daniel L.; Walter, Eric J.; Krakauer, Henry

2011-09-01

First-principles density functional theory oxygen chemical shift tensors were calculated for A(B,B')O3 perovskite alloys Pb(Zr1/2Ti1/2)O3 (PZT) and Pb(Mg1/3Nb2/3)O3 (PMN). Quantum chemistry methods for embedded clusters and the gauge including projector augmented waves (GIPAW) method [C. J. Pickard and F. Mauri, Phys. Rev. B 63, 245101 (2001)], 10.1103/PhysRevB.63.245101 for periodic boundary conditions were used. Results from both methods are in good agreement for PZT and prototypical perovskites. PMN results were obtained using only GIPAW. Both isotropic δiso and axial δax chemical shifts were found to vary approximately linearly as a function of the nearest-distance transition-metal/oxygen bond length, rs. Using these results, we argue against Ti clustering in PZT, as conjectured from recent 17O NMR magic-angle-spinning measurements. Our findings indicate that 17O NMR measurements, coupled with first-principles calculations, can be an important probe of local structure in complex perovskite solid solutions.

The Crystal-Chemical Effect of REE Separation in Minerals: Causes and Practical Values

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.

2018-03-01

Contrast variations in the type of REE distribution from a distinctly negative mode to a positive mode is revealed in zonal fluorites of Eastern Transbaikal, with a pronounced decrease in the Ce/Y ratios in successive zones of increasing Y accompanied by a gradual decrease in the temperature and salinity of fluid inclusions in the fluorites. It is assumed that these facts are caused by the appearance of nm-size phases of REE minerals characterized by various crystalline structures and demonstrating selective concentrations of lanthanides, i.e., exhibiting a crystal-chemical differentiation of REEs that is widespread in the processes of mineral formation. Based on this natural mechanism, the development of a procedure of selective REE extraction from the concentrates is proposed. The primary laboratory experiments resulted in the discovery of the difference in REE concentrations in the sediment and filtrate with the separation coefficient varying by a factor of 76. The results obtained allow one to expect a true separation possibility for Nd along with the medium and heavy REEs. In view of the data obtained, the crystalline-chemical separation of REEs has some advantages compared to the processes currently used, especially extraction.

Controlling enhanced absorption in graphene metamaterial

NASA Astrophysics Data System (ADS)

Zhou, Qihui; Liu, Peiguo; Bian, Li-an; Liu, Hanqing; Liu, Chenxi; Chen, Genghui

2018-04-01

In this paper, a controllable terahertz (THz) metamaterial absorber (MA) is designed with the circuit analog method. Taking advantage of the patterned graphene on SiO2/doped Si/polyimide substrates with a gold reflector, the controllable MA achieves perfect absorption at 0.75 THz. The chemical potential of graphene is regulated by controlling the voltage between graphene and doped Si layers. As the chemical potential varies from 0 eV to 0.5 eV, the MA is changed from reflection (<0.37) to absorption (>0.99). The distributions of surface current and electric field are illustrated to analyze the resonant characteristic of patterned graphene. According to the resonant characteristic, we introduce patterned graphene elements with different dimension in a unit cell, which effectively extends the effective absorption bandwidth (absorption > 0 . 9) from 0.67-0.93 THz to 0.52-0.95 THz. Moreover, replacing part of the graphene structure with gold, the switchable MA is turned into a frequency tunable MA. The absorption peak moves from 0.62 THz to 0.92 THz as the chemical potential increases from 0.1 eV to 0.5 eV. These designs overcome limitation of traditional absorbers and exhibit great potentials in many practical applications.

Synthesis of nanocrystalline diamonds by microwave plasma

NASA Astrophysics Data System (ADS)

Purohit, V. S.; Jain, Deepti; Sathe, V. G.; Ganesan, V.; Bhoraskar, S. V.

2007-03-01

Nanocrystalline diamonds, varying in size from 40 to 400 nm, with random faceting were grown without the help of initial nucleation sites on nickel substrates as seen by scanning electron micrographs. These carbonaceous films were deposited in a microwave plasma reactor using hexane/nitrogen based chemical vapour deposition. The substrate temperatures during deposition were varied from 400 to 600 °C. The morphological investigations obtained by scanning electron micrographs and atomic force microscopy revealed the presence of nanocrystallites with multifaceted structures. Micro Raman investigations were carried out on the deposited films, which conclusively inferred that the growth of nanodiamond crystallites seen in the scanning electron micrographs correlate with clear Raman peaks appearing at 1120 and 1140 cm-1. Nanoindentation analysis with atomic force microscopy has revealed that the carbonaceous deposition identified by the Raman line at ~1140 cm-1, in fact, is related to nanodiamond on account of its hardness which was ~30 GPa. X-ray diffraction data supported this fact.

Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines.

PubMed

Sersen, Frantisek; Gregan, Fridrich; Kotora, Peter; Kmetova, Jarmila; Filo, Juraj; Loos, Dusan; Gregan, Juraj

2017-05-29

Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene)-N'-[2,6-dinitro-4-(trifluoromethyl)]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR), and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

Design and UV-curable behaviour of boron based reactive diluent for epoxy acrylate oligomer used for flame retardant wood coating

PubMed Central

Chambhare, Sachin U.; Lokhande, Gunawant P.; Jagtap, Ramanand N.

2017-01-01

Abstract Difunctional boron-containing reactive flame retardant for UV-curable epoxy acrylate oligomer was synthesized from phenyl boronic acid and glycidyl methacrylate. The synthesized reactive diluent was utilized to formulate ultraviolet (UV)-curable wood coatings. The weight fractions of reactive diluent in coatings formulation was varied from 5 to 25 wt % with constant photoinitiator concentration. The molecular structure of reactive flame retardant was confirmed by Fourier-transform infrared, Nuclear magnetic resonance (NMR) and 11B NMR spectral analysis. Further, the efficacy of flame retardant behaviour of coatings was evaluated using limiting oxygen index and UL-94 vertical burning test. Thermal stability of cured coatings films were estimated from thermogravimetric and differential scanning calorimetry analysis. The effects of varying concentration of reactive diluent on the viscosity of coatings formulation along with optical, mechanical and chemical resistance properties of coatings were also evaluated. The coatings gel content, water absorption behaviour, contact angle analysis and stain resistance were also studied. PMID:29491786

Silver Teflon blanket: LDEF tray C-08

NASA Technical Reports Server (NTRS)

Crutcher, E. Russ; Nishimura, L. S.; Warner, K. J.; Wascher, W. W.

1992-01-01

A study of the Teflon blanket surface at the edge of tray C-08 illustrates the complexity of the microenvironments on the Long Duration Exposure Facility (LDEF). The distribution of particulate contaminants varied dramatically over a distance of half a centimeter (quarter of an inch) near the edge of the blanket. The geometry and optical effects of the atomic oxygen erosion varied significantly over the few centimeters where the blanket folded over the edge of the tray resulting in a variety of orientations to the atomic oxygen flux. A very complex region of combined mechanical and atomic oxygen damage occurred where the blanket contacted the edge of the tray. A brown film deposit apparently fixed by ultraviolet light traveling by reflection through the Teflon film was conspicuous beyond the tray contract zone. Chemical and structural analysis of the surface of the brown film and beyond toward the protected edge of the blanket indicated some penetration of energetic atomic oxygen at least five millimeters past the blanket-tray contact interface.

Methods to determine hydration states of minerals and cement hydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com; Matschei, Thomas; Scrivener, Karen L.

2014-11-15

This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate aremore » presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.« less

The Latest on the Venus Thermospheric General Circulation Model: Capabilities and Simulations

NASA Technical Reports Server (NTRS)

Brecht, A. S.; Bougher, S. W.; Parkinson, C. D.

2017-01-01

Venus has a complex and dynamic upper atmosphere. This has been observed many times by ground-based, orbiters, probes, and fly-by missions going to other planets. Two over-arching questions are generally asked when examining the Venus upper atmosphere: (1) what creates the complex structure in the atmosphere, and (2) what drives the varying dynamics. A great way to interpret and connect observations to address these questions utilizes numerical modeling; and in the case of the middle and upper atmosphere (above the cloud tops), a 3D hydrodynamic numerical model called the Venus Thermospheric General Circulation Model (VTGCM) can be used. The VTGCM can produce climatological averages of key features in comparison to observations (i.e. nightside temperature, O2 IR nightglow emission). More recently, the VTGCM has been expanded to include new chemical constituents and airglow emissions, as well as new parameterizations to address waves and their impact on the varying global circulation and corresponding airglow distributions.

Paracrystalline Disorder from Phosphate Ion Orientation and Substitution in Synthetic Bone Mineral.

PubMed

Marisa, Mary E; Zhou, Shiliang; Melot, Brent C; Peaslee, Graham F; Neilson, James R

2016-12-05

Hydroxyapatite is an inorganic mineral closely resembling the mineral phase in bone. However, as a biological mineral, it is highly disordered, and its composition and atomistic structure remain poorly understood. Here, synchrotron X-ray total scattering and pair distribution function analysis methods provide insight into the nature of atomistic disorder in a synthetic bone mineral analogue, chemically substituted hydroxyapatite. By varying the effective hydrolysis rate and/or carbonate concentration during growth of the mineral, compounds with varied degrees of paracrystallinity are prepared. From advanced simulations constrained by the experimental pair distribution function and density functional theory, the paracrystalline disorder prevalent in these materials appears to result from accommodation of carbonate in the lattice through random displacement of the phosphate groups. Though many substitution modalities are likely to occur in concert, the most predominant substitution places carbonate into the mirror plane of an ideal phosphate site. Understanding the mineralogical imperfections of a biologically analogous hydroxyapatite is important not only to potential bone grafting applications but also to biological mineralization processes themselves.

Structural and mechanical characterization of boron doped biphasic calcium phosphate produced by wet chemical method and subsequent thermal treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albayrak, Onder, E-mail: albayrakonder@mersin.edu.tr

In the current study, boron doped biphasic calcium phosphate bioceramics consisting of a mixture of boron doped hydroxyapatite (BHA) and beta tricalcium phosphate (β-TCP) of varying BHA/β-TCP ratios were obtained after sintering stage. The effects of varying boron contents and different sintering temperatures on the BHA/β-TCP ratios and on the sinterability of the final products were investigated. Particle sizes and morphologies of the obtained precipitates were determined using SEM. XRD and FTIR investigation were conducted to detect the boron formation in the structure of HA and quantitative analysis was performed to determine the BHA/β-TCP ratio before and after sintering stage.more » In order to determine the sinterability of the obtained powders, pellets were prepared and sintered; the rates of densification were calculated and obtained results were correlated by SEM images. Also Vickers microhardness values of the sintered samples were determined. The experimental results verified that boron doped hydroxyapatite powders were obtained after sintering stage and the structure consists of a mixture of BHA and β-TCP. As the boron content used in the precipitation stage increases, β-TCP content of the BHA/β-TCP ratio increases but sinterability, density and microhardness deteriorate. As the sintering temperature increases, β-TCP content, density and microhardness of the samples increase and sinterability improves. - Highlights: • This is the first paper about boron doped biphasic calcium phosphate bioceramics. • Boron doping affects the structural and mechanical properties. • BHA/β-TCP ratio can be adjustable with boron content and sintering temperature.« less

Choline-amino acid ionic liquids: past and recent achievements about the structure and properties of these really "green" chemicals.

PubMed

Gontrani, Lorenzo

2018-06-01

The structure of choline-amino acid ionic liquids, atoxic task-specific solvents composed of materials originated from renewable feedstocks, is reviewed in this letter. The varied and strong interactions that these liquids are capable of establishing are largely dependent on their structure and confer them outstanding solvating properties with respect to a large number of different solutes. Among the experimental methods capable of yielding structural insight, the energy-dispersive version of X-Ray diffraction, that uses the Bremsstrahlung radiation of the X-Ray tube, is a technique very well suited to investigate these liquid systems. The diffraction spectra of five choline-amino acid ionic liquids, recently measured, are reported and discussed; in particular, the presence or absence of the medium-range order pre-peak is related to the presence of polar groups within the amino acid side chain that destroys the hydrophobic interactions between aliphatic chains. In the final section, a recent example of choline-amino acid ionic liquids as for ancient paper preservation and two other interesting results are discussed at the end.

Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kong, Zueqian

2010-01-01

Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-anglemore » X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration range of a working fuel cell, while dispersed water molecules and polymer ribbons account for the structures at low and high hydration levels, respectively.« less

Peculiarities of structural transformations in metal nanoparticles at high speed collisions

NASA Astrophysics Data System (ADS)

Zolnikov, K. P.; Kryzhevich, D. S.; Korchuganov, A. V.

2018-01-01

A molecular dynamics simulation of nanosized particle collision under the electrical explosion of metal wires of different types was conducted. Interatomic interactions were described on the base of the embedded atom method. Used potentials allowed describing with high accuracy many mechanical and physical properties which are very important for the simulations of nanoparticle collisions with high velocities. The dynamics of the nanosized particle formation at the electric pulse explosion of metal wires of different types was studied. Features of particle collisions on the example of nanoscale particles of copper and nickel, whose velocities varied from 50 to 1500 m/s were investigated. The peculiarities of structural transformations in the colliding particles depending on the velocity of collision were determined. The intervals of collision velocities in which interaction between particles is elastic or leads to the formation of structural defects or melting were calculated. The analysis of the structure and distribution of chemical elements over the cross section of the particles which were synthesized under simultaneous explosions of different metal wires was carried out.

Engineering of InN epilayers by repeated deposition of ultrathin layers in pulsed MOCVD growth

NASA Astrophysics Data System (ADS)

Mickevičius, J.; Dobrovolskas, D.; Steponavičius, T.; Malinauskas, T.; Kolenda, M.; Kadys, A.; Tamulaitis, G.

2018-01-01

Capabilities of repeated deposition of ultrathin layers by pulsed metalorganic chemical vapor deposition (MOCVD) for improvement of structural and luminescence properties of InN thin films on GaN/sapphire templates were studied by varying the growth temperature and the durations of pulse and pause in the delivery of In precursor. X-ray diffraction, atomic force microscopy, and spatially-resolved photoluminescence (PL) spectroscopy were exploited to characterize the structural quality, surface morphology and luminescence properties. Better structural quality is achieved by using longer trimethylindium pulses. However, it is shown that the luminescence properties of InN epilayers correlate with the pause and pulse ratio rather than with their absolute lengths, and the deposition of 1.5-2 monolayers of InN during one growth cycle is optimal to achieve the highest PL intensity. Moreover, the use of temperature ramping enabled achieving the highest PL intensity and the smallest blue shift of the PL band. The luminescence parameters are linked with the structural properties, and domain-like patterns of InN layers are revealed.

Rapid and reliable protein structure determination via chemical shift threading.

