Structural resolution of inorganic nanotubes with complex stoichiometry.

PubMed

Monet, Geoffrey; Amara, Mohamed S; Rouzière, Stéphan; Paineau, Erwan; Chai, Ziwei; Elliott, Joshua D; Poli, Emiliano; Liu, Li-Min; Teobaldi, Gilberto; Launois, Pascale

2018-05-23

Determination of the atomic structure of inorganic single-walled nanotubes with complex stoichiometry remains elusive due to the too many atomic coordinates to be fitted with respect to X-ray diffractograms inherently exhibiting rather broad features. Here we introduce a methodology to reduce the number of fitted variables and enable resolution of the atomic structure for inorganic nanotubes with complex stoichiometry. We apply it to recently synthesized methylated aluminosilicate and aluminogermanate imogolite nanotubes of nominal composition (OH) 3 Al 2 O 3 Si(Ge)CH 3 . Fitting of X-ray scattering diagrams, supported by Density Functional Theory simulations, reveals an unexpected rolling mode for these systems. The transferability of the approach opens up for improved understanding of structure-property relationships of inorganic nanotubes to the benefit of fundamental and applicative research in these systems.

Laser-induced breakdown spectroscopy (LIBS) technique for the determination of the chemical composition of complex inorganic materials

NASA Astrophysics Data System (ADS)

Łazarek, Łukasz; Antończak, Arkadiusz J.; Wójcik, Michał R.; Kozioł, Paweł E.; Stepak, Bogusz; Abramski, Krzysztof M.

2014-08-01

Laser-induced breakdown spectroscopy (LIBS) is a fast, fully optical method, that needs little or no sample preparation. In this technique qualitative and quantitative analysis is based on comparison. The determination of composition is generally based on the construction of a calibration curve namely the LIBS signal versus the concentration of the analyte. Typically, to calibrate the system, certified reference materials with known elemental composition are used. Nevertheless, such samples due to differences in the overall composition with respect to the used complex inorganic materials can influence significantly on the accuracy. There are also some intermediate factors which can cause imprecision in measurements, such as optical absorption, surface structure, thermal conductivity etc. This paper presents the calibration procedure performed with especially prepared pellets from the tested materials, which composition was previously defined. We also proposed methods of post-processing which allowed for mitigation of the matrix effects and for a reliable and accurate analysis. This technique was implemented for determination of trace elements in industrial copper concentrates standardized by conventional atomic absorption spectroscopy with a flame atomizer. A series of copper flotation concentrate samples was analyzed for contents of three elements, that is silver, cobalt and vanadium. It has been shown that the described technique can be used to qualitative and quantitative analyses of complex inorganic materials, such as copper flotation concentrates.

Properties- and applications of quasicrystals and complex metallic alloys.

PubMed

Dubois, Jean-Marie

2012-10-21

This article aims at an account of what is known about the potential for applications of quasicrystals and related compounds, the so-called family of Complex Metallic Alloys (CMAs‡). Attention is focused at aluminium-based CMAs, which comprise a large number of crystalline compounds and quasicrystals made of aluminium alloyed with transition metals (like Fe or Cu) or normal metals like Mg. Depending on composition, the structural complexity varies from a few atoms per unit cell up to thousands of atoms. Quasicrystals appear then as CMAs of ultimate complexity and exhibit a lattice that shows no periodicity anymore in the usual 3-dimensional space. Properties change dramatically with lattice complexity and turn the metal-type behaviour of simple Al-based crystals into a far more complex behaviour, with a fingerprint of semi-conductors that may be exploited in various applications, potential or realised. An account of the ones known to the author is given in the light of the relevant properties, namely light absorption, reduced adhesion and friction, heat insulation, reinforcement of composites for mechanical devices, and few more exotic ones. The role played by the search for applications of quasicrystals in the development of the field is briefly addressed in the concluding section.

Structural building principles of complex face-centered cubic intermetallics.

PubMed

Dshemuchadse, Julia; Jung, Daniel Y; Steurer, Walter

2011-08-01

Fundamental structural building principles are discussed for all 56 known intermetallic phases with approximately 400 or more atoms per unit cell and space-group symmetry F43m, Fd3m, Fd3, Fm3m or Fm3c. Despite fundamental differences in chemical composition, bonding and electronic band structure, their complex crystal structures show striking similarities indicating common building principles. We demonstrate that the structure-determining elements are flat and puckered atomic {110} layers stacked with periodicities 2p. The atoms on this set of layers, which intersect each other, form pentagon face-sharing endohedral fullerene-like clusters arranged in a face-centered cubic packing (f.c.c.). Due to their topological layer structure, all these crystal structures can be described as (p × p × p) = p(3)-fold superstructures of a common basic structure of the double-diamond type. The parameter p, with p = 3, 4, 7 or 11, is determined by the number of layers per repeat unit and the type of cluster packing, which in turn are controlled by chemical composition.

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

Stair, Peter C.

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supportedmore » metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.« less

Bimetallic Platinum-Rhodium Alloy Nanodendrites as Highly Active Electrocatalyst for the Ethanol Oxidation Reaction.