PubMed

Hafsa, Noor E; Berjanskii, Mark V; Arndt, David; Wishart, David S

2018-01-01

Protein structure determination using nuclear magnetic resonance (NMR) spectroscopy can be both time-consuming and labor intensive. Here we demonstrate how chemical shift threading can permit rapid, robust, and accurate protein structure determination using only chemical shift data. Threading is a relatively old bioinformatics technique that uses a combination of sequence information and predicted (or experimentally acquired) low-resolution structural data to generate high-resolution 3D protein structures. The key motivations behind using NMR chemical shifts for protein threading lie in the fact that they are easy to measure, they are available prior to 3D structure determination, and they contain vital structural information. The method we have developed uses not only sequence and chemical shift similarity but also chemical shift-derived secondary structure, shift-derived super-secondary structure, and shift-derived accessible surface area to generate a high quality protein structure regardless of the sequence similarity (or lack thereof) to a known structure already in the PDB. The method (called E-Thrifty) was found to be very fast (often < 10 min/structure) and to significantly outperform other shift-based or threading-based structure determination methods (in terms of top template model accuracy)-with an average TM-score performance of 0.68 (vs. 0.50-0.62 for other methods). Coupled with recent developments in chemical shift refinement, these results suggest that protein structure determination, using only NMR chemical shifts, is becoming increasingly practical and reliable. E-Thrifty is available as a web server at http://ethrifty.ca .

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

2014-03-11

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

Chemical treatments for improving compressive strength of linerboard at high moisture conditions

Treesearch

D. J. Fahey

1964-01-01

Various chemical treatments have been investigated at the Forest Products Laboratory for improving the compressive strength of linerboard exposed at high humidities and after water-soaking. Phenolic resins have been among the more promising chemicals studied, but they vary in performance. The low-condensed water-soluble phenolic resins have given some of the highest...

SPATIAL VARIATION OF PM 2.5 CHEMICAL SPECIES AND SOURCE-APPORTIONED MASS CONCENTRATIONS IN NEW YORK CITY. (R827351C001)

EPA Science Inventory

Particulate matter (PM) is a chemically non-specific pollutant, and may originate or be derived from different emission source types. Thus, its toxicity may well vary depending on its chemical composition. If the PM toxicity could be determined based on source types, the regul...

The Banning of Chemical Weapons: Tantalus Revisited.

DTIC Science & Technology

1983-04-14

of Chemical and Biological Warfare, by Robert Harris and Jeremy Paxman. Chemical and Engineering News, Vol. 60, No. 47, 22 November 1982, p. 34. 3...1 AD-A127 792 THE BANNING OF CHEMICAL WEAPONS: TANTALUS REVISITED(U) 1/1 IARMY WAR COLL CARLISLE BARRACKS PA F N DUREL 14 APR 8 UNCLASSIFIED F/G 15/2...number) Since the mid-ninetenth century, nations have sought to limit the u.s Of chemical weapons with varying degrees of success. On-going

Chemically Layered Porous Solids

NASA Technical Reports Server (NTRS)

Koontz, Steve

1991-01-01

Aerogels and other porous solids in which surfaces of pores have chemical properties varying with depth below macroscopic surfaces prepared by sequences of chemical treatments. Porous glass or silica bead treated to make two depth zones having different chemical properties. Beads dropped along tube filled with flowing gas containing atomic oxygen, generated in microwave discharge. General class of materials treatable include oxides of aluminum, silicon, zirconium, tin, titanium, and nickel, and mixtures of these oxides. Potential uses of treated materials include chromatographic separations, membrane separations, controlled releases of chemicals, and catalysis.

Concurrent Increases and Decreases in Local Stability and Conformational Heterogeneity in Cu, Zn Superoxide Dismutase Variants Revealed by Temperature-Dependence of Amide Chemical Shifts.

PubMed

Doyle, Colleen M; Rumfeldt, Jessica A; Broom, Helen R; Sekhar, Ashok; Kay, Lewis E; Meiering, Elizabeth M

2016-03-08

The chemical shifts of backbone amide protons in proteins are sensitive reporters of local structural stability and conformational heterogeneity, which can be determined from their readily measured linear and nonlinear temperature-dependences, respectively. Here we report analyses of amide proton temperature-dependences for native dimeric Cu, Zn superoxide dismutase (holo pWT SOD1) and structurally diverse mutant SOD1s associated with amyotrophic lateral sclerosis (ALS). Holo pWT SOD1 loses structure with temperature first at its periphery and, while having extremely high global stability, nevertheless exhibits extensive conformational heterogeneity, with ∼1 in 5 residues showing evidence for population of low energy alternative states. The holo G93A and E100G ALS mutants have moderately decreased global stability, whereas V148I is slightly stabilized. Comparison of the holo mutants as well as the marginally stable immature monomeric unmetalated and disulfide-reduced (apo(2SH)) pWT with holo pWT shows that changes in the local structural stability of individual amides vary greatly, with average changes corresponding to differences in global protein stability measured by differential scanning calorimetry. Mutants also exhibit altered conformational heterogeneity compared to pWT. Strikingly, substantial increases as well as decreases in local stability and conformational heterogeneity occur, in particular upon maturation and for G93A. Thus, the temperature-dependence of amide shifts for SOD1 variants is a rich source of information on the location and extent of perturbation of structure upon covalent changes and ligand binding. The implications for potential mechanisms of toxic misfolding of SOD1 in disease and for general aspects of protein energetics, including entropy-enthalpy compensation, are discussed.

The crystal structure of tetranatrolite from Mont Saint-Hilaire, Quebec, and its chemical and structural relationship to paranatrolite and gonnardite

USGS Publications Warehouse

Evans, H.T.; Konnert, J.A.; Ross, M.

2000-01-01

The structure of tetranatrolite from Mont Saint-Hilaire, Quebec (U.S. National Museum sample R1830) with a = 13.197(7) A, c = 6.630(9) A, and space group I42d, was refined using single-crystal X-ray data. A representative formula of tetranatrolite determined from electron microprobe analysis is Na12.50K0.01Ca2.93Sr0.11Al19.09 Si20.91O79.74??nH2O. The structure has the basic natrolite Si-Al-O framework configuration with Na, Ca, Sr, and K residing within inter-framework cages. Aluminum is disordered over the T1 and T2 tetrahedral sites, with T2 > T1. Water molecules O4 and O5 coordinate the intercage atoms and have high displacement parameters, indicating disorder within the cages. The Mont Saint-Hilaire tetranatrolite structure is compared to four previously determined structures, two tetranatrolite samples from Khibiny and Lovozero, Russia and two "gonnardite" samples from Tvedalen, Norway and Gignat, France. Observations are given to indicate that the Norwegian sample deduced to be tetranatrolite rather than gonnardite. Although the crystal structures of tetranatrolite and gonnardite are very similar, it is shown that the tetranatrolite compositions differ significantly from those of gonnardite. The tetranatrolite composition series varies along the join Na16Al16Si24O80-Na12 Ca4Al20Si20O80, and is represented by the formula Na16-xCaxAl16+xSi24-x O80??nH2O, where x extends from approximately 2.4 to 3.9. In contrast, gonnardites from Arkansas and Austria have compositions that vary along the join Na16Al16Si24O80-Na4 Ca8Al20Si20O80, which are represented by the formula ???xNa16-3xCa2xAl16+x Si24-xO80??nH2O and where ??? indicates vacant intercage cation sites and x varies from approximately 0.3 to 3.2. Tetranatrolite is a dehydration product of paranatrolite and probably does not have a true stability field.

Growth of diamond by RF plasma-assisted chemical vapor deposition

NASA Technical Reports Server (NTRS)

Meyer, Duane E.; Ianno, Natale J.; Woollam, John A.; Swartzlander, A. B.; Nelson, A. J.

1988-01-01

A system has been designed and constructed to produce diamond particles by inductively coupled radio-frequency, plasma-assisted chemical vapor deposition. This is a low-pressure, low-temperature process used in an attempt to deposit diamond on substrates of glass, quartz, silicon, nickel, and boron nitride. Several deposition parameters have been varied including substrate temperature, gas concentration, gas pressure, total gas flow rate, RF input power, and deposition time. Analytical methods employed to determine composition and structure of the deposits include scanning electron microscopy, absorption spectroscopy, scanning Auger microprobe spectroscopy, and Raman spectroscopy. Analysis indicates that particles having a thin graphite surface, as well as diamond particles with no surface coatings, have been deposited. Deposits on quartz have exhibited optical bandgaps as high as 4.5 eV. Scanning electron microscopy analysis shows that particles are deposited on a pedestal which Auger spectroscopy indicates to be graphite. This is a phenomenon that has not been previously reported in the literature.

Natural antioxidant extracts as food preservatives.

PubMed

Santos-Sánchez, Norma F; Salas-Coronado, Raúl; Valadez-Blanco, Rogelio; Hernández-Carlos, Beatriz; Guadarrama-Mendoza, Paula C

2017-01-01

The food industry is becoming more specialized and processing methods are continuously being developed to meet consumer needs. Consumers demand products that are safe and preferably free of synthetic additives. These additives are associated with health effects, in most cases without reasonable justification. Consequently, consumers are looking for clearly labelled products that guarantee the absence of synthetic additives. This has led to the need to search for natural additives, which the food industry claims arenatural antioxidant preservatives. The sources of natural antioxidants can be extremely varied, because practically all plants contain antioxidants that allow them to protect themselves from solar radiation and pests, as well as to regulate the production of chemical energy. However, the best alternatives for the food industry are fruits and spices, because they are already foods themselves. This article will describe fruits and spices considered as important sources of phenolic antioxidants. The main medicinal properties are related to phenolic compounds and their uses as additives, depending on their chemical structure.

Effect of substrate temperature and gas flow ratio on the nanocomposite TiAlBN coating

NASA Astrophysics Data System (ADS)

Rosli, Z. M.; Kwan, W. L.; Juoi, J. M.

2016-07-01

Nanocomposite TiAlBN (nc-TiAlBN) coatings were successfully deposited via RF magnetron sputtering by varying the nitrogen-to-total gas flow ratio (RN), and substrate temperature (TS). All coatings were deposited on AISI 316 substrates using single Ti-Al-BN hot-pressed disc as a target. The grain size, phases, and chemical composition of the coatings were evaluated using glancing angle X-ray diffraction analysis (GAXRD) and X-ray photoelectron spectroscopy (XPS). Results showed that the grains size of the deposited nc-TiAlBN coatings were in the range of 3.5 to 5.7 nm and reached a nitride saturation state as early as 15 % RN. As the nitrogen concentration decreases, boron concentration increased from 9 at.% to 16.17 at.%. and thus, increase the TiB2 phase within the coatings. The TS, however, showed no significant effect either on the crystallographic structure, grain size, or in the chemical composition of the deposited nc-TiAlBN coating.

Boron Nitride Nanotubes for Engineering Applications

NASA Technical Reports Server (NTRS)

Hurst, Janet; Hull, David; Gorican, Daniel

2005-01-01

Boron nitride nanotubes (BNNT) are of significant interest to the scientific and technical communities for many of the same reasons that carbon nanotubes (CNT) have attracted wide attention. Both materials have potentially unique and important properties for structural and electronic applications. However of even more consequence than their similarities may be the complementary differences between carbon and boron nitride nanotubes While BNNT possess a very high modulus similar to CNT, they also possess superior chemical and thermal stability. Additionally, BNNT have more uniform electronic properties, with a uniform band gap of 5.5 eV while CNT vary from semi-conductive to highly conductive behavior. Boron nitride nanotubes have been synthesized both in the literature and at NASA Glenn Research Center, by a variety of methods such as chemical vapor deposition, arc discharge and reactive milling. Consistent large scale production of a reliable product has proven difficult. Progress in the reproducible synthesis of 1-2 gram sized batches of boron nitride nanotubes will be discussed as well as potential uses for this unique material.

Synthesis of Boron Nitride Nanotubes for Engineering Applications

NASA Technical Reports Server (NTRS)

Hurst, Janet; Hull, David; Gorican, Dan

2005-01-01

Boron Nitride nanotubes (BNNT) are of interest to the scientific and technical communities for many of the same reasons that carbon nanotubes (CNT) have attracted large amounts of attention. Both materials have potentially unique and significant properties which may have important structural and electronic applications in the future. However of even more interest than their similarities may be the differences between carbon and boron nanotubes. Whilt boron nitride nanotubes possess a very high modulus similaar to CNT, they are also more chemically and thermally inert. Additionally BNNT possess more uniform electronic properties, having a uniform band gap of approximately 5.5 eV while CNT vary from semi-conductin to conductor behavior. Boron Nitride nanotubes have been synthesized by a variety of methods such as chemical vapor deposition, arc discharge and reactive milling. Consistently producing a reliable product has proven difficult. Progress in synthesis of 1-2 gram sized batches of Boron Nitride nanotubes will be discussed as well as potential uses for this unique material.

Investigation of carbonates in the Sutter's Mill meteorite grains with hyperspectral infrared imaging micro-spectroscopy

NASA Astrophysics Data System (ADS)

Yesiltas, Mehmet

2018-04-01

Synchrotron-based high spatial resolution hyperspectral infrared imaging technique provides thousands of infrared spectra with high resolution, thus allowing us to acquire detailed spatial maps of chemical molecular structures for many grains in short times. Utilizing this technique, thousands of infrared spectra were analyzed at once instead of inspecting each spectrum separately. Sutter's Mill meteorite is a unique carbonaceous type meteorite with highly heterogeneous chemical composition. Multiple grains from the Sutter's Mill meteorite have been studied using this technique and the presence of both hydrous and anhydrous silicate minerals have been observed. It is observed that the carbonate mineralogy varies from simple to more complex carbonates even within a few microns in the meteorite grains. These variations, the type and distribution of calcite-like vs. dolomite-like carbonates are presented by means of hyperspectral FTIR imaging spectroscopy with high resolution. Various scenarios for the formation of different carbonate compositions in the Sutter's Mill parent body are discussed.

Chemical Synthesis of Oligosaccharides Related to the Cell Walls of Plants and Algae.

PubMed

Kinnaert, Christine; Daugaard, Mathilde; Nami, Faranak; Clausen, Mads H

2017-09-13

Plant cell walls are composed of an intricate network of polysaccharides and proteins that varies during the developmental stages of the cell. This makes it very challenging to address the functions of individual wall components in cells, especially for highly complex glycans. Fortunately, structurally defined oligosaccharides can be used as models for the glycans, to study processes such as cell wall biosynthesis, polysaccharide deposition, protein-carbohydrate interactions, and cell-cell adhesion. Synthetic chemists have focused on preparing such model compounds, as they can be produced in good quantities and with high purity. This Review contains an overview of those plant and algal polysaccharides that have been elucidated to date. The majority of the content is devoted to detailed summaries of the chemical syntheses of oligosaccharide fragments of cellulose, hemicellulose, pectin, and arabinogalactans, as well as glycans unique to algae. Representative synthetic routes within each class are discussed in detail, and the progress in carbohydrate chemistry over recent decades is highlighted.

Spatio-temporal variability of airborne bacterial communities and their correlation with particulate matter chemical composition across two urban areas.