PubMed

Bai, Juan; Xiao, Xue; Xue, Yuan-Yuan; Jiang, Jia-Xing; Zeng, Jing-Hui; Li, Xi-Fei; Chen, Yu

2018-06-13

Rationally designing and manipulating composition and morphology of precious metal-based bimetallic nanostructures can markedly enhance their electrocatalytic performance, including selectivity, activity, and durability. We herein report the synthesis of bimetallic PtRh alloy nanodendrites (ANDs) with tunable composition by a facile complex-reduction synthetic method under hydrothermal conditions. The structural/morphologic features, formation mechanism, and electrocatalytic performance of PtRh ANDs are investigated thoroughly by various physical characterization and electrochemical methods. The preformed Rh crystal nuclei effectively catalyze the reduction of Pt 2+ precursor, resulting in PtRh alloy generation due to the catalytic growth and atoms interdiffusion process. The Pt atoms deposition distinctly interferes in Rh atoms deposition on Rh crystal nuclei, resulting in dendritic morphology of PtRh ANDs. For the ethanol oxidation reaction (EOR), PtRh ANDs display the chemical composition and solution pH co-dependent electrocatalytic activity. Because of the alloy effect and particular morphologic feature, Pt 1 Rh 1 ANDs with optimized composition exhibit better reactivity and stability for the EOR than commercial Pt nanocrystals electrocatalyst.

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

Chumakov, Yu. M.; Paholnitcaia, A. Yu.; Petrenko, P. A.

Two crystal modifications of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper (I and II) and two modifications of chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordinationmore » polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated (2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper possesses antitumor activity.« less

Complexation of molecular clips containing fragments of diphenylglycoluril and benzocrown ethers with paraquat and its derivatives

PubMed Central

Kikot', Leonid S; Kulygina, Catherine Yu; Lyapunov, Alexander Yu; Shishkina, Svetlana V; Zubatyuk, Roman I; Bogaschenko, Tatiana Yu

2017-01-01

The complexation of molecular clips containing fragments of diphenylglycoluril and benzocrown ethers with paraquat and its derivatives has been studied both in solution and in the solid state. In this paper we studied the influence of the crown ether ring size and the nature of the substituents at the nitrogen atoms of the paraquat derivatives on the composition and stability of these complexes. PMID:29062427

Role of chemically and thermally induced crystal lattice distortion in enhancing the Seebeck coefficient in complex tellurides

DOE PAGES

Levin, E. M.; Iowa State Univ., Ames, IA; Kramer, M. J.; ...

2016-07-14

Composition and crystal structure of complex materials can significantly change the Seebeck effect, i.e., heat to electrical energy conversion, which is utilized in thermoelectric materials. Despite decades of studies of various thermoelectric materials and their application, the fundamental understanding of this effect still is limited. One of the most efficient groups of thermoelectric materials is based on GeTe, where Ge is replaced by [Ag + Sb], i.e., Ag xSb xGe 50-2xTe 50 alloys, traditionally shown as (GeTe) m(AgSbTe 2) 100-m (TAGS-m series). Here, in this article, we report on the discovery of two unique phenomena in TAGS materials attributed tomore » the effects from [Ag + Sb] atoms: (i) a linear relation between the Seebeck coefficient and rhombohedral lattice distortion, and (ii) resonance-like temperature-induced behavior of the contribution to the Seebeck coefficient produced by [Ag + Sb] atoms. Finally, our findings show that heat to electrical energy conversion strongly depends on the temperature- and compositionally-induced rhombohedral to cubic transformation where [Ag + Sb] atoms play a crucial mediating role.« less

He-Ion Microscopy as a High-Resolution Probe for Complex Quantum Heterostructures in Core-Shell Nanowires.

PubMed

Pöpsel, Christian; Becker, Jonathan; Jeon, Nari; Döblinger, Markus; Stettner, Thomas; Gottschalk, Yeanitza Trujillo; Loitsch, Bernhard; Matich, Sonja; Altzschner, Marcus; Holleitner, Alexander W; Finley, Jonathan J; Lauhon, Lincoln J; Koblmüller, Gregor

2018-06-13

Core-shell semiconductor nanowires (NW) with internal quantum heterostructures are amongst the most complex nanostructured materials to be explored for assessing the ultimate capabilities of diverse ultrahigh-resolution imaging techniques. To probe the structure and composition of these materials in their native environment with minimal damage and sample preparation calls for high-resolution electron or ion microscopy methods, which have not yet been tested on such classes of ultrasmall quantum nanostructures. Here, we demonstrate that scanning helium ion microscopy (SHeIM) provides a powerful and straightforward method to map quantum heterostructures embedded in complex III-V semiconductor NWs with unique material contrast at ∼1 nm resolution. By probing the cross sections of GaAs-Al(Ga)As core-shell NWs with coaxial GaAs quantum wells as well as short-period GaAs/AlAs superlattice (SL) structures in the shell, the Al-rich and Ga-rich layers are accurately discriminated by their image contrast in excellent agreement with correlated, yet destructive, scanning transmission electron microscopy and atom probe tomography analysis. Most interestingly, quantitative He-ion dose-dependent SHeIM analysis of the ternary AlGaAs shell layers and of compositionally nonuniform GaAs/AlAs SLs reveals distinct alloy composition fluctuations in the form of Al-rich clusters with size distributions between ∼1-10 nm. In the GaAs/AlAs SLs the alloy clustering vanishes with increasing SL-period (>5 nm-GaAs/4 nm-AlAs), providing insights into critical size dimensions for atomic intermixing effects in short-period SLs within a NW geometry. The straightforward SHeIM technique therefore provides unique benefits in imaging the tiniest nanoscale features in topography, structure and composition of a multitude of diverse complex semiconductor nanostructures.