PubMed

Gandolfi, I; Bertolini, V; Bestetti, G; Ambrosini, R; Innocente, E; Rampazzo, G; Papacchini, M; Franzetti, A

2015-06-01

The study of spatio-temporal variability of airborne bacterial communities has recently gained importance due to the evidence that airborne bacteria are involved in atmospheric processes and can affect human health. In this work, we described the structure of airborne microbial communities in two urban areas (Milan and Venice, Northern Italy) through the sequencing, by the Illumina platform, of libraries containing the V5-V6 hypervariable regions of the 16S rRNA gene and estimated the abundance of airborne bacteria with quantitative PCR (qPCR). Airborne microbial communities were dominated by few taxa, particularly Burkholderiales and Actinomycetales, more abundant in colder seasons, and Chloroplasts, more abundant in warmer seasons. By partitioning the variation in bacterial community structure, we could assess that environmental and meteorological conditions, including variability between cities and seasons, were the major determinants of the observed variation in bacterial community structure, while chemical composition of atmospheric particulate matter (PM) had a minor contribution. Particularly, Ba, SO4 (2-) and Mg(2+) concentrations were significantly correlated with microbial community structure, but it was not possible to assess whether they simply co-varied with seasonal shifts of bacterial inputs to the atmosphere, or their variation favoured specific taxa. Both local sources of bacteria and atmospheric dispersal were involved in the assembling of airborne microbial communities, as suggested, to the one side by the large abundance of bacteria typical of lagoon environments (Rhodobacterales) observed in spring air samples from Venice and to the other by the significant effect of wind speed in shaping airborne bacterial communities at all sites.

Elucidation of the effect of ionic liquid pretreatment on rice husk via structural analyses

PubMed Central

2012-01-01

Background In the present study, three ionic liquids, namely 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc), and 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM]DEP), were used to partially dissolve rice husk, after which the cellulose were regenerated by the addition of water. The aim of the investigation is to examine the implications of the ionic liquid pretreatments on rice husk composition and structure. Results From the attenuated total reflectance Fourier transform-infrared (ATR FT-IR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) results, the regenerated cellulose were more amorphous, less crystalline, and possessed higher structural disruption compared with untreated rice husk. The major component of regenerated cellulose from [BMIM]Cl and [EMIM]DEP pretreatments was cellulose-rich material, while cellulose regenerated from [EMIM]OAc was a matrix of cellulose and lignin. Cellulose regenerated from ionic pretreatments could be saccharified via enzymatic hydrolysis, and resulted in relatively high reducing sugars yields, whereas enzymatic hydrolysis of untreated rice husk did not yield reducing sugars. Rice husk residues generated from the ionic liquid pretreatments had similar chemical composition and amorphousity to that of untreated rice husk, but with varying extent of surface disruption and swelling. Conclusions The structural architecture of the regenerated cellulose and rice husk residues showed that they could be used for subsequent fermentation or derivation of cellulosic compounds. Therefore, ionic liquid pretreatment is an alternative in the pretreatment of lignocellulosic biomass in addition to the conventional chemical pretreatments. PMID:22958710

Structure and function of natural sulphide-oxidizing microbial mats under dynamic input of light and chemical energy

PubMed Central

Klatt, Judith M; Meyer, Steffi; Häusler, Stefan; Macalady, Jennifer L; de Beer, Dirk; Polerecky, Lubos

2016-01-01

We studied the interaction between phototrophic and chemolithoautotrophic sulphide-oxidizing microorganisms in natural microbial mats forming in sulphidic streams. The structure of these mats varied between two end-members: one characterized by a layer dominated by large sulphur-oxidizing bacteria (SOB; mostly Beggiatoa-like) on top of a cyanobacterial layer (B/C mats) and the other with an inverted structure (C/B mats). C/B mats formed where the availability of oxygen from the water column was limited (<5 μm). Aerobic chemolithotrophic activity of the SOB depended entirely on oxygen produced locally by cyanobacteria during high light conditions. In contrast, B/C mats formed at locations where oxygen in the water column was comparatively abundant (>45 μM) and continuously present. Here SOB were independent of the photosynthetic activity of cyanobacteria and outcompeted the cyanobacteria in the uppermost layer of the mat where energy sources for both functional groups were concentrated. Outcompetition of photosynthetic microbes in the presence of light was facilitated by the decoupling of aerobic chemolithotrophy and oxygenic phototrophy. Remarkably, the B/C mats conserved much less energy than the C/B mats, although similar amounts of light and chemical energy were available. Thus ecosystems do not necessarily develop towards optimal energy usage. Our data suggest that, when two independent sources of energy are available, the structure and activity of microbial communities is primarily determined by the continuous rather than the intermittent energy source, even if the time-integrated energy flux of the intermittent energy source is greater. PMID:26405833

An XPS study on the chemical bond structure at the interface between SiO{sub x}N{sub y} and N doped polyethylene terephthalate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding Wanyu; Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024; Li Li

2013-03-14

The super-thin silicon oxynitride (SiO{sub x}N{sub y}) films were deposited onto the N doped polyethylene terephthalate (PET) surface. Varying the N doping parameters, the different chemical bond structures were obtained at the interface between the SiO{sub x}N{sub y} film and the PET surface. X-ray photoelectron spectra results showed that at the initial stage of SiO{sub x}N{sub y} film growth, the C=N bonds could be broken and C-N-Si crosslink bonds could be formed at the interface of SiO{sub x}N{sub y}/PET, which C=N bonds could be formed onto the PET surface during the N doping process. At these positions, the SiO{sub x}N{submore » y} film could be crosslinked well onto the PET surface. Meanwhile, the doped N could crosslink the [SiO{sub 4}] and [SiN{sub 4}] tetrahedrons, which could easily form the dense layer structure at the initial stage of SiO{sub x}N{sub y} film growth, instead of the ring and/or chain structures of [SiO{sub 4}] tetrahedrons crosslinked by O. Finally, from the point of applying SiO{sub x}N{sub y}/PET complex as the substrate, the present work reveals a simple way to crosslink them, as well as the crosslink model and physicochemical mechanism happened at the interface of complex.« less

Effects of soil and space on the woody species composition and vegetation structure of three Cerrado phytophysiognomies in the Cerrado-Amazon transition.

PubMed

Maracahipes-Santos, L; Lenza, E; Santos, J O; Mews, H A; Oliveira, B

2017-11-01

The Cerrado Biome is considered one of the world's biodiversity hotspots because of its rich biodiversity, the high level of endemism and the increasing threat. The Cerrado is composed by a mosaic of different vegetation types, including physiognomies that vary from grasslands (campo limpo) to savannas (typical cerrado or cerrado sensu stricto) and cerrado woodlands (cerradão). However, the factors that determine the composition of the Cerrado's flora and the structure of the physiognomies that compose this biome are still poorly understood. Here, we investigate the influence of the chemical and granulometric properties of the soil and the effect of geographic distance on the occurrence and abundance of woody species in three Cerrado phytophysiognomies - cerrado woodland (cerradão), dense cerrado savanna and typical cerrado savanna - in the Cerrado-Amazon transition. We tested the hypothesis that the edaphic characteristics and geographic space determine the species composition and the structure of the woody vegetation of these three phytophysiognomies. We demonstrate that the dissimilarities in the structure and composition of the three sites were determined more by space (13% of explanation) than edaphic properties (1%), but primarily by the interaction between these two factors (26%). We conclude that, in situations where the chemical and granulometric properties of the soil are relatively homogeneous, as we found in the present study, geographic distance between sites has a greater influence than variation in the substrate's properties on modelling the occurrence and abundance of the woody plant species in the Cerrado.

A toxicologic and dermatologic assessment of cinnamyl phenylpropyl materials when used as fragrance ingredients.

PubMed

Belsito, D; Bickers, D; Bruze, M; Calow, P; Dagli, M; Fryer, A D; Greim, H; Miyachi, Y; Saurat, J H; Sipes, I G

2011-12-01

The cinnamyl phenylpropyl fragrance ingredients are a diverse group of chemical structures that have similar metabolic and toxicity profiles. A toxicological and dermatological review of these fragrance ingredients is presented. The common characteristic structural element of cinnamyl phenylpropyl materials is an aryl substituted primary alcohol/aldehyde/ester. For high end users, calculated maximum dermal exposures vary from 0.14% to 0.72%; systemic exposures vary from 0.0002 to 0.0280 mg/kg/day. Human dermatological studies show that these materials are not generally irritants or sensitizers at lower exposures from consumer products. Reactions (0.9%) in fragrance sensitive patients were observed with 3-phenyl-1-propanol at 5% in petrolatum. The cinnamyl phenylpropyl materials had low acute toxicity and no significant toxicity in repeat dose oral or dermal toxicity studies. No mutagenic or genotoxic activity in bacteria and mammalian cell line assays was observed. The cinnamyl phenylpropyl alcohol materials participate in the same beta oxidation pathways as their parent cinnamic acid derivatives, including common routes of absorption, distribution, and metabolic detoxification, and exhibit similar toxicological endpoints. Based on the review of available data, it is concluded that these materials would not present a safety concern at current levels of use as fragrance ingredients. Copyright © 2011 Elsevier Ltd. All rights reserved.

Making a Healthier Home: Cast Toxins From Your Living Space

MedlinePlus

... can make a chemical harmful. The amount that’s “safe” varies for each substance. NIH-funded researchers are working to learn more about how chemicals in the environment can affect our health, so we can better ...

Analysis of transient receptor potential ankyrin 1 (TRPA1) in frogs and lizards illuminates both nociceptive heat and chemical sensitivities and coexpression with TRP vanilloid 1 (TRPV1) in ancestral vertebrates.

PubMed

Saito, Shigeru; Nakatsuka, Kazumasa; Takahashi, Kenji; Fukuta, Naomi; Imagawa, Toshiaki; Ohta, Toshio; Tominaga, Makoto

2012-08-31

Transient receptor potential ankyrin 1 (TRPA1) and TRP vanilloid 1 (V1) perceive noxious temperatures and chemical stimuli and are involved in pain sensation in mammals. Thus, these two channels provide a model for understanding how different genes with similar biological roles may influence the function of one another during the course of evolution. However, the temperature sensitivity of TRPA1 in ancestral vertebrates and its evolutionary path are unknown as its temperature sensitivities vary among different vertebrate species. To elucidate the functional evolution of TRPA1, TRPA1s of the western clawed (WC) frogs and green anole lizards were characterized. WC frog TRPA1 was activated by heat and noxious chemicals that activate mammalian TRPA1. These stimuli also activated native sensory neurons and elicited nocifensive behaviors in WC frogs. Similar to mammals, TRPA1 was functionally co-expressed with TRPV1, another heat- and chemical-sensitive nociceptive receptor, in native sensory neurons of the WC frog. Green anole TRPA1 was also activated by heat and noxious chemical stimulation. These results suggest that TRPA1 was likely a noxious heat and chemical receptor and co-expressed with TRPV1 in the nociceptive sensory neurons of ancestral vertebrates. Conservation of TRPV1 heat sensitivity throughout vertebrate evolution could have changed functional constraints on TRPA1 and influenced the functional evolution of TRPA1 regarding temperature sensitivity, whereas conserving its noxious chemical sensitivity. In addition, our results also demonstrated that two mammalian TRPA1 inhibitors elicited different effect on the TRPA1s of WC frogs and green anoles, which can be utilized to clarify the structural bases for inhibition of TRPA1.

Analysis of Transient Receptor Potential Ankyrin 1 (TRPA1) in Frogs and Lizards Illuminates Both Nociceptive Heat and Chemical Sensitivities and Coexpression with TRP Vanilloid 1 (TRPV1) in Ancestral Vertebrates*

PubMed Central

Saito, Shigeru; Nakatsuka, Kazumasa; Takahashi, Kenji; Fukuta, Naomi; Imagawa, Toshiaki; Ohta, Toshio; Tominaga, Makoto

2012-01-01

Transient receptor potential ankyrin 1 (TRPA1) and TRP vanilloid 1 (V1) perceive noxious temperatures and chemical stimuli and are involved in pain sensation in mammals. Thus, these two channels provide a model for understanding how different genes with similar biological roles may influence the function of one another during the course of evolution. However, the temperature sensitivity of TRPA1 in ancestral vertebrates and its evolutionary path are unknown as its temperature sensitivities vary among different vertebrate species. To elucidate the functional evolution of TRPA1, TRPA1s of the western clawed (WC) frogs and green anole lizards were characterized. WC frog TRPA1 was activated by heat and noxious chemicals that activate mammalian TRPA1. These stimuli also activated native sensory neurons and elicited nocifensive behaviors in WC frogs. Similar to mammals, TRPA1 was functionally co-expressed with TRPV1, another heat- and chemical-sensitive nociceptive receptor, in native sensory neurons of the WC frog. Green anole TRPA1 was also activated by heat and noxious chemical stimulation. These results suggest that TRPA1 was likely a noxious heat and chemical receptor and co-expressed with TRPV1 in the nociceptive sensory neurons of ancestral vertebrates. Conservation of TRPV1 heat sensitivity throughout vertebrate evolution could have changed functional constraints on TRPA1 and influenced the functional evolution of TRPA1 regarding temperature sensitivity, whereas conserving its noxious chemical sensitivity. In addition, our results also demonstrated that two mammalian TRPA1 inhibitors elicited different effect on the TRPA1s of WC frogs and green anoles, which can be utilized to clarify the structural bases for inhibition of TRPA1. PMID:22791718

Predicting Odor Pleasantness from Odorant Structure: Pleasantness as a Reflection of the Physical World

DTIC Science & Technology

2009-11-01

34 ( Engen , 1982). We next reduced the dimensionality of physico- chemical properties, and identified a primary axis of physico- chemical space. This axis...words, there is no scientist or perfumer who can predict the smell of a novel molecule by its physico- chemical structure, or the physico- chemical ...structure of a novel smell. Understanding this link between physico- chemical structure and percept has been elusive because the percept is in large

A novel approach: chemical relational databases, and the role of the ISSCAN database on assessing chemical carcinogenicity.

PubMed

Benigni, Romualdo; Bossa, Cecilia; Richard, Ann M; Yang, Chihae

2008-01-01

Mutagenicity and carcinogenicity databases are crucial resources for toxicologists and regulators involved in chemicals risk assessment. Until recently, existing public toxicity databases have been constructed primarily as "look-up-tables" of existing data, and most often did not contain chemical structures. Concepts and technologies originated from the structure-activity relationships science have provided powerful tools to create new types of databases, where the effective linkage of chemical toxicity with chemical structure can facilitate and greatly enhance data gathering and hypothesis generation, by permitting: a) exploration across both chemical and biological domains; and b) structure-searchability through the data. This paper reviews the main public databases, together with the progress in the field of chemical relational databases, and presents the ISSCAN database on experimental chemical carcinogens.

ACToR Chemical Structure processing using Open Source ...

EPA Pesticide Factsheets

ACToR (Aggregated Computational Toxicology Resource) is a centralized database repository developed by the National Center for Computational Toxicology (NCCT) at the U.S. Environmental Protection Agency (EPA). Free and open source tools were used to compile toxicity data from over 1,950 public sources. ACToR contains chemical structure information and toxicological data for over 558,000 unique chemicals. The database primarily includes data from NCCT research programs, in vivo toxicity data from ToxRef, human exposure data from ExpoCast, high-throughput screening data from ToxCast and high quality chemical structure information from the EPA DSSTox program. The DSSTox database is a chemical structure inventory for the NCCT programs and currently has about 16,000 unique structures. Included are also data from PubChem, ChemSpider, USDA, FDA, NIH and several other public data sources. ACToR has been a resource to various international and national research groups. Most of our recent efforts on ACToR are focused on improving the structural identifiers and Physico-Chemical properties of the chemicals in the database. Organizing this huge collection of data and improving the chemical structure quality of the database has posed some major challenges. Workflows have been developed to process structures, calculate chemical properties and identify relationships between CAS numbers. The Structure processing workflow integrates web services (PubChem and NIH NCI Cactus) to d

Dynamics of ligand substitution in labile cobalt complexes resolved by ultrafast T-jump

PubMed Central

Ma, Hairong; Wan, Chaozhi; Zewail, Ahmed H.