Chemical Evolution of a Protoplanetary Disk

NASA Astrophysics Data System (ADS)

Semenov, Dmitry A.

2011-12-01

In this paper we review recent progress in our understanding of the chemical evolution of protoplanetary disks. Current observational constraints and theoretical modeling on the chemical composition of gas and dust in these systems are presented. Strong variations of temperature, density, high-energy radiation intensities in these disks, both radially and vertically, result in a peculiar disk chemical structure, where a variety of processes are active. In hot, dilute and heavily irradiated atmosphere only the most photostable simple radicals and atoms and atomic ions exist, formed by gas-phase processes. Beneath the atmosphere a partly UV-shielded, warm molecular layer is located, where high-energy radiation drives rich ion-molecule and radical-radical chemistry, both in the gas phase and on dust surfaces. In a cold, dense, dark disk midplane many molecules are frozen out, forming thick icy mantles where surface chemistry is active and where complex polyatomic (organic) species are synthesized. Dynamical processes affect disk chemical composition by enriching it in abundances of complex species produced via slow surface processes, which will become detectable with ALMA.

Identifying Nanoscale Structure-Function Relationships Using Multimodal Atomic Force Microscopy, Dimensionality Reduction, and Regression Techniques.

PubMed

Kong, Jessica; Giridharagopal, Rajiv; Harrison, Jeffrey S; Ginger, David S

2018-05-31

Correlating nanoscale chemical specificity with operational physics is a long-standing goal of functional scanning probe microscopy (SPM). We employ a data analytic approach combining multiple microscopy modes, using compositional information in infrared vibrational excitation maps acquired via photoinduced force microscopy (PiFM) with electrical information from conductive atomic force microscopy. We study a model polymer blend comprising insulating poly(methyl methacrylate) (PMMA) and semiconducting poly(3-hexylthiophene) (P3HT). We show that PiFM spectra are different from FTIR spectra, but can still be used to identify local composition. We use principal component analysis to extract statistically significant principal components and principal component regression to predict local current and identify local polymer composition. In doing so, we observe evidence of semiconducting P3HT within PMMA aggregates. These methods are generalizable to correlated SPM data and provide a meaningful technique for extracting complex compositional information that are impossible to measure from any one technique.

Analysis of Nanodomain Composition in High-Impact Polypropylene by Atomic Force Microscopy-Infrared.

PubMed

Tang, Fuguang; Bao, Peite; Su, Zhaohui

2016-05-03

In this paper, compositions of nanodomains in a commercial high-impact polypropylene (HIPP) were investigated by an atomic force microscopy-infrared (AFM-IR) technique. An AFM-IR quantitative analysis method was established for the first time, which was then employed to analyze the polyethylene content in the nanoscopic domains of the rubber particles dispersed in the polypropylene matrix. It was found that the polyethylene content in the matrix was close to zero and was high in the rubbery intermediate layers, both as expected. However, the major component of the rigid cores of the rubber particles was found to be polypropylene rather than polyethylene, contrary to what was previously believed. The finding provides new insight into the complicated structure of HIPPs, and the AFM-IR quantitative method reported here offers a useful tool for assessing compositions of nanoscopic domains in complex polymeric systems.

Modeling the structural, dynamical, and magnetic properties of liquid Al1-xMnx ( x=0.14 , 0.2, and 0.4): A first-principles investigation

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2007-07-01

We report the results of first-principles molecular dynamics simulations of liquid Al1-xMnx alloys at three different compositions. The local structure as defined by the Bhatia-Thornton partial structure factors is found to display significant changes at x=0.4 . In addition, a structural analysis using three-dimensional pair-analysis techniques evidences a fivefold symmetry around x=0.14 , in agreement with the experimental quasicrystal-forming range, and an increasing complexity of the Frank-Kasper polytetrahedral symmetry around Mn atoms at x=0.4 . We also examine the time evolution of the configurations at the three compositions in terms of the mean-square displacements and self-diffusion coefficients. Finally, we show a strong interplay between the structural changes and the evolution of the magnetic properties of the Mn atoms as a function of composition.

Nanoscale Charge Balancing Mechanism in Calcium-Silicate-Hydrate Gels: Novel Complex Disordered Materials from First-principles

NASA Astrophysics Data System (ADS)

Ozcelik, Ongun; White, Claire

Alkali-activated materials which have augmented chemical compositions as compared to ordinary Portland cement are sustainable technologies that have the potential to lower CO2 emissions associated with the construction industry. In particular, calcium-silicate-hydrate (C-S-H) gel is altered at the atomic scale due to changes in its chemical composition. Here, based on first-principles calculations, we predict a charge balancing mechanism at the molecular level in C-S-H gels when alkali atoms are introduced into their structure. This charge balancing process is responsible for the formation of novel structures which possess superior mechanical properties compared to their charge unbalanced counterparts. Different structural representations are obtained depending on the level of substitution and the degree of charge balancing incorporated in the structures. The impact of these charge balancing effects on the structures is assessed by analyzing their formation energies, local bonding environments, diffusion barriers and mechanical properties. These results provide information on the phase stability of alkali/aluminum containing C-S-H gels, shedding light on the fundamental mechanisms that play a crucial role in these complex disordered materials. We acknowledge funding from the Princeton Center for Complex Materials, a MRSEC supported by NSF.

SIMSISH Technique Does Not Alter the Apparent Isotopic Composition of Bacterial Cells

PubMed Central

Chapleur, Olivier; Wu, Ting-Di; Guerquin-Kern, Jean-Luc; Mazéas, Laurent; Bouchez, Théodore

2013-01-01

In order to identify the function of uncultured microorganisms in their environment, the SIMSISH method, combining in situ hybridization (ISH) and nanoscale secondary ion mass spectrometry (nanoSIMS) imaging, has been proposed to determine the quantitative uptake of specific labelled substrates by uncultured microbes at the single cell level. This technique requires the hybridization of rRNA targeted halogenated DNA probes on fixed and permeabilized microorganisms. Exogenous atoms are introduced into cells and endogenous atoms removed during the experimental procedures. Consequently differences between the original and the apparent isotopic composition of cells may occur. In the present study, the influence of the experimental procedures of SIMSISH on the isotopic composition of carbon in E. coli cells was evaluated with nanoSIMS and compared to elemental analyser-isotopic ratio mass spectrometer (EA-IRMS) measurements. Our results show that fixation and hybridization have a very limited, reproducible and homogeneous influence on the isotopic composition of cells. Thereby, the SIMSISH procedure minimizes the contamination of the sample by exogenous atoms, thus providing a means to detect the phylogenetic identity and to measure precisely the carbon isotopic composition at the single cell level. This technique was successfully applied to a complex sample with double bromine – iodine labelling targeting a large group of bacteria and a specific archaea to evaluate their specific 13C uptake during labelled methanol anaerobic degradation. PMID:24204855

Interaction centres of pyrimidine nucleotides: cytidine-5'-diphosphate (CDP) and cytidine-5'-triphosphate (CTP) in their reactions with tetramines and Cu(II) ions.

PubMed

Gasowska, A

2005-08-01

The interactions between pyrimidine nucleotides: cytidine-5'-diphosphate (CDP) and cytidine-5'-triphosphate (CTP) and Cu(II) ions, spermine (Spm) and 1,11-diamino-4,8-diazaundecane (3,3,3-tet) have been studied. The composition and stability constants of the complexes formed have been determined by means of the potentiometric method, while the centres of interactions in the ligands have been identified by the spectral methods (UV-Vis, Ultraviolet and Visible spectroscopy; EPR, electron spin resonance; NMR). In the systems without metal, formation of the molecular complexes nucleotide-polyamine with the interaction centres at the endocyclic nitrogen atom of purine ring N3, the oxygen atoms of the phosphate group from the nucleotide and protonated nitrogen atoms of the polyamine have been detected. Significant differences have been found in the metallation between the systems with Spm and with 3,3,3-tet. In the systems with spermine, mainly protonated species are formed with the phosphate group of the nucleotide and deprotonated nitrogen atoms of the polyamine making the coordination centres, while the donor nitrogen atom of the nucleotide N3 is involved in the intramolecular interligand interactions, additionally stabilising the complex. In the systems with 3,3,3-tet, the MLL' type species are formed in which the oxygen atoms of the phosphate group and nitrogen atoms of the polyamine are involved in metallation, whereas the N3 atom from the pyrimidine ring of the nucleotide is located outside the inner coordination sphere of copper ion. The main centre of Cu(II) interaction in the nucleotide, both in the system with Spm and 3,3,3-tet is the phosphate group of the nucleotide.

Synthesis, crystal structures, and characterization of double complex salts [Au(en)2][Rh(NO2)6]·2H2O and [Au(en)2][Rh(NO2)6

NASA Astrophysics Data System (ADS)

Plyusnin, Pavel E.; Makotchenko, Evgenia V.; Shubin, Yury V.; Baidina, Iraida A.; Korolkov, Ilya V.; Sheludyakova, Liliya A.; Korenev, Sergey V.