2008-01-01

Ligand exchange of hydrated metal complexes is common in chemical and biological systems. Using the ultrafast T-jump, we examined this process, specifically the transformation of aqua cobalt (II) complexes to their fully halogenated species. The results reveal a stepwise mechanism with time scales varying from hundreds of picoseconds to nanoseconds. The dynamics are significantly faster when the structure is retained but becomes rate-limited when the octahedral-to-tetrahedral structural change bottlenecks the transformation. Evidence is presented, from bimolecular kinetics and energetics (enthalpic and entropic), for a reaction in which the ligand assists the displacement of water molecules, with the retention of the entering ligand in the activated state. The reaction time scale deviates by one to two orders of magnitude from that of ionic diffusion, suggesting the involvement of a collisional barrier between the ion and the much larger complex. PMID:18725628

Structural and dielectric properties of Al x Zn1- x O ( x = 0, 0.02, 0.04, 0.06, 0.08 and 0.10) nanoparticles

NASA Astrophysics Data System (ADS)

Sharma, Neha; Kumar, Sanjay; Sharma, Varun

2018-05-01

The chemical precipitation method is followed for the synthesis of Al-doped ZnO nanoparticles (NPs) with varying doping concentrations (0, 0.02, 0.04, 0.06, 0.08, and 0.10 M). A single hexagonal crystalline phase of wurtzite structure has been confirmed for all the samples by X-ray diffraction. Crystalline size and microstrain of the un-doped and doped ZnO (NPs) is determined by the Williamson-Hall (W-H) analysis. The optical properties like band gap and Urbach energy are found out by the UV-visible spectroscopy. The functional bonds are detailed by Fourier transmission infrared spectroscopy. The dielectric properties have been shown by doped sample due to hopping mechanisms as compared to the undoped. The loss factor (tan δ) follows an inverse direction as correspond to frequency due to the presence of dielectric dispersion.

Influencing Antibody-Mediated Attenuation of Methamphetamine CNS Distribution through Vaccine Linker Design.

PubMed

Gooyit, Major; Miranda, Pedro O; Wenthur, Cody J; Ducime, Alex; Janda, Kim D

2017-03-15

Active vaccination examining a single hapten engendered with a series of peptidic linkers has resulted in the production of antimethamphetamine antibodies. Given the limited chemical complexity of methamphetamine, the structure of the linker species embedded within the hapten could have a substantial effect on the ultimate efficacy of the resulting vaccines. Herein, we investigate linker effects by generating a series of methamphetamine haptens that harbor a linker with varying amino acid identity, peptide length, and associated carrier protein. Independent changes in each of these parameters were found to result in alterations in both the quantity and quality of the antibodies induced by vaccination. Although it was found that the consequence of the linker design was also dependent on the identity of the carrier protein, we demonstrate overall that the inclusion of a short, structurally simple, amino acid linker benefits the efficacy of a methamphetamine vaccine in limiting brain penetration of the free drug.

A theoretical study of thorium titanium-based alloys

NASA Astrophysics Data System (ADS)

Obodo, K. O.; Chetty, N.

2013-09-01

Using theoretical quantum chemical methods, we investigate the dearth of ordered alloys involving thorium and titanium. Whereas both these elements are known to alloy very readily with various other elements, for example with oxygen, current experimental data suggests that Th and Ti do not alloy very readily with each other. In this work, we consider a variety of ordered alloys at varying stoichiometries involving these elements within the framework of density functional theory using the generalized gradient approximation for the exchange and correlation functional. By probing the energetics, electronic, phonon and elastic properties of these systems, we confirm the scarcity of ordered alloys involving Th and Ti, since for a variety of reasons many of the systems that we considered were found to be unfavorable. However, our investigations resulted in one plausible ordered structure: We propose ThTi3 in the Cr3Si structure as a metastable ordered alloy.

RNA Crystallization

NASA Technical Reports Server (NTRS)

Golden, Barbara L.; Kundrot, Craig E.

2003-01-01

RNA molecules may be crystallized using variations of the methods developed for protein crystallography. As the technology has become available to syntheisize and purify RNA molecules in the quantities and with the quality that is required for crystallography, the field of RNA structure has exploded. The first consideration when crystallizing an RNA is the sequence, which may be varied in a rational way to enhance crystallizability or prevent formation of alternate structures. Once a sequence has been designed, the RNA may be synthesized chemically by solid-state synthesis, or it may be produced enzymatically using RNA polymerase and an appropriate DNA template. Purification of milligram quantities of RNA can be accomplished by HPLC or gel electrophoresis. As with proteins, crystallization of RNA is usually accomplished by vapor diffusion techniques. There are several considerations that are either unique to RNA crystallization or more important for RNA crystallization. Techniques for design, synthesis, purification, and crystallization of RNAs will be reviewed here.

Optimization of a growth process for as-grown 2D materials-based devices

NASA Astrophysics Data System (ADS)

Lindquist, Miles; Khadka, Sudiksha; Aleithan, Shrouq; Blumer, Ari; Wickramasinghe, Thushan; Thorat, Ruhi; Kordesch, Martin; Stinaff, Eric

We will present the effects of varying key parameters of a deterministic growth method for producing self-contacted 2D transition metal dichalcogenides. Chemical vapor deposition is used to grow a film of 2D material nucleated around and seeded from metallic features prepared by photolithography and sputtering on a Si/SiO2 substrate prior to growth. We will focus on a particular method of growing variable MoS2 based device structures. The goal of this work is to arrive at robust platform for growing a variety of device structures by systematically altering parameters such as the amount of reactants used, the heat of the substrate and oxide powder, and the flow rate of argon gas used. These results will help advance a comprehensive process for the scalable production of as-grown, complex, 2D materials-based device architectures.

Laser-induced dewetting of silver-doped chalcogenide glasses

NASA Astrophysics Data System (ADS)

Douaud, Alexandre; Messaddeq, Sandra Helena; Boily, Olivier; Messaddeq, Younès

2018-07-01

We report the observation of laser-induced dewetting responsible for the formation of periodic relief structures in silver-based chalcogenide thin-films. By varying the concentration of silver in the Agx(As20S80)100-x system (with x = 0, 4, 9 and 36), different surface relief structures are formed. The evolution of the surface changes as a function of laser parameters (power density, duration of exposure, and polarisation) as well as film thickness and silver concentration has been investigated. The scanning electron microscopy and atomic force microscopy images of irradiated spots show periodic ripples aligned perpendicularly to the electric field of incident light. Our results show that addition of silver into sulphur-rich chalcogenide thin-films improves the dewetting when compared to pure As20S80 thin-films. The changes in surface morphology were attributable to photo-induced chemical modifications and a laser-driven molecular rearrangement.

Zernike phase-contrast electron cryotomography applied to marine cyanobacteria infected with cyanophages.

PubMed

Dai, Wei; Fu, Caroline; Khant, Htet A; Ludtke, Steven J; Schmid, Michael F; Chiu, Wah

2014-11-01

Advances in electron cryotomography have provided new opportunities to visualize the internal 3D structures of a bacterium. An electron microscope equipped with Zernike phase-contrast optics produces images with markedly increased contrast compared with images obtained by conventional electron microscopy. Here we describe a protocol to apply Zernike phase plate technology for acquiring electron tomographic tilt series of cyanophage-infected cyanobacterial cells embedded in ice, without staining or chemical fixation. We detail the procedures for aligning and assessing phase plates for data collection, and methods for obtaining 3D structures of cyanophage assembly intermediates in the host by subtomogram alignment, classification and averaging. Acquiring three or four tomographic tilt series takes ∼12 h on a JEM2200FS electron microscope. We expect this time requirement to decrease substantially as the technique matures. The time required for annotation and subtomogram averaging varies widely depending on the project goals and data volume.

Automated extraction of chemical structure information from digital raster images

PubMed Central

Park, Jungkap; Rosania, Gus R; Shedden, Kerby A; Nguyen, Mandee; Lyu, Naesung; Saitou, Kazuhiro

2009-01-01

Background To search for chemical structures in research articles, diagrams or text representing molecules need to be translated to a standard chemical file format compatible with cheminformatic search engines. Nevertheless, chemical information contained in research articles is often referenced as analog diagrams of chemical structures embedded in digital raster images. To automate analog-to-digital conversion of chemical structure diagrams in scientific research articles, several software systems have been developed. But their algorithmic performance and utility in cheminformatic research have not been investigated. Results This paper aims to provide critical reviews for these systems and also report our recent development of ChemReader – a fully automated tool for extracting chemical structure diagrams in research articles and converting them into standard, searchable chemical file formats. Basic algorithms for recognizing lines and letters representing bonds and atoms in chemical structure diagrams can be independently run in sequence from a graphical user interface-and the algorithm parameters can be readily changed-to facilitate additional development specifically tailored to a chemical database annotation scheme. Compared with existing software programs such as OSRA, Kekule, and CLiDE, our results indicate that ChemReader outperforms other software systems on several sets of sample images from diverse sources in terms of the rate of correct outputs and the accuracy on extracting molecular substructure patterns. Conclusion The availability of ChemReader as a cheminformatic tool for extracting chemical structure information from digital raster images allows research and development groups to enrich their chemical structure databases by annotating the entries with published research articles. Based on its stable performance and high accuracy, ChemReader may be sufficiently accurate for annotating the chemical database with links to scientific research articles. PMID:19196483

Teaching Structural Formulas in Chemistry: How Students Relate Structural Formulas to the Solubility of Substances.

ERIC Educational Resources Information Center

Goedhart, Martin; van Duin, Yvonne

Structural formulas give professional chemists information about physical and chemical properties of corresponding compounds. In chemistry education at secondary schools, structural formulas are introduced in the context of chemical bonding. Structural formulas are not introduced as representations of the properties of chemical compounds. This…

Coherent Raman Imaging of Live Muscle Sarcomeres Assisted by SFG Microscopy.

PubMed

Kim, Hyunmin; Kim, Do-Young; Joo, Kyung-Il; Kim, Jung-Hye; Jeong, Soon Moon; Lee, Eun Seong; Hahm, Jeong-Hoon; Kim, Kyuhyung; Moon, Dae Woon

2017-08-23

In this study, we used spectrally focused coherent anti-Stokes Raman scattering (spCARS) microscopy assisted by sum-frequency generation (SFG) to monitor the variations in the structural morphology and molecular vibrations of a live muscle of Caenorhabditis elegans. The subunits of the muscle sarcomeres, such as the M-line, myosin, dense body, and α-actinin, were alternatively observed using spCARS microscopy for different sample orientations, with the guidance of a myosin positional marker captured by SFG microscopy. Interestingly enough, the beam polarization dependence of the spCARS contrasts for two parallel subunits (dense body and myosin) showed a ~90° phase difference. The chemically sensitive spCARS spectra induced by the time-varying overlap of two pulses allowed (after a robust subtraction of the non-resonant background using a modified Kramers-Krönig transformation method) high-fidelity detection of various genetically modified muscle sarcomeres tuned to the C-H vibration (2800-3100 cm -1 ). Conversely, SFG image mapping assisted by phase-retrieved spCARS spectra also facilitated label-free monitoring of the changes in the muscle content of C. elegans that are associated with aging, based on the hypothesis that the C-H vibrational modes could serve as qualitative chemical markers sensitive to the amount and/or structural modulation of the muscle.

Pleurotus ostreatus decreases cornstalk lignin content, potentially improving its suitability for animal feed.

PubMed

Chen, Ying; Fan, Huan; Meng, Fanrui

2017-03-01

The capacity of Pleurotus ostreatus to degrade lignin was investigated in the fermentation of cornstalk. Cornstalk was incubated with P. ostreatus for 30 days, and acid-soluble and acid-insoluble lignins were assessed. The microscopic structure of cornstalk samples was studied by scanning electron microscopy (SEM), and spectroscopic characteristics were measured by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance ( 13 C NMR) spectroscopy. During fermentation of cornstalk, the proportion of acid-soluble lignin did not vary significantly (P > 0.05), but that of acid-insoluble lignin decreased gradually from 17.8% on day 0 to 7.6% on day 30 (P < 0.01). SEM revealed that the surface of cornstalk was gradually damaged with cavities increasing in number and size, forming a quasi-network structure. Crystallinity decreased from 35.0 on day 0 to 15.2 on day 30. FTIR and cross-polarization magic angle spinning (CPMAS) 13 C NMR spectra showed that the intensity of the peaks corresponding to lignin, cellulose and hemicellulose also decreased gradually over 30 days. Cornstalk can be effectively degraded by P. ostreatus within 30 days. Pleurotus ostreatus decreases cornstalk lignin content, potentially improving its suitability for animal feed. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

USGS Publications Warehouse

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using extended X-ray absorption fine structure (EXAFS) and microfocused synchrotron X-ray fluorescence (μSXRF) mapping, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and microfocused EXAFS spectra of Zn in the biogenic Mn oxide coating are indicative of Zn forming triple-corner-sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to the decrease in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in the solid/solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating that desorption is not controlled by dissolution of secondary Zn phases. In summary, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process of Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present.

N-(4-Nitrobenzoyl)-N'-(1,5-dimethyl-3-oxo-2-phenyl-1H-3(2H)-pyrazolyl)-thiourea hydrate: Synthesis, spectroscopic characterization, X-ray structure and DFT studies

NASA Astrophysics Data System (ADS)

Arslan, N. Burcu; Kazak, Canan; Aydın, Fatma

2012-04-01

The title molecule (C19H17N5O4S·H2O) was synthesized and characterized by IR-NMR spectroscopy, MS and single-crystal X-ray diffraction. The molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the ground state have been calculated by using the density functional theory (DFT) method with 6-31G(d) basis set, and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. The calculated results show that the optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies and 1H and 13C NMR chemical shift values show good agreement with experimental data. To determine conformational flexibility, the molecular energy profile of the title compound was obtained with respect to the selected torsion angle, which was varied from -180° to +180° in steps of 10°. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis and thermodynamic properties of the compound were investigated by theoretical calculations.

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna-Reactor Plasmonic Photocatalysis.