2015-11-01

Double complex salts of rhodium(III) and gold(III) of the composition [Au(en)2][Rh(NO2)6]·2H2O (1) and [Au(en)2][Rh(NO2)6] (2) have been prepared. Crystal structures of the compounds have been determined by single crystal X-ray diffraction. The compounds have been characterized by PXRD, IR, far-IR, CHN and DTA. The complexes have a layered structures. The presence of water in 1 makes the structure of the hydrated DCS less dense as compared to the anhydrous one. The environment of the cation and the anion in the two structures is the same, oxygen atoms of the nitro groups are involved in hydrogen bonds N-H⋯O, N⋯O distances being approximately the same. The structures of 1 and 2 are notable in having shortened contacts between the gold atoms and the oxygen atoms of the nitro groups of the neighboring complex anions. The thermal behavior of the complexes in a hydrogen atmosphere was investigated. The final product of thermolysis prepared at the temperature 600°C is a two-phase mixture of pure metallic gold and the solid solution Rh0.93Au0.07.

Multi-scale simulations of apatite-collagen composites: from molecules to materials

NASA Astrophysics Data System (ADS)

Zahn, Dirk

2017-03-01

We review scale-bridging simulation studies for the exploration of atomicto-meso scale processes that account for the unique structure and mechanic properties of apatite-protein composites. As the atomic structure and composition of such complex biocomposites only partially is known, the first part (i) of our modelling studies is dedicated to realistic crystal nucleation scenarios of inorganic-organic composites. Starting from the association of single ions, recent insights range from the mechanisms of motif formation, ripening reactions and the self-organization of nanocrystals, including their interplay with growth-controlling molecular moieties. On this basis, (ii) reliable building rules for unprejudiced scale-up models can be derived to model bulk materials. This is exemplified for (enamel-like) apatite-protein composites, encompassing up to 106 atom models to provide a realistic account of the 10 nm length scale, whilst model coarsening is used to reach μm length scales. On this basis, a series of deformation and fracture simulation studies were performed and helped to rationalize biocomposite hardness, plasticity, toughness, self-healing and fracture mechanisms. Complementing experimental work, these modelling studies provide particularly detailed insights into the relation of hierarchical composite structure and favorable mechanical properties.

Synthesis, structural, photophysical and thermal studies of benzoate bridged Sm(III) complexes

NASA Astrophysics Data System (ADS)

Singh, Udai P.; Kumar, Rajeev; Upreti, Shailesh

2007-04-01

One samarium coordination polymer (chain like) 1 with composition [{Sm(OBz) 3(MeO) 2} 2] n has been prepared from the reaction of SmCl 3 and sodium benzoate in 1:3 ratio whereas four binuclear samarium complexes with chemical composition [{(tp)Sm(μ- p-X-OBz) 2} 2] have been prepared by the reaction of SmCl 3, potassium hydrotris(pyrazol-1-yl)borate [K(tp)] and sodium p-X-benzoate (where X = H, Cl, F, NO 2) in 1:1:2 ratio. These complexes have been characterized by elemental analysis, IR spectroscopy, thermogravimetry, optical properties, X-ray and magnetic measurement studies. The X-ray structure shows that the complexes 2- 5 are isostructural whereas the structure of 1 is different. The coordination number around metal center in 1 is eight whereas in complexes 2- 5, each samarium is seven coordinate. The X-ray studies indicate that the complex 1 crystallizes in monoclinic space group P2(1)/ c with the cell dimensions a = 9.75(7), b = 21.83(15), c = 22.28(15) Å, whereas the complexes 2 and 3 crystallizes isostructurally in the triclinic space group P1¯ with the cell dimension a = 11.77(10), b = 12.60(10), c = 17.57(13) Å and a = 9.55(3), b = 12.80(4), c = 14.47(5) Å, respectively. The samarium ions in 2 and 3 are coordinated by three N atoms of pyrazolylborate ligand and four O atoms from benzoate groups. The photophysical properties of above complexes have been studied with ultraviolet absorption, excitation and emission spectral studies. The complexes 1- 5 excited at 240 nm wavelength produced characteristic luminescence features, arising mostly due to the f-f transitions.

Interactions of 1,12-diamino-4,9-dioxadodecane (OSpm) and Cu(II) ions with pyrimidine and purine nucleotides: adenosine-5'-monophosphate (AMP) and cytidine-5'-monophosphate (CMP).

PubMed

Lomozik, L; Gasowska, A; Krzysko, G

2006-11-01

The interactions of Cu(II) ions with adenosine-5'-monophosphate (AMP), cytidine-5'-monophosphate (CMP) and 1,12-diamino-4,9-dioxadodecane (OSpm) were studied. A potentiometric method was applied to determine the composition and stability constants of complexes formed, while the mode of interactions was analysed by spectral methods (ultraviolet and visible spectroscopy (UV-Vis), electron paramagnetic resonance (EPR), (13)C NMR, (31)P NMR). In metal-free systems, molecular complexes nucleotide-polyamine (NMP)H(x)(OSpm) were formed. The endocyclic nitrogen atoms of the purine ring N(1), N(7), the nitrogen atom of the pyrimidine ring N(3), the oxygen atoms of the phosphate group of the nucleotide and the protonated nitrogen atoms of the polyamine were the reaction centres. The mode of interaction of the metal ion with OSpm and the nucleotides (AMP or CMP) in the coordination compounds was established. In the system Cu(II)/OSpm the dinuclear complex Cu(2)(OSpm) forms, while in the ternary systems Cu(II)/nucleotide/OSpm the species type MH(x)LL' and MLL' appear. In the MH(x)LL' type species, the main centres of copper (II) ion binding in the nucleotide are the phosphate groups. The protonated amino groups of OSpm are involved in non-covalent interaction with the nitrogen atoms N(1), N(7) or N(3) of the purine or pyrimidine ring, whereas at higher pH, deprotonated nitrogen atoms of polyamine are engaged in metallation in MLL' species.

The influence of voxel size on atom probe tomography data.

PubMed

Torres, K L; Daniil, M; Willard, M A; Thompson, G B

2011-05-01

A methodology for determining the optimal voxel size for phase thresholding in nanostructured materials was developed using an atom simulator and a model system of a fixed two-phase composition and volume fraction. The voxel size range was banded by the atom count within each voxel. Some voxel edge lengths were found to be too large, resulting in an averaging of compositional fluctuations; others were too small with concomitant decreases in the signal-to-noise ratio for phase identification. The simulated methodology was then applied to the more complex experimentally determined data set collected from a (Co(0.95)Fe(0.05))(88)Zr(6)Hf(1)B(4)Cu(1) two-phase nanocomposite alloy to validate the approach. In this alloy, Zr and Hf segregated to an intergranular amorphous phase while Fe preferentially segregated to a crystalline phase during the isothermal annealing step that promoted primary crystallization. The atom probe data analysis of the volume fraction was compared to transmission electron microscopy (TEM) dark-field imaging analysis and a lever rule analysis of the volume fraction within the amorphous and crystalline phases of the ribbon. Copyright © 2011 Elsevier B.V. All rights reserved.

The coordination structure of the extracted copper(II) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and n-hexyl 3-pyridinecarboxylate ester

NASA Astrophysics Data System (ADS)

Zhu, Shan; Hu, Huiping; Hu, Jiugang; Li, Jiyuan; Hu, Fang; Wang, Yongxi

2017-09-01

In continuation of our interest in the coordination structure of the nickel(II) complex with dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC), it was observed that the coordination sphere was completed by the coordination of two N atoms of pyridine rings in ligands 4PC and four water molecules while no direct interaction between Ni(II) and deprotonated HDNNS was observed. To investigate whether the coordination structure of nickel(II) with the synergistic mixture containing HDNNS and 4PC predominates or not in the copper(II) complex with the synergistic mixtures containing HDNNS and pyridinecarboxylate esters, a copper(II) synergist complex with n-hexyl 3-pyridinecarboxylate ester (L) and naphthalene-2-sulfonic acid (HNS, the short chain analogue of HDNNS), was prepared and studied by X-ray single crystal diffraction, elemental analyses and thermo gravimetric analysis (TGA), respectively. It was shown that the composition of the copper(II) synergist complex was [Cu(H2O)2(L)2(NS)2] and formed a trans-form distorted octahedral coordination structure. Two oxygen atoms of the two coordinated water molecules and two N atoms of the pyridine rings in the ligands L defined the basal plane while two O atoms from two sulfonate anions of the deprotonated HNS ligands occupied the apical positions by direct coordination with Cu(II), which was distinguished from the coordination structure of the nickel(II) synergist complex as reported in our previous work. In the crystal lattice, neighboring molecules [Cu(H2O)2L2(NS)2] were linked through the intermolecular hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the sulfonate anions in the copper(II) synergist complex to form a 2D plane. In order to bridge the gap between the solid state structure of the copper(II) synergist complex and the solution structure of the extracted copper(II) complex with the actual synergistic mixture containing L and HDNNS in the non-polar organic phase, the structures of the two copper(II) complexes were further investigated by Fourier transform infrared spectroscopy (FT-IR) and electrospray ionization mass spectrometry (ESI-MS), and the results indicated that the extracted copper(II) complex in the non-polar organic phase might possess a similar coordination structure as the copper(II) synergist complex.

Atomic Weights and Isotopic Compositions

National Institute of Standards and Technology Data Gateway

SRD 144 Atomic Weights and Isotopic Compositions (Web, free access)   The atomic weights are available for elements 1 through 111, and isotopic compositions or abundances are given when appropriate.

Atom probe trajectory mapping using experimental tip shape measurements.