PubMed

Li, Kun; Hogan, Nathaniel J; Kale, Matthew J; Halas, Naomi J; Nordlander, Peter; Christopher, Phillip

2017-06-14

Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction. Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g., Ag) is coupled to the catalytic properties of the nonplasmonic metal nanoparticle (e.g., Pt) to enable chemical transformations. With an eye toward sustainable solar driven photocatalysis, we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light-limited regime, where all photons need to be effectively utilized. By synthesizing core@shell/satellite (Ag@SiO 2 /Pt) antenna-reactor complexes with varying Ag nanoparticle diameters and performing photocatalytic CO oxidation, we observed plasmon-enhanced photocatalysis only for antenna-reactor complexes with antenna components of intermediate sizes (25 and 50 nm). Optimal photocatalytic performance was shown to be determined by a balance between maximized local field enhancements at the catalytically active Pt surface, minimized collective scattering of photons out of the catalyst bed by the complexes, and minimal light absorption in the Ag nanoparticle antenna. These results elucidate the critical aspects of local field enhancement, light scattering, and absorption in plasmonic photocatalyst design, especially under light-limited illumination conditions.

Effects of Ni content on nanocrystalline Fe-Co-Ni ternary alloys synthesized by a chemical reduction method

NASA Astrophysics Data System (ADS)

Chokprasombat, Komkrich; Pinitsoontorn, Supree; Maensiri, Santi

2016-05-01

Magnetic properties of Fe-Co-Ni ternary alloys could be altered by changing of the particle size, elemental compositions, and crystalline structures. In this work, Fe50Co50-xNix nanoparticles (x=10, 20, 40, and 50) were prepared by the novel chemical reduction process. Hydrazine monohydrate was used as a reducing agent under the concentrated basic condition with the presence of poly(vinylpyrrolidone). We found that the nanoparticles were composed of Fe, Co and Ni with compositions according to the molar ratio of the metal sources. Interestingly, the particles were well-crystalline at the as-prepared state without post-annealing at high temperature. Increasing Ni content resulted in phase transformation from body centered cubic (bcc) to face centered cubic (fcc). For the fcc phase, the average particle size decreased when increased the Ni content; the Fe50Ni50 nanoparticles had the smallest average size with the narrowest size distribution. In additions, the particles exhibited ferromagnetic properties at room temperature with the coercivities higher than 300 Oe, and the saturation magnetiation decreased with increasing Ni content. These results suggest that the structural and magnetic properties of Fe-Co-Ni alloys could be adjusted by varying the Ni content.

Fabrication of silica ceramic membrane via sol-gel dip-coating method at different nitric acid amount

NASA Astrophysics Data System (ADS)

Kahlib, N. A. Z.; Daud, F. D. M.; Mel, M.; Hairin, A. L. N.; Azhar, A. Z. A.; Hassan, N. A.

2018-01-01

Fabrication of silica ceramics via the sol-gel method has offered more advantages over other methods in the fabrication of ceramic membrane, such as simple operation, high purity homogeneous, well defined-structure and complex shapes of end products. This work presents the fabrication of silica ceramic membrane via sol-gel dip-coating methods by varying nitric acid amount. The nitric acid plays an important role as catalyst in fabrication reaction which involved hydrolysis and condensation process. The tubular ceramic support, used as the substrate, was dipped into the sol of Tetrethylorthosilicate (TEOS), distilled water and ethanol with the addition of nitric acid. The fabricated silica membrane was then characterized by (Field Emission Scanning Electron Microscope) FESEM and (Fourier transform infrared spectroscopy) FTIR to determine structural and chemical properties at different amount of acids. From the XRD analysis, the fabricated silica ceramic membrane showed the existence of silicate hydrate in the final product. FESEM images indicated that the silica ceramic membrane has been deposited on the tubular ceramic support as a substrate and penetrate into the pore walls. The intensity peak of FTIR decreased with increasing of amount of acids. Hence, the 8 ml of acid has demonstrated the appropriate amount of catalyst in fabricating good physical and chemical characteristic of silica ceramic membrane.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zorn, Gilad, E-mail: zorn@ge.com; Castner, David G.; Tyagi, Anuradha

Perfluorophenylazide (PFPA) chemistry is a novel method for tailoring the surface properties of solid surfaces and nanoparticles. It is general and versatile, and has proven to be an efficient way to immobilize graphene, proteins, carbohydrates, and synthetic polymers. The main thrust of this work is to provide a detailed investigation on the chemical composition and surface density of the PFPA tailored surface. Specifically, gold surfaces were treated with PFPA-derivatized (11-mercaptoundecyl)tetra(ethylene glycol) (PFPA-MUTEG) mixed with 2-[2-(2-mercaptoethoxy)ethoxy]ethanol (MDEG) at varying solution mole ratios. Complementary analytical techniques were employed to characterize the resulting films including Fourier transform infrared spectroscopy to detect fingerprints ofmore » the PFPA group, x-ray photoelectron spectroscopy and ellipsometry to study the homogeneity and uniformity of the films, and near edge x-ray absorption fine structures to study the electronic and chemical structure of the PFPA groups. Results from these studies show that the films prepared from 90:10 and 80:20 PFPA-MUTEG/MDEG mixed solutions exhibited the highest surface density of PFPA and the most homogeneous coverage on the surface. A functional assay using surface plasmon resonance with carbohydrates covalently immobilized onto the PFPA-modified surfaces showed the highest binding affinity for lectin on the PFPA-MUTEG/MDEG film prepared from a 90:10 solution.« less

Worldwide variation in within-canopy photosynthetic acclimation: differences in temporal and environmental controls among plant functional types

NASA Astrophysics Data System (ADS)

Niinemets, Ülo; Keenan, Trevor

2017-04-01

Major light gradients, characteristically 10- to 50-fold, constitute the most prominent feature of plant canopies. These gradients drive within-canopy variation in foliage structural, chemical and physiological traits. As a key acclimation response to variation in light availability, foliage photosynthetic capacity per area (Aarea) increases with increasing light availability within the canopy, maximizing whole canopy photosynthesis. Recently, a worldwide database including 831 within-canopy gradients with standardized light estimates for 304 species belonging to major vascular plant functional types was constructed and within-canopy variation in photosynthetic acclimation was characterized (Niinemets Ü, Keenan TF, Hallik L (2015) Tansley review. A worldwide analysis of within-canopy variations in leaf structural, chemical and physiological traits across plant functional types. The New Phytologist 205: 973-993). However, the understanding of how within-canopy photosynthetic gradients vary during the growing season and in response to site and stand characteristics is still limited. Here we analyzed temporal, environmental and site (nutrient availability, stand density, ambient CO2 concentration, water availability) sources of variation in within-canopy photosynthetic acclimation in different plant functional types. Variation in key structural (leaf dry mass per unit area, MA), chemical (nitrogen content per dry mass, NM, and area, NA) and physiological (photosynthetic nitrogen use efficiency, EN) photosynthetic capacity per dry mass, Amass and area, Aarea) was examined. The analysis demonstrates major, typically 1.5-2-fold, time-, environment and site-dependent modifications in within-canopy variation in foliage photosynthetic capacity. However, the magnitude and direction of temporal and environmental variations in plasticity significantly varied among functional types. Species with longer leaf life span and low rates of canopy expansion or flush-type canopy formation had lower within canopy plasticity during the growing season and in response to environmental and site modifications than species with high rates of canopy expansion and leaf turnover. The fast canopy-expanding species that grow in highly dynamic light environments, actively modified Aarea by nitrogen reallocation among and partitioning within leaves. In contrast, species with low rate of leaf turnover generally exhibited a passive acclimation response with variation in Aarea primarily determined by light-dependent modifications in leaf structure during leaf growth. Due to limited reacclimation capacity in species with low leaf turnover, within-canopy variation in Aarea decreased with increasing leaf age in these species. Furthermore, the plasticity responded less to modifications in environmental and site characteristics than in species with faster leaf turnover. This analysis concludes that the rate of leaf turnover is the key trait determining the temporal variation and environmental responses of canopy photosynthetic acclimation.

Effect of Thermochemical Synthetic Conditions on the Structure and Dielectric Properties of Ga1.9Fe0.1O3 Compounds.

PubMed

Roy, Swadipta; Ramana, C V

2018-02-05

We report on the tunable and controlled dielectric properties of iron (Fe)-doped gallium oxide (Ga 2 O 3 ; Ga 1.9 Fe 0.1 O 3 , referred to as GFO) inorganic compounds. The GFO materials were synthesized using a standard high-temperature, solid-state chemical reaction method by varying the thermochemical processing conditions, namely, different calcination and sintering environments. Structural characterization by X-ray diffraction revealed that GFO compounds crystallize in the β-Ga 2 O 3 phase. The Fe doping has induced slight lattice strain in GFO, which is evident in structural analysis. The effect of the sintering temperature (T sint ), which was varied in the range of 900-1200 °C, is significant, as revealed by electron microscopy analysis. T sint influences the grain size and microstructure evolution, which, in turn, influences the dielectric and electrical properties of GFO compounds. The energy-dispersive X-ray spectrometry and mapping data demonstrate the uniform distribution of the elemental composition over the microstructure. The temperature- and frequency-dependent dielectric measurements indicate the characteristic features that are specifically due to Fe doping in Ga 2 O 3 . The spreading factor and relaxation time, calculated using Cole-Cole plots, are in the ranges of 0.65-0.76 and 10 -4 s, respectively. The results demonstrate that densification and control over the microstructure and properties of GFO can be achieved by optimizing T sint .

Spatial variability structure of soil CO2 emission and soil physical and chemical properties characterized by fractal dimension in sugarcane areas

NASA Astrophysics Data System (ADS)

Bicalho, E. S.; Teixeira, D. B.; Panosso, A. R.; Perillo, L. I.; Iamaguti, J. L.; Pereira, G. T.; La Scala, N., Jr.

2012-04-01

Soil CO2 emission (FCO2) is influenced by chemical, physical and biological factors that affect the production of CO2 in the soil and its transport to the atmosphere, varying in time and space depending on environmental conditions, including the management of agricultural area. The aim of this study was to investigate the structure of spatial variability of FCO2 and soil properties by using fractal dimension (DF), derived from isotropic variograms at different scales, and construction of fractograms. The experimental area consisted of a regular grid of 60 × 60 m on sugarcane area under green management, containing 141 points spaced at minimum distances ranging from 0.5 to 10 m. Soil CO2 emission, soil temperature and soil moisture were evaluated over a period of 7 days, and soil chemical and physical properties were determined by sampling at a depth of 0.0 to 0.1 m. FCO2 showed an overall average of 1.51 µmol m-2 s-1, correlated significantly (p < 0.05) with soil physical factors such as soil bulk density, air-filled pore space, macroporosity and microporosity. Significant DF values were obtained in the characterization of FCO2 in medium and large scales (from 20 m). Variations in DF with the scale, which is the fractogram, indicate that the structure of FCO2 variability is similar to that observed for the soil temperature and total pore volume, and reverse for the other soil properties, except for macroporosity, sand content, soil organic matter, carbon stock, C/N ratio and CEC, which fractograms were not significantly correlated to the FCO2 fractogram. Thus, the structure of spatial variability for most soil properties, characterized by fractogram, presents a significant relationship with the structure of spatial variability of FCO2, generally with similar or dissimilar behavior, indicating the possibility of using the fractogram as tool to better observe the behavior of the spatial dependence of the variables along the scale.

An NMR study of microvoids in polymers

NASA Technical Reports Server (NTRS)

Toy, James; Mattix, Larry

1995-01-01

An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the line width (delta upsilon = 2.5 kHz).

Molecular environmental geochemistry

NASA Astrophysics Data System (ADS)

O'Day, Peggy A.

1999-05-01

The chemistry, mobility, and bioavailability of contaminant species in the natural environment are controlled by reactions that occur in and among solid, aqueous, and gas phases. These reactions are varied and complex, involving changes in chemical form and mass transfer among inorganic, organic, and biochemical species. The field of molecular environmental geochemistry seeks to apply spectroscopic and microscopic probes to the mechanistic understanding of environmentally relevant chemical processes, particularly those involving contaminants and Earth materials. In general, empirical geochemical models have been shown to lack uniqueness and adequate predictive capability, even in relatively simple systems. Molecular geochemical tools, when coupled with macroscopic measurements, can provide the level of chemical detail required for the credible extrapolation of contaminant reactivity and bioavailability over ranges of temperature, pressure, and composition. This review focuses on recent advances in the understanding of molecular chemistry and reaction mechanisms at mineral surfaces and mineral-fluid interfaces spurred by the application of new spectroscopies and microscopies. These methods, such as synchrotron X-ray absorption and scattering techniques, vibrational and resonance spectroscopies, and scanning probe microscopies, provide direct chemical information that can elucidate molecular mechanisms, including element speciation, ligand coordination and oxidation state, structural arrangement and crystallinity on different scales, and physical morphology and topography of surfaces. Nonvacuum techniques that allow examination of reactions in situ (i.e., with water or fluids present) and in real time provide direct links between molecular structure and reactivity and measurements of kinetic rates or thermodynamic properties. Applications of these diverse probes to laboratory model systems have provided fundamental insight into inorganic and organic reactions at mineral surfaces and mineral-water interfaces. A review of recent studies employing molecular characterizations of soils, sediments, and biological samples from contaminated sites exemplifies the utility and benefits, as well as the challenge, of applying molecular probes to complicated natural materials. New techniques, technological advances, and the crossover of methods from other disciplines such as biochemistry and materials science promise better examination of environmental chemical processes in real time and at higher resolution, and will further the integration of molecular information into field-scale chemical and hydrologic models.

USING SUBSURFACE TRANSPORT RESEARCH TO ACHIEVE AGENCY OUTCOMES

EPA Science Inventory

Gasoline leaks from underground storage tanks can cause ground water contamination because there are a number of organic chemicals in gasoline. These chemicals have varying properties that influence how far contamination extends from the release. Research on transport of these ...

DEVELOPMENTAL TOXICITY OF PFOS AND PFOA

EPA Science Inventory

Perfluoroalkyl acids (PFAA) are fully-fluorinated organic chemicals with a carbon backbone (typically varying from C-4 to C-14) and a functional group (usually carboxylic acid or sulfonic acid). These chemicals are man-made, exceptionally stable to metabolic and environmental de...

The effect of nitrogen incorporation on the bonding structure of hydrogenated carbon nitride films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camero, M.; Buijnsters, J. G.; Gomez-Aleixandre, C.