PubMed

Haley, D; Petersen, T; Ringer, S P; Smith, G D W

2011-11-01

Atom probe tomography is an accurate analytical and imaging technique which can reconstruct the complex structure and composition of a specimen in three dimensions. Despite providing locally high spatial resolution, atom probe tomography suffers from global distortions due to a complex projection function between the specimen and detector which is different for each experiment and can change during a single run. To aid characterization of this projection function, this work demonstrates a method for the reverse projection of ions from an arbitrary projection surface in 3D space back to an atom probe tomography specimen surface. Experimental data from transmission electron microscopy tilt tomography are combined with point cloud surface reconstruction algorithms and finite element modelling to generate a mapping back to the original tip surface in a physically and experimentally motivated manner. As a case study, aluminium tips are imaged using transmission electron microscopy before and after atom probe tomography, and the specimen profiles used as input in surface reconstruction methods. This reconstruction method is a general procedure that can be used to generate mappings between a selected surface and a known tip shape using numerical solutions to the electrostatic equation, with quantitative solutions to the projection problem readily achievable in tens of minutes on a contemporary workstation. © 2011 The Authors Journal of Microscopy © 2011 Royal Microscopical Society.

Atom Probe Tomographic Analysis of Biological Systems Enabled by Advanced Specimen Preparation Approaches

NASA Astrophysics Data System (ADS)

Perea, D. E.; Evans, J. E.

2017-12-01

The ability to image biointerfaces over nanometer to micrometer length scales is fundamental to correlating biological composition and structure to physiological function, and is aided by a multimodal approach using advanced complementary microscopic and spectroscopic characterization techniques. Atom Probe Tomography (APT) is a rapidly expanding technique for atomic-scale three-dimensional structural and chemical analysis. However, the regular application of APT to soft biological materials is lacking in large part due to difficulties in specimen preparation and inabilities to yield meaningful tomographic reconstructions that produce atomic scale compositional distributions as no other technique currently can. Here we describe the atomic-scale tomographic analysis of biological materials using APT that is facilitated by an advanced focused ion beam based approach. A novel specimen preparation strategy is used in the analysis of horse spleen ferritin protein embedded in an organic polymer resin which provides chemical contrast to distinguish the inorganic-organic interface of the ferrihydrite mineral core and protein shell of the ferritin protein. One-dimensional composition profiles directly reveal an enhanced concentration of P and Na at the surface of the ferrihydrite mineral core. We will also describe the development of a unique multifunctional environmental transfer hub allowing controlled cryogenic transfer of specimens under vacuum pressure conditions between an Atom Probe and cryo-FIB/SEM. The utility of the environmental transfer hub is demonstrated through the acquisition of previously unavailable mass spectral analysis of an intact organometallic molecule made possible via controlled cryogenic transfer. The results demonstrate a viable application of APT analysis to study complex biological organic/inorganic interfaces relevant to energy and the environment. References D.E. Perea et al. An environmental transfer hub for multimodal atom probe tomography, Adv. Struct. Chem. Imag, 2017, 3:12 The research was performed at the Environmental Molecular Sciences Laboratory; a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research located at Pacific Northwest National Laboratory.

Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

DOEpatents

Farmer, Joseph C; Wong, Frank M.G.; Haslam, Jeffery J; Ji, Xiaoyan; Day, Sumner D; Blue, Craig A; Rivard, John D.K.; Aprigliano, Louis F; Kohler, Leslie K; Bayles, Robert; Lemieux, Edward J; Yang, Nancy; Perepezko, John H; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J

2013-09-03

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings

DOEpatents

Farmer, Joseph C.; Wong, Frank M. G.; Haslam, Jeffery J.; Ji, Xiaoyan; Day, Sumner D.; Blue, Craig A.; Rivard, John D. K.; Aprigliano, Louis F.; Kohler, Leslie K.; Bayles, Robert; Lemieux, Edward J.; Yang, Nancy; Perepezko, John H.; Kaufman, Larry; Heuer, Arthur; Lavernia, Enrique J.

2013-07-09

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

Local configurations and atomic intermixing in as-quenched and annealed Fe1-xCrx and Fe1-xMox ribbons

NASA Astrophysics Data System (ADS)

Stanciu, A. E.; Greculeasa, S. G.; Bartha, C.; Schinteie, G.; Palade, P.; Kuncser, A.; Leca, A.; Filoti, G.; Birsan, A.; Crisan, O.; Kuncser, V.

2018-04-01

Local atomic configuration, phase composition and atomic intermixing in Fe-rich Fe1-xCrx and Fe1-xMox ribbons (x = 0.05, 0.10, 0.15), of potential interest for high-temperature applications and nuclear devices, are investigated in this study in relation to specific processing and annealing routes. The Fe-based thin ribbons have been prepared by induction melting, followed by melt spinning and further annealed in He at temperatures up to 1250 °C. The complex structural, compositional and atomic configuration characterisation has been performed by means of X-ray diffraction (XRD), transmission Mössbauer spectroscopy and differential scanning calorimetry (TG-DSC). The XRD analysis indicates the formation of the desired solid solutions with body-centred cubic (bcc) structure in the as-quenched state. The Mössbauer spectroscopy results have been analysed in terms of the two-shell model. The distribution of Cr/Mo atoms in the first two coordination spheres is not homogeneous, especially after annealing, as supported by the short-range order parameters. In addition, high-temperature annealing treatments give rise to oxidation of Fe (to haematite, maghemite and magnetite) at the surface of the ribbons. Fe1-xCrx alloys are structurally more stable than the Mo counterpart under annealing at 700 °C. Annealing at 1250 °C in He enhances drastically the Cr clustering around Fe nuclei.

Experimental and theoretical insight into the cooperativity effect in composite wax powder and ternary complex of coronene with CH4 and Mn+ (Mn+ = Li+, Na+, K+, Be2+, Mg2+ or Ca2+)

NASA Astrophysics Data System (ADS)

Jiang, Le-tao; Bai, Pei-kang; Wang, Jian-hong; Liu, Bin; Li, Yu-xin

2018-01-01

The experimental infrared (IR) spectrum of composite wax powder was investigated. The frequency shifts of the C=C anti-symmetrical stretching mode were observed and the experimental cooperativity effect involving Na+...π interaction was suggested. In order to further reveal the nature of cooperativity effect, the interaction energies in Mn+...coronene...CH4 (Mn+ = Li+, Na+, K+, Be2+, Mg2+ or Ca2+) as the model systems of composite wax powder were calculated by using the B3LYP, M06-2X and MP2 methods with 6-311++G** basis set. The results show that the Mn+...π interactions were strengthened upon the formation of ternary complexes. Although the changes of absolute values of the interactions between CH4 and coronene were not obvious, the relative values were considerably significant upon the formation of ternary complexes. The cooperativity effect was perhaps the reason for the formation of notable advantage of composite wax powder upon the introduction of surfactant with cation into wax powder. Reduced density gradient and atoms-in-molecules analysis confirm the cooperativity effect in Mn+...coronene...CH4, and reveal the nature of the formation of the predominant advantage of composite wax powder.

Gamma irradiation assisted fungal degradation of the polypropylene/biomass composites

NASA Astrophysics Data System (ADS)

Butnaru, Elena; Darie-Niţă, Raluca Nicoleta; Zaharescu, Traian; Balaeş, Tiberius; Tănase, Cătălin; Hitruc, Gabriela; Doroftei, Florica; Vasile, Cornelia

2016-08-01

White-rot fungus Bjerkandera adusta has been tested for its ability to degrade some biocomposites materials based on polypropylene and biomass (Eucalyptus globulus, pine cones, and Brassica rapa). γ-irradiation was applied to initiate the degradation of relatively inert polypropylene matrix. The degradation process has been studied by scanning electron microscopy, atomic force microscopy, infrared spectroscopy, contact angle measurements, rheological and chemiluminescence tests. These analyses showed that the polypropylene/biomass composites properties are worsen under the action of the selected microorganism. The formation of cracks and scrap particles over the entire matrix surface and the decrease of the complex viscosity values, as well as the dynamic moduli of gamma irradiated PP/biomass composite and exposed to Bjerkandera adusta fungus, indicate fungal efficiency in composite degradation.

Effect of carbon and alloying solute atoms on helium behaviors in α-Fe

NASA Astrophysics Data System (ADS)

Zhang, Yange; You, Yu-Wei; Xu, Yichun; Liu, C. S.; Chen, J. L.; Luo, G.-N.

2017-02-01

Helium bubbles could strongly degrade the mechanical properties of ferritic steels in fission and fusion systems. The formation of helium bubble is directly affected by the interactions between helium and the compositions in steels, such as solute atoms, carbon and irradiation defects. We thereby performed systematical first-principles calculations to investigate the interactions of solute-helium and carbon-solute-helium. It is found that substitutional helium is more attractive than interstitial helium to all the considered 3p, 4p, 5p and 6p solutes. The attraction between carbon and substitutional helium suggests the carbon-solute-helium complex can be formed stably. By examining the charge density difference and thermal stability, it is found that the ternary complex shows stronger attraction with He than that of solute-helium pair for some solutes (S, Se, In, Te, Pb and Bi) and the complex could existed in iron stably at 700 K. The present theoretical results may be helpful for exploring alloy additions to mitigate the formation of large helium bubbles.

The neuronal porosome complex in health and disease

PubMed Central

Naik, Akshata R; Lewis, Kenneth T

2015-01-01

Cup-shaped secretory portals at the cell plasma membrane called porosomes mediate the precision release of intravesicular material from cells. Membrane-bound secretory vesicles transiently dock and fuse at the base of porosomes facing the cytosol to expel pressurized intravesicular contents from the cell during secretion. The structure, isolation, composition, and functional reconstitution of the neuronal porosome complex have greatly progressed, providing a molecular understanding of its function in health and disease. Neuronal porosomes are 15 nm cup-shaped lipoprotein structures composed of nearly 40 proteins, compared to the 120 nm nuclear pore complex composed of >500 protein molecules. Membrane proteins compose the porosome complex, making it practically impossible to solve its atomic structure. However, atomic force microscopy and small-angle X-ray solution scattering studies have provided three-dimensional structural details of the native neuronal porosome at sub-nanometer resolution, providing insights into the molecular mechanism of its function. The participation of several porosome proteins previously implicated in neurotransmission and neurological disorders, further attest to the crosstalk between porosome proteins and their coordinated involvement in release of neurotransmitter at the synapse. PMID:26264442

Atomic scale dynamics of a solid state chemical reaction directly