2007-03-15

This work describes the composition and bonding structure of hydrogenated carbon nitride (a-CN{sub x}:H) films synthesized by electron cyclotron resonance chemical vapor deposition using as precursor gases argon, methane, and nitrogen. The composition of the films was derived from Rutherford backscattering and elastic recoil detection analysis and the bonding structure was examined by infrared (IR) spectroscopy and x-ray absorption near edge spectroscopy (XANES). By varying the nitrogen to methane ratio in the applied gas mixture, polymeric a-CN{sub x}:H films with N/C contents varying from 0.06 to 0.49 were obtained. Remarkably, the H content of the films ({approx}40 at. %) wasmore » rather unaffected by the nitrogenation process. The different bonding states as detected in the measured XANES C(1s) and N(1s) spectra have been correlated with those of a large number of reference samples. The XANES and IR spectroscopy results indicate that N atoms are efficiently incorporated into the amorphous carbon network and can be found in different bonding environments, such as pyridinelike, graphitelike, nitrilelike, and amino groups. The nitrogenation of the films results in the formation of N-H bonding environments at the cost of C-H structures. Also, the insertion of N induces a higher fraction of double bonds in the structure at the expense of the linear polymerlike chains, hence resulting in a more cross-linked solid. The formation of double bonds takes place through complex C=N structures and not by formation of graphitic aromatic rings. Also, the mechanical and tribological properties (hardness, friction, and wear) of the films have been studied as a function of the nitrogen content. Despite the major modifications in the bonding structure with nitrogen uptake, no significant changes in these properties are observed.« less

Graphene based tunable fractal Hilbert curve array broadband radar absorbing screen for radar cross section reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Xianjun, E-mail: xianjun.huang@manchester.ac.uk; College of Electronic Science and Engineering, National University of Defense Technology, Changsha 410073; Hu, Zhirun

2014-11-15

This paper proposes a new type of graphene based tunable radar absorbing screen. The absorbing screen consists of Hilbert curve metal strip array and chemical vapour deposition (CVD) graphene sheet. The graphene based screen is not only tunable when the chemical potential of the graphene changes, but also has broadband effective absorption. The absorption bandwidth is from 8.9GHz to 18.1GHz, ie., relative bandwidth of more than 68%, at chemical potential of 0eV, which is significantly wider than that if the graphene sheet had not been employed. As the chemical potential varies from 0 to 0.4eV, the central frequency of themore » screen can be tuned from 13.5GHz to 19.0GHz. In the proposed structure, Hilbert curve metal strip array was designed to provide multiple narrow band resonances, whereas the graphene sheet directly underneath the metal strip array provides tunability and averagely required surface resistance so to significantly extend the screen operation bandwidth by providing broadband impedance matching and absorption. In addition, the thickness of the screen has been optimized to achieve nearly the minimum thickness limitation for a nonmagnetic absorber. The working principle of this absorbing screen is studied in details, and performance under various incident angles is presented. This work extends applications of graphene into tunable microwave radar cross section (RCS) reduction applications.« less

A study of the sea-salt chemistry using size-segregated aerosol measurements at coastal Antarctic station Neumayer

NASA Astrophysics Data System (ADS)

Teinilä, K.; Frey, A.; Hillamo, R.; Tülp, H. C.; Weller, R.

2014-10-01

Aerosol chemical and physical properties were measured in 2010 at Neumayer research station, Antarctica. Samples for chemical analysis (ion chromatography) were collected using a Teflon/Nylon filter combination (TNy) sampler, and with a multi stage low pressure impactor (SDI). Particle number concentration was measured continuously with a Grimm OPC optical particle counter. Total particle number concentration varied largely throughout the year, and the highest number concentrations for particles larger than 0.3 μm were observed simultaneously with the highest sea salt concentrations. About 50% of the sea salt aerosol mass was found in the submicron size range. Below 0.2 μm of particle aerodynamic diameter the contribution of sea salt aerosols was negligible. Further analysis showed that sea salt aerosols had undergone physico-chemical processes, either during the transportation, or during their formation. High degree of chloride depletion was observed during austral summer, when the presence of acidic gases exhibit their characteristic seasonal maximum. Apart from chloride depletion, excess chloride relating to sodium was also detected in one SDI sample, indicating actually a sodium depletion by mirabilite formation on freshly formed sea ice areas. Analysis of selected episodes showed that the concentration of sea salt particles, their modal structure, and their chemical composition is connected with their source areas, their formation mechanisms, and local transport history.

Chemical evaluation of electronic cigarettes.

PubMed

Cheng, Tianrong

2014-05-01

To review the available evidence evaluating the chemicals in refill solutions, cartridges, aerosols and environmental emissions of electronic cigarettes (e-cigarettes). Systematic literature searches were conducted to identify research related to e-cigarettes and chemistry using 5 reference databases and 11 search terms. The search date range was January 2007 to September 2013. The search yielded 36 articles, of which 29 were deemed relevant for analysis. The levels of nicotine, tobacco-specific nitrosamines (TSNAs), aldehydes, metals, volatile organic compounds (VOCs), flavours, solvent carriers and tobacco alkaloids in e-cigarette refill solutions, cartridges, aerosols and environmental emissions vary considerably. The delivery of nicotine and the release of TSNAs, aldehydes and metals are not consistent across products. Furthermore, the nicotine level listed on the labels of e-cigarette cartridges and refill solutions is often significantly different from measured values. Phenolic compounds, polycyclic aromatic hydrocarbons and drugs have also been reported in e-cigarette refill solutions, cartridges and aerosols. Varying results in particle size distributions of particular matter emissions from e-cigarettes across studies have been observed. Methods applied for the generation and chemical analyses of aerosols differ across studies. Performance characteristics of e-cigarette devices also vary across and within brands. Additional studies based on knowledge of e-cigarette user behaviours and scientifically validated aerosol generation and chemical analysis methods would be helpful in generating reliable measures of chemical quantities. This would allow comparisons of e-cigarette aerosol and traditional smoke constituent levels and would inform an evaluation of the toxicity potential of e-cigarettes.

On the nature of the lowest electron transitions in the borine dye derivatives benz[cd]indole

NASA Astrophysics Data System (ADS)

Kachkovsky, O. D.; Yashchuk, V. M.; Navozenko, O. M.; Naumenko, A. P.; Slominskii, Yu. L.

2014-09-01

The fluorescence and absorption spectra of new boron-containing dyes have been analyzed in detail basing on the results of quantum chemical calculations that were performed to obtain the equilibrium molecular geometry and electron structure of the dye molecules. It has been found that the cyclization of both terminal groups by BF2 bridge changes the total charge in the symmetrical dyes and practically does not change the bond lengths in the π-electron system which increases the quantum yield of fluorescence. The possibility to vary the absorption region and total neutral charge makes these dyes promising for using as additives in light emitting layers of OLED deposited by vacuum evaporation.

Structural and optical properties of Ga auto-incorporated InAlN epilayers

NASA Astrophysics Data System (ADS)

Taylor, E.; Smith, M. D.; Sadler, T. C.; Lorenz, K.; Li, H. N.; Alves, E.; Parbrook, P. J.; Martin, R. W.

2014-12-01

InAlN epilayers deposited on thick GaN buffer layers grown by metalorganic chemical vapour deposition (MOCVD) revealed an auto-incorporation of Ga when analysed by wavelength dispersive x-ray (WDX) spectroscopy and Rutherford backscattering spectrometry (RBS). Samples were grown under similar conditions with the change in reactor flow rate resulting in varying Ga contents of 12-24%. The increase in flow rate from 8000 to 24 000 sccm suppressed the Ga auto-incorporation which suggests that the likely cause is from residual Ga left behind from previous growth runs. The luminescence properties of the resultant InAlGaN layers were investigated using cathodoluminescence (CL) measurements.

Luminescence properties of In(Zn)P alloy core/ZnS shell quantum dots

NASA Astrophysics Data System (ADS)

Thuy, Ung Thi Dieu; Reiss, Peter; Liem, Nguyen Quang

2010-11-01

Chemically synthesized InP/ZnS core/shell quantum dots (QDs) are studied using time-resolved photoluminescence spectroscopy and x-ray diffraction. Zinc stearate, which is added during the synthesis of the InP core, significantly improves the optical characteristics of the QDs. The luminescence quantum yield (QY) reaches 60%-70% and the emission is tunable from 485 to 586 nm by varying the Zn2+:In3+ molar ratio and growth temperature. The observed increased Stokes shift, luminescence decay time, and QY in the presence of Zn are rationalized by the formation of an In(Zn)P alloy structure that causes band-edge fluctuation to enhance the confinement of the excited carriers.

Wikipedia Chemical Structure Explorer: substructure and similarity searching of molecules from Wikipedia.

PubMed

Ertl, Peter; Patiny, Luc; Sander, Thomas; Rufener, Christian; Zasso, Michaël

2015-01-01

Wikipedia, the world's largest and most popular encyclopedia is an indispensable source of chemistry information. It contains among others also entries for over 15,000 chemicals including metabolites, drugs, agrochemicals and industrial chemicals. To provide an easy access to this wealth of information we decided to develop a substructure and similarity search tool for chemical structures referenced in Wikipedia. We extracted chemical structures from entries in Wikipedia and implemented a web system allowing structure and similarity searching on these data. The whole search as well as visualization system is written in JavaScript and therefore can run locally within a web page and does not require a central server. The Wikipedia Chemical Structure Explorer is accessible on-line at www.cheminfo.org/wikipedia and is available also as an open source project from GitHub for local installation. The web-based Wikipedia Chemical Structure Explorer provides a useful resource for research as well as for chemical education enabling both researchers and students easy and user friendly chemistry searching and identification of relevant information in Wikipedia. The tool can also help to improve quality of chemical entries in Wikipedia by providing potential contributors regularly updated list of entries with problematic structures. And last but not least this search system is a nice example of how the modern web technology can be applied in the field of cheminformatics. Graphical abstractWikipedia Chemical Structure Explorer allows substructure and similarity searches on molecules referenced in Wikipedia.

Inorganic Biominerals in Crustaceans are Structurally Independent of Organic Framework

NASA Astrophysics Data System (ADS)

Mergelsberg, S. T.; Michel, F. M.; Mukhopadhyay, B.; Dove, P. M.

2015-12-01

Biomineralization of calcium carbonate (CaCO3) as crystalline calcite or amorphous CaCO3 (ACC) occurs in the exoskeletons of all crustaceans. These cuticles are complex composites of inorganic mineral and organic macromolecules with highly divergent morphologies that are adapted to the extreme variations in environmental pressures within their diverse ecological niches. The remarkable variations and adaptations that form, infer a highly efficient and regulated mechanism for biomineralization that is most likely orchestrated by a myriad of biomacromolecules (Ziegler A 2012). The roles of these peptides and organic metabolites during CaCO3 biomineralization are not well understood. In part, this is due to a lack of knowledge of crustacean homeostasis. In a step toward understanding cuticle mineralization in crustaceans, this study asks: Which molecules affect biomineralization? Do the biomineral-active molecules vary greatly between species and body parts? Recent studies of polysaccharide controls on mineralization also raise the question of whether small heterogeneities in chitin, the most abundant biopolymer of the composite, could be primarily responsible for differences in CaCO3 crystallinity. This study used a novel spectroscopic approach to characterize the mineral and organic components of exoskeletons from three Malacostraca organisms — American Lobster (Homarus americanus), Dungeness Crab (Metacarcinus magister), and Red Rock Crab (Cancer productus). Using high-energy x-ray diffraction and Raman spectroscopy, the cuticles of three major body parts from these organisms were analyzed for the structure and bulk chemistry of its chitin and CaCO3 components. The findings indicate that Raman spectroscopy provides adequate resolution to show that crystallinity of chitin and the CaCO3 mineral component are chemically independent of each other, although their crystallinities co-vary for Brachyura species (Dungeness and Red Rock Crabs). Insights from this study suggest chitin provides the structural framework of the cuticle, without direct chemical control on the biomineralization of CaCO3. Peptides and small metabolites are likely to be more directly involved in the mechanisms controlling polymerization, crystallization, and composition of both chitin and CaCO3.

Seasonal variations in physico-chemical characteristics of Tuticorin coastal waters, southeast coast of India

NASA Astrophysics Data System (ADS)

Balakrishnan, S.; Chelladurai, G.; Mohanraj, J.; Poongodi, J.

2017-07-01

Physico-chemical parameters were determined along the Vellapatti, Tharuvaikulam and Threspuram coastal waters, southeast coast of India. All the physico-chemical parameters such as sea surface temperature, salinity, pH, total alkalinity, total suspended solids, dissolved oxygen and nutrients like nitrate, nitrite, inorganic phosphate and reactive silicate were studied for a period of 12 months (June 2014-May 2015). Sea surface temperature varied from 26.4 to 29.7 °C. Salinity varied from 26.1 and 36.2 ‰, hydrogen ion concentration ranged between 8.0 and 8.5. Variation in dissolved oxygen content was from 4.125 to 4.963 mg l-1. Total alkalinity ranged from 64 to 99 mg/l. Total suspended solids ranged from 24 to 97 mg/l. Concentrations of nutrients, viz. nitrates (2.047-4.007 μM/l), nitrites (0.215-0.840 μM/l), phosphates (0.167-0.904 µM/l), total phosphorus (1.039-3.479 μM/l), reactive silicates (3.737-8.876 μM/l) ammonia (0.078-0.526 μM/l) and also varied independently.

Distributed Structure Searchable Toxicity

EPA Pesticide Factsheets

The Distributed Structure Searchable Toxicity (DSSTox) online resource provides high quality chemical structures and annotations in association with toxicity data. It helps to build a data foundation for improved structure-activity relationships and predictive toxicology. DSSTox publishes summarized chemical activity representations for structure-activity modeling and provides a structure browser. This tool also houses the chemical inventories for the ToxCast and Tox21 projects.

Tidal river sediments in the Washington, D.C. area. 111 Biological effects associated with sediment contamination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schlekat, C.E.; McGee, B.L.; Boward, D.M.

1994-06-01

Sediment toxicity and benthic marcroinvertebrate community structure were measured as one component of a study conceived to determine the distribution and effect of sediment contamination in tidal freshwater portions of the Potomac and Anacostia rivers in the Washington, D.C., area. Samples were collected at 15 sites. Analyses included a partial life cycle (28 d) whole sediment test using the amphipod Hyalella azteca (Talitridae) and an assessment of benthic community structure. Survival and growth (as estimated by amphipod length) were experimental endpoints for the toxicity test. Significant mortality was observed in 5 to 10 sites in the lower Anacostia River basinmore » and at the main channel Potomac River site. Sublethal toxicity, as measured by inhibition of amphipod growth, was not observed. Toxicity test results were in general agreement with synoptically measured sediment contaminant concentrations. Porewater total ammonia (NH{sub 3} + NH{sub 4}{sup +}) appears to be responsible for the toxicity of sediments from the Potomac River, while correlation analysis and simultaneously extracted metals: acid volatile sulfide (SEM:AVA) results suggest that the toxicity associated with Anacostia River sediments was due to organic compounds. Twenty-eight macroinvertebrate taxa were identified among all sites, with richness varying from 5 to 17 taxa per site. Groups of benthic assemblages identified by group-average cluster analysis exhibited variable agreement with sediment chemical and sediment toxicity results. Integration of toxicological, chemical, and ecological components suggests that adverse environmental effects manifest in lower Anacostia River benthos result from chemical contamination of sediment. 37 refs., 2 figs., 7 tabs.« less

The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2016-04-09

An in-depth review is presented on the science of lithium-ion battery (LIB) solid electrolyte interphase (SEI) formation on the graphite anode, including structure, morphology, chemical composition, electrochemistry, formation mechanism, and LIB formation cycling. During initial operation of LIBs, the SEI layer forms on the graphite surfaces, the most commonly used anode material, due to side reactions with the electrolyte solvent/salt at low electro-reduction potentials. It is accepted that the SEI layer is essential to the long-term performance of LIBs, and it also has an impact on its initial capacity loss, self-discharge characteristics, cycle life, rate capability, and safety. While themore » presence of the anode SEI layer is vital, it is difficult to control its formation and growth, as the chemical composition, morphology, and stability depend on several factors. These factors include the type of graphite, electrolyte composition, electrochemical conditions, and cell temperature. Thus, SEI layer formation and electrochemical stability over long-term operation should be a primary topic of future investigation in the development of LIB technology. We review the progression of knowledge gained about the anode SEI, from its discovery in 1979 to the current state of understanding, and covers its formation process, differences in the chemical and structural makeup when cell materials and components are varied, methods of characterization, and associated reactions with the liquid electrolyte phase. It also discusses the relationship of the SEI layer to the LIB formation step, which involves both electrolyte wetting and subsequent slow charge-discharge cycles to grow the SEI.« less

PREDICTING EVAPORATION RATES AND TIMES FOR SPILLS OF CHEMICAL MIXTURES

EPA Science Inventory

Spreadsheet and short-cut methods have been developed for predicting evaporation rates and evaporation times for spills (and constrained baths) of chemical mixtures. Steady-state and time-varying predictions of evaporation rates can be made for six-component mixtures, includ...

How does EPA assess risks of chemicals to birds?

EPA Science Inventory

The U.S. Environmental Protection Agency (EPA) evaluates the risk of chemicals to birds and other non-target organisms using Ecological Risk Assessment (ERA). The specific evaluations conducted under an ERA typically vary by statutory authority and available data. Under the Fede...

USING PROTEOMICS TO MONITOR PROTEIN EXPRESSION IN HUMAN CELLS EXPOSED TO CARCINOGENS

EPA Science Inventory

People are continuously exposed exogenously to varying amounts of chemicals that have been shown to have carcinogenic properties in experimental systems. It has been estimated that exposure to environmental chemical carcinogens in the environment may contribute significantly to t...

MIXING RATIO INFLUENCES HALOACETIC ACID (HAA) MIXTURE TOXICITY

EPA Science Inventory

Mixtures of the same type (for example, disinfection byproduct mixtures) often contain the same chemicals, but at varying concentrations. The objective of the present study was to examine the influence of mixing ratio (the concentrations of chemicals relative to one another) on ...

Sensitivity of ab Initio vs Empirical Methods in Computing Structural Effects on NMR Chemical Shifts for the Example of Peptides.

PubMed

Sumowski, Chris Vanessa; Hanni, Matti; Schweizer, Sabine; Ochsenfeld, Christian

2014-01-14

The structural sensitivity of NMR chemical shifts as computed by quantum chemical methods is compared to a variety of empirical approaches for the example of a prototypical peptide, the 38-residue kaliotoxin KTX comprising 573 atoms. Despite the simplicity of empirical chemical shift prediction programs, the agreement with experimental results is rather good, underlining their usefulness. However, we show in our present work that they are highly insensitive to structural changes, which renders their use for validating predicted structures questionable. In contrast, quantum chemical methods show the expected high sensitivity to structural and electronic changes. This appears to be independent of the quantum chemical approach or the inclusion of solvent effects. For the latter, explicit solvent simulations with increasing number of snapshots were performed for two conformers of an eight amino acid sequence. In conclusion, the empirical approaches neither provide the expected magnitude nor the patterns of NMR chemical shifts determined by the clearly more costly ab initio methods upon structural changes. This restricts the use of empirical prediction programs in studies where peptide and protein structures are utilized for the NMR chemical shift evaluation such as in NMR refinement processes, structural model verifications, or calculations of NMR nuclear spin relaxation rates.

Toxic Environmental Chemicals: The Role of Reproductive Health Professionals In Preventing Harmful Exposures

PubMed Central

SUTTON, Patrice; WOODRUFF, Tracey J.; PERRON, Joanne; STOTLAND, Naomi; CONRY, Jeanne A.; MILLER, Mark D.; GIUDICE, Linda C.

2015-01-01

Every pregnant woman in the U.S. is exposed to many and varied environmental chemicals. Rapidly accumulating scientific evidence documents that widespread exposure to environmental chemicals at levels encountered in daily life can adversely impact reproductive and developmental health. Preconception and prenatal exposure to environmental chemicals are of particular import because they may have a profound and lasting impact on health across the life course. Thus, preventing developmental exposures to environmental chemicals would benefit greatly from the active participation of reproductive health professionals in clinical and policy arenas. PMID:22405527

Constraints on Lunar Structure from Combined Geochemical, Mineralogical, and Geophysical modeling

NASA Astrophysics Data System (ADS)

Bremner, P. M.; Fuqua, H.; Mallik, A.; Diamond, M. R.; Lock, S. J.; Panovska, S.; Nishikawa, Y.; Jiménez-Pérez, H.; Shahar, A.; Panero, W. R.; Lognonne, P. H.; Faul, U.

2016-12-01

The internal physical and geochemical structure of the Moon is still poorly constrained. Here, we take a multidisciplinary approach to attempt to constrain key parameters of the lunar structure. We use an ensemble of 1-D lunar compositional models with chemically and mineralogically distinct layers, and forward calculated physical parameters, in order to constrain the internal structure. We consider both a chemically well-mixed model with uniform bulk composition, and a chemically stratified model that includes a mantle with preserved mineralogical stratigraphy from magma ocean crystallization. Additionally, we use four different lunar temperature profiles that span the range of proposed selenotherms, giving eight separate sets of lunar models. In each set, we employed a grid search and a differential evolution genetic search algorithm to extensively explore model space, where the thickness of individual compositional layers was varied. In total, we forward calculated over one hundred thousand lunar models. It has been proposed that a dense, partially molten layer exists at the CMB to explain the lack of observed far-side deep moonquakes, the observation of reflected seismic phases from deep moonquakes, and enhanced tidal dissipation. However, subsequent models have proposed that these observables can be explained in other ways. In this study, using a variety of modeling techniques, we find that such a layer may have been formed by overturn of an ilmenite-rich layer, formed after the crystallization of a magma ocean. We therefore include a denser layer (modeled as an ilmenite-rich layer) at both the top and bottom of the lunar mantle in our models. For each set of models, we find models that explain the observed lunar mass and moment of inertia. We find that only a narrow range of core radii are consistent with the mass and moment of inertia constraints. Furthermore, in the chemically well-mixed models, we find that a dense layer is required in the upper mantle to meet the moment of inertia requirement. In no set of models is the mass of the lower dense layer well constrained. For the models that fit the observed mass and moment of inertia, we calculated 1-D seismic velocity profiles, the majority of which compare well with those determined by inverting the Apollo seismic data (Garcia et al., 2011 and Weber et al., 2011).

Automated compound classification using a chemical ontology.

PubMed

Bobach, Claudia; Böhme, Timo; Laube, Ulf; Püschel, Anett; Weber, Lutz

2012-12-29

Classification of chemical compounds into compound classes by using structure derived descriptors is a well-established method to aid the evaluation and abstraction of compound properties in chemical compound databases. MeSH and recently ChEBI are examples of chemical ontologies that provide a hierarchical classification of compounds into general compound classes of biological interest based on their structural as well as property or use features. In these ontologies, compounds have been assigned manually to their respective classes. However, with the ever increasing possibilities to extract new compounds from text documents using name-to-structure tools and considering the large number of compounds deposited in databases, automated and comprehensive chemical classification methods are needed to avoid the error prone and time consuming manual classification of compounds. In the present work we implement principles and methods to construct a chemical ontology of classes that shall support the automated, high-quality compound classification in chemical databases or text documents. While SMARTS expressions have already been used to define chemical structure class concepts, in the present work we have extended the expressive power of such class definitions by expanding their structure-based reasoning logic. Thus, to achieve the required precision and granularity of chemical class definitions, sets of SMARTS class definitions are connected by OR and NOT logical operators. In addition, AND logic has been implemented to allow the concomitant use of flexible atom lists and stereochemistry definitions. The resulting chemical ontology is a multi-hierarchical taxonomy of concept nodes connected by directed, transitive relationships. A proposal for a rule based definition of chemical classes has been made that allows to define chemical compound classes more precisely than before. The proposed structure-based reasoning logic allows to translate chemistry expert knowledge into a computer interpretable form, preventing erroneous compound assignments and allowing automatic compound classification. The automated assignment of compounds in databases, compound structure files or text documents to their related ontology classes is possible through the integration with a chemical structure search engine. As an application example, the annotation of chemical structure files with a prototypic ontology is demonstrated.

Automated compound classification using a chemical ontology

PubMed Central

2012-01-01

Background Classification of chemical compounds into compound classes by using structure derived descriptors is a well-established method to aid the evaluation and abstraction of compound properties in chemical compound databases. MeSH and recently ChEBI are examples of chemical ontologies that provide a hierarchical classification of compounds into general compound classes of biological interest based on their structural as well as property or use features. In these ontologies, compounds have been assigned manually to their respective classes. However, with the ever increasing possibilities to extract new compounds from text documents using name-to-structure tools and considering the large number of compounds deposited in databases, automated and comprehensive chemical classification methods are needed to avoid the error prone and time consuming manual classification of compounds. Results In the present work we implement principles and methods to construct a chemical ontology of classes that shall support the automated, high-quality compound classification in chemical databases or text documents. While SMARTS expressions have already been used to define chemical structure class concepts, in the present work we have extended the expressive power of such class definitions by expanding their structure-based reasoning logic. Thus, to achieve the required precision and granularity of chemical class definitions, sets of SMARTS class definitions are connected by OR and NOT logical operators. In addition, AND logic has been implemented to allow the concomitant use of flexible atom lists and stereochemistry definitions. The resulting chemical ontology is a multi-hierarchical taxonomy of concept nodes connected by directed, transitive relationships. Conclusions A proposal for a rule based definition of chemical classes has been made that allows to define chemical compound classes more precisely than before. The proposed structure-based reasoning logic allows to translate chemistry expert knowledge into a computer interpretable form, preventing erroneous compound assignments and allowing automatic compound classification. The automated assignment of compounds in databases, compound structure files or text documents to their related ontology classes is possible through the integration with a chemical structure search engine. As an application example, the annotation of chemical structure files with a prototypic ontology is demonstrated. PMID:23273256

Effects of Dissolved Organic Matter Properties on Formation and Composition of Mineral-Organic Co-Precipitates at the Nanometer Scale

NASA Astrophysics Data System (ADS)

Possinger, A. R.; Zachman, M.; Lehmann, J.

2016-12-01

An important, yet largely overlooked case of soil organic carbon (SOC) stabilization through mineral-organic associations is the co-precipitation of dissolved organic matter (DOM) into mineral precipitates as they form. The contribution of co-precipitated DOM to the mineral-stabilized SOC pool is expected to be greatest in soil environments with frequent mineral dissolution and precipitation processes. Compared to surface adsorption, properties of mineral-organic co-precipitates are expected to differ at both the particle scale (e.g., total carbon (C) content and composition) and the molecular scale (e.g., impurities in mineral structure), with potential implications for stability and C turnover; additionally, these properties vary across C sources, amounts, and forms. Consequently, high-resolution visualization and characterization combined with bulk chemical measurements is needed to provide a more complete understanding of co-precipitate formation processes and properties, especially as a function of C co-precipitant characteristics. In this study, we evaluate the effect of model C compound and DOM chemical properties (e.g., iron-binding affinity) on the formation, structure, and chemical properties of ferrihydrite (Fh) (Fe3+3O2 •0.5H2O) co-precipitates. Salicylic acid (SA), sucrose and water-extractable DOM from coniferous or deciduous-dominated organic soils were either adsorbed to pre-formed Fh or co-precipitated with Fh. At a C/Fe ratio 10, the amount of co-precipitated C differed among all organic compounds, and for DOM, was more than 2X greater for co-precipitation than adsorption, suggesting a greater capacity for C retention. To probe the molecular-scale C spatial distribution of Fh-SA particles, we obtained Scanning Transmission Electron Microscopy with Electron Energy Loss Spectroscopy (STEM-EELS) maps at a nanometer-scale spatial pixel resolution. Additionally, we will present chemical characteristics of organic-Fh co-precipitates and adsorption complexes investigated in bulk using C Near-Edge X-ray Absorption Fine Structure (NEXAFS) and Fourier Transform Infrared (FT-IR) spectroscopy. Ultimately, these observations of model co-precipitation systems will be used to better interpret observations of putative co-precipitated OM in natural soils.

Structure-activity relationship of chemical penetration enhancers in transdermal drug delivery.

PubMed

Kanikkannan, N; Kandimalla, K; Lamba, S S; Singh, M

2000-06-01

Transdermal drug delivery (TDD) is the administration of therapeutic agents through intact skin for systemic effect. TDD offers several advantages over the conventional dosage forms such as tablets, capsules and injections. Currently there are about eight drugs marketed as transdermal patches. Examples of such products include nitroglycerin (angina pectoris), clonidine (hypertension), scopolamine (motion sickness), nicotine (smoking cessation), fentanil (pain) and estradiol (estrogen deficiency). Since skin is an excellent barrier for drug transport, only potent drugs with appropriate physicochemical properties (low molecular weight, adequate solubility in aqueous and non-aqueous solvents, etc) are suitable candidates for transdermal delivery. Penetration enhancement technology is a challenging development that would increase significantly the number of drugs available for transdermal administration. The permeation of drugs through skin can be enhanced by physical methods such as iontophoresis (application of low level electric current) and phonophoresis (use of ultra sound energy) and by chemical penetration enhancers (CPE). In this review, we have discussed about the CPE which have been investigated for TDD. CPE are compounds that enhance the permeation of drugs across the skin. The CPE increase skin permeability by reversibly altering the physicochemical nature of the stratum corneum, the outer most layer of skin, to reduce its diffusional resistance. These compounds increase skin permeability also by increasing the partition coefficient of the drug into the skin and by increasing the thermodynamic activity of the drug in the vehicle. This review compiles the various CPE used for the enhancement of TDD, the mechanism of action of different chemical enhancers and the structure-activity relationship of selected and extensively studied enhancers such as fatty acids, fatty alcohols and terpenes. Based on the chemical structure of penetration enhancers (such as chain length, polarity, level of unsaturation and presence of some special groups such as ketones), the interaction between the stratum corneum and penetration enhancers may vary which will result in significant differences in penetration enhancement. Our review also discusses the various factors to be considered in the selection of an appropriate penetration enhancer for the development of transdermal delivery systems.

Influence of ammonium hydroxide solution on LiMn2O4 nanostructures prepared by modified chemical bath method

NASA Astrophysics Data System (ADS)

Koao, Lehlohonolo F.; Motloung, Setumo V.; Motaung, Tshwafo E.; Kebede, Mesfin A.

2018-04-01

LiMn2O4 (LMO) powders were prepared by modified chemical bath deposition (CBD) method by varying ammonium hydroxide solution (AHS). The volume of the AHS was varied from 5 to 120 mL in order to determine the optimum volume that is needed for preparation of LMO powders. The effect of AHS volume on the structure, morphology, and electrochemical properties of LMO powders was investigated. The X-ray diffraction (XRD) patterns of the LMO powders correspond to the cubic spinel LMO phase. It was found that the XRD peaks increased in intensity with increasing volume of the AHS up to 20 mL. The estimated average grain sizes calculated using the XRD patterns were found to be in the order of 66 ± 1 nm. It was observed that the estimated average grain sizes increased up to 20 mL of AHS. The scanning electron microscopy (SEM) results revealed that the AHS volume does not influence the surface morphology of the prepared nano-powders. Elemental energy dispersive (EDS) analysis mapping conducted on the samples revealed homogeneous distribution of Mn and O for the sample synthesized with 120 mL of AHS. The UV-Vis spectra showed a red shift with an increase in AHS up 20 mL. The cyclic voltammetry and galvanostatic charge/discharge cycle testing confirmed that 20 mL of AHS has superior lithium ion kinetics and electrochemical performance.

Shining light on the differences in molecular structural chemical makeup and the cause of distinct degradation behavior between malting- and feed-type barley using synchrotron FTIR microspectroscopy: a novel approach.

PubMed

Yu, Peiqiang; Doiron, Kevin; Liu, Dasen

2008-05-14

The objective of this study was to use advanced synchrotron-sourced FTIR microspectroscopy (SFTIRM) as a novel approach to identify the differences in protein and carbohydrate molecular structure (chemical makeup) between these two varieties of barley and illustrate the exact causes for their significantly different degradation kinetics. Items assessed included (1) molecular structural differences in protein amide I to amide II intensities and their ratio within cellular dimensions, (2) molecular structural differences in protein secondary structure profile and their ratios, and (3) molecular structural differences in carbohydrate component peak profile. Our hypothesis was that molecular structure (chemical makeup) affects barley quality, fermentation, and degradation behavior in both humans and animals. Using SFTIRM, the protein and carbohydrate molecular structural chemical makeup of barley was revealed and identified. The protein molecular structural chemical makeup differed significantly between the two varieties of barleys. No difference in carbohydrate molecular structural chemical makeup was detected. Harrington was lower than Valier in protein amide I, amide II, and protein amide I to amide II ratio, while Harrington was relatively higher in model-fitted protein alpha-helix and beta-sheet, but lower in the others (beta-turn and random coil). These results indicated that it is the molecular structure of protein (chemical makeup) that may play a major role in the different degradation kinetics between the two varieties of barleys (not the molecular structure of carbohydrate). It is believed that use of the advanced synchrotron technology will make a significant step and an important contribution to research in examining the molecular structure (chemical makeup) of plant, feed, and seeds.

Digital image processing based identification of nodes and internodes of chopped biomass stems

USDA-ARS?s Scientific Manuscript database

Chemical composition of biomass feedstock is an important parameter for optimizing the yield and economics of various bioconversion pathways. Although understandably, the chemical composition of biomass varies among species, varieties, and plant components, there is distinct variation even among ste...

Environmental chemical mixtures: Assessing ecological exposure and effects in streams

EPA Science Inventory

This product is a USGS fact sheet that describes a collaborative effort between USGS and US EPA to characterize exposures to chemical mixtures and associated biological effects for a diverse range of US streams representing varying watershed size, land-use patterns, and ecotypes.

Greener Syntheses and Chemical Transformations: Sustainable Alternative Methods and Applications of Nano-Catalysts. (Florence, Italy)

EPA Science Inventory

The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions. The synthesis of heterocyclic compounds, coupling reactions, and a vari...

Chemical synthesis of erythropoietin glycoforms for insights into the relationship between glycosylation pattern and bioactivity

PubMed Central

Murakami, Masumi; Kiuchi, Tatsuto; Nishihara, Mika; Tezuka, Katsunari; Okamoto, Ryo; Izumi, Masayuki; Kajihara, Yasuhiro

2016-01-01

The role of sialyloligosaccharides on the surface of secreted glycoproteins is still unclear because of the difficulty in the preparation of sialylglycoproteins in a homogeneous form. We selected erythropoietin (EPO) as a target molecule and designed an efficient synthetic strategy for the chemical synthesis of a homogeneous form of five EPO glycoforms varying in glycosylation position and the number of human-type biantennary sialyloligosaccharides. A segment coupling strategy performed by native chemical ligation using six peptide segments including glycopeptides yielded homogeneous EPO glycopeptides, and folding experiments of these glycopeptides afforded the correctly folded EPO glycoforms. In an in vivo erythropoiesis assay in mice, all of the EPO glycoforms displayed biological activity, in particular the EPO bearing three sialyloligosaccharides, which exhibited the highest activity. Furthermore, we observed that the hydrophilicity and biological activity of the EPO glycoforms varied depending on the glycosylation pattern. This knowledge will pave the way for the development of homogeneous biologics by chemical synthesis. PMID:26824070

Quantitative Analysis of Electron Beam Damage in Organic Thin Films

PubMed Central

2017-01-01

In transmission electron microscopy (TEM) the interaction of an electron beam with polymers such as P3HT:PCBM photovoltaic nanocomposites results in electron beam damage, which is the most important factor limiting acquisition of structural or chemical data at high spatial resolution. Beam effects can vary depending on parameters such as electron dose rate, temperature during imaging, and the presence of water and oxygen in the sample. Furthermore, beam damage will occur at different length scales. To assess beam damage at the angstrom scale, we followed the intensity of P3HT and PCBM diffraction rings as a function of accumulated electron dose by acquiring dose series and varying the electron dose rate, sample preparation, and the temperature during acquisition. From this, we calculated a critical dose for diffraction experiments. In imaging mode, thin film deformation was assessed using the normalized cross-correlation coefficient, while mass loss was determined via changes in average intensity and standard deviation, also varying electron dose rate, sample preparation, and temperature during acquisition. The understanding of beam damage and the determination of critical electron doses provides a framework for future experiments to maximize the information content during the acquisition of images and diffraction patterns with (cryogenic) transmission electron microscopy. PMID:28553431

Theoretical studies of ground and excited electronic States in a series of rhenium(i) bipyridine complexes containing diarylethynyl-based structure.

PubMed

Yang, Li; Ren, Ai-Min; Feng, Ji-Kang; Liu, Xiao-Dong; Ma, Yu-Guang; Zhang, Hong-Xing

2004-09-20

The photophysical properties, which vary as X is varied, of Re(I)-halide complexes (X2-bpy)ReICl(CO)3 (where X=ph, DAE, DNE, and DPE; ph = phenyl (1); DAE = di(amineoethynylbenzene) (2); DPE = di(phenylethynylbenzene) (3); DNE = di(nitroethynylbenzene) (4); bpy=2,2'bipyridine), are investigated using density functional theory (DFT). The electronic properties of the neutral molecules, in addition to the positive and negative ions, are studied using B3LYP functional. Excited singlet and triplet states are examined using time-dependent density functional theory (TDDFT). The low-lying excited-state geometries are optimized at the ab initio configuration interaction singlets level. As shown, the diarylethynyl-based structure is an integral component of the bpy pi-conjugated network, which results in a good planar structure. The occupied orbitals involved in the transitions have a significant mixture of metal Re and group Cl, and the lowest unoccupied orbital is a pi orbital, which extends from ligand bpy to diarylethynyl-based substituents. The luminescence for each complex originates from the lowest triplet excited states and is assigned to the mixing of MLCT and LLCT characters. Significant insights on the effects of these diarylethynyl conjugated structure and ending substituents (NH2, ph, and NO2) on absorption and emission spectra are observed by analysis of the results of the TDDFT method. The diarylethynyl-based pi-conjugated network makes both the absorption and emission spectra red-shifted compared with simple complex (bpy)ReICl(CO)3. Furthermore, an electron-releasing group (NH2) makes absorption and emission spectra blue-shift and an electron-withdrawing group (NO2) makes them red-shift. Copyright 2004 American Chemical Society

Cruel disease, cruel medicine: self-treatment of cutaneous leishmaniasis with harmful chemical substances in Suriname.

PubMed

Ramdas, Sahienshadebie

2012-09-01

Why are potentially harmful, non-biomedical chemical substances, such as battery acid, chlorine, herbicides, and insecticides, used in the treatment of cutaneous leishmaniasis (CL)? What drives people to use these products as medicine? This article is about perceptions of CL, and the quest for a cure, in Suriname, South America. It highlights the associative style of reasoning behind health seeking and discusses the use of harmful chemical substances as medicines. Cutaneous leishmaniasis, a parasitic disease, affects 1 to 1.5 million people globally. It has a spectrum of clinical manifestations, but the most prominent and disfiguring elements are extensive dermatological ulceration and scar formation from lesions. The data upon which this article is based are derived from anthropological research carried out in different parts of Suriname between September 2009 and December 2010. Data was collected through mainly qualitative methods, including interviewing 205 CL patients using structured questionnaires at the Dermatological Service in the capital Paramaribo. Almost all people with CL said they tried self-treatment, varying from the use of ethno-botanical products to non-biomedical chemical solutions. This article presents and interprets the views and practices of CL patients who sought treatment using harsh chemicals. It argues that a confluence of contextual factors - environmental, occupational, infrastructural, geographical, socio-cultural, economic, socio-psychological - leads to the use of harmful chemical substances to treat CL sores. This study is the first in Suriname - and one of the few done globally - focusing on social and cultural aspects related to CL health seeking. It aims to encourage health policy makers and health professionals to carefully initiate, provide, and evaluate CL treatment and prevention programs. Copyright © 2012 Elsevier Ltd. All rights reserved.

ECOSAR model performance with a large test set of industrial chemicals.

PubMed

Reuschenbach, Peter; Silvani, Maurizio; Dammann, Martina; Warnecke, Dietmar; Knacker, Thomas

2008-05-01

The widely used ECOSAR computer programme for QSAR prediction of chemical toxicity towards aquatic organisms was evaluated by using large data sets of industrial chemicals with varying molecular structures. Experimentally derived toxicity data covering acute effects on fish, Daphnia and green algae growth inhibition of in total more than 1,000 randomly selected substances were compared to the prediction results of the ECOSAR programme in order (1) to assess the capability of ECOSAR to correctly classify the chemicals into defined classes of aquatic toxicity according to rules of EU regulation and (2) to determine the number of correct predictions within tolerance factors from 2 to 1,000. Regarding ecotoxicity classification, 65% (fish), 52% (Daphnia) and 49% (algae) of the substances were correctly predicted into the classes "not harmful", "harmful", "toxic" and "very toxic". At all trophic levels about 20% of the chemicals were underestimated in their toxicity. The class of "not harmful" substances (experimental LC/EC(50)>100 mg l(-1)) represents nearly half of the whole data set. The percentages for correct predictions of toxic effects on fish, Daphnia and algae growth inhibition were 69%, 64% and 60%, respectively, when a tolerance factor of 10 was allowed. Focussing on those experimental results which were verified by analytically measured concentrations, the predictability for Daphnia and algae toxicity was improved by approximately three percentage points, whereas for fish no improvement was determined. The calculated correlation coefficients demonstrated poor correlation when the complete data set was taken, but showed good results for some of the ECOSAR chemical classes. The results are discussed in the context of literature data on the performance of ECOSAR and other QSAR models.

Field-assisted synthesis of SERS-active silver nanoparticles using conducting polymers

NASA Astrophysics Data System (ADS)

Xu, Ping; Jeon, Sea-Ho; Mack, Nathan H.; Doorn, Stephen K.; Williams, Darrick J.; Han, Xijiang; Wang, Hsing-Lin

2010-08-01

A gradient of novel silver nanostructures with widely varying sizes and morphologies is fabricated on a single conducting polyaniline-graphite (P-G) membrane with the assistance of an external electric field. It is believed that the formation of such a silver gradient is a synergetic consequence of the generation of a silver ion concentration gradient along with an electrokinetic flow of silver ions in the field-assisted model, which greatly influences the nucleation and growth mechanism of Ag particles on the P-G membrane. The produced silver dendrites, flowers and microspheres, with sharp edges, intersections and bifurcations, all present strong surface enhanced Raman spectroscopy (SERS) responses toward an organic target molecule, mercaptobenzoic acid (MBA). This facile field-assisted synthesis of Ag nanoparticles via chemical reduction presents an alternative approach to nanomaterial fabrication, which can yield a wide range of unique structures with enhanced optical properties that were previously inaccessible by other synthetic routes.A gradient of novel silver nanostructures with widely varying sizes and morphologies is fabricated on a single conducting polyaniline-graphite (P-G) membrane with the assistance of an external electric field. It is believed that the formation of such a silver gradient is a synergetic consequence of the generation of a silver ion concentration gradient along with an electrokinetic flow of silver ions in the field-assisted model, which greatly influences the nucleation and growth mechanism of Ag particles on the P-G membrane. The produced silver dendrites, flowers and microspheres, with sharp edges, intersections and bifurcations, all present strong surface enhanced Raman spectroscopy (SERS) responses toward an organic target molecule, mercaptobenzoic acid (MBA). This facile field-assisted synthesis of Ag nanoparticles via chemical reduction presents an alternative approach to nanomaterial fabrication, which can yield a wide range of unique structures with enhanced optical properties that were previously inaccessible by other synthetic routes. Electronic supplementary information (ESI) available: EDAX, XRD, and SEM images. See DOI: 10.1039/c0nr00106f

Tautomerism in chemical information management systems

NASA Astrophysics Data System (ADS)

Warr, Wendy A.

2010-06-01

Tautomerism has an impact on many of the processes in chemical information management systems including novelty checking during registration into chemical structure databases; storage of structures; exact and substructure searching in chemical structure databases; and depiction of structures retrieved by a search. The approaches taken by 27 different software vendors and database producers are compared. It is hoped that this comparison will act as a discussion document that could ultimately improve databases and software for researchers in the future.

Identification of nodes and internodes of chopped biomass stems by Image analysis

USDA-ARS?s Scientific Manuscript database

Separating the morphological components of biomass leads to better handling, more efficient processing as well as value added product generation, as these components vary in their chemical composition and can be preferentially utilized. Nodes and internodes of biomass stems have distinct chemical co...

Mapping Pesticide Partition Coefficients By Electromagnetic Induction

USDA-ARS?s Scientific Manuscript database

A potential method for reducing pesticide leaching is to base application rates on the leaching potential of a specific chemical and soil combination. However, leaching is determined in part by the partitioning of the chemical between the soil and soil solution, which varies across a field. Standard...

Development of a nonlocal convective mixing scheme with varying upward mixing rates for use in air quality and chemical transport models.

PubMed

Mihailović, Dragutin T; Alapaty, Kiran; Sakradzija, Mirjana

2008-06-01

Asymmetrical convective non-local scheme (CON) with varying upward mixing rates is developed for simulation of vertical turbulent mixing in the convective boundary layer in air quality and chemical transport models. The upward mixing rate form the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. This scheme provides a less rapid mass transport out of surface layer into other layers than other asymmetrical convective mixing schemes. In this paper, we studied the performance of a nonlocal convective mixing scheme with varying upward mixing in the atmospheric boundary layer and its impact on the concentration of pollutants calculated with chemical and air-quality models. This scheme was additionally compared versus a local eddy-diffusivity scheme (KSC). Simulated concentrations of NO(2) and the nitrate wet deposition by the CON scheme are closer to the observations when compared to those obtained from using the KSC scheme. Concentrations calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme (of the order of 15-20%). Nitrate wet deposition calculated with the CON scheme are in general higher and closer to the observations than those obtained by the KSC scheme. To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO(2)) and nitrate wet deposition was compared for the year 2002. The comparison was made for the whole domain used in simulations performed by the chemical European Monitoring and Evaluation Programme Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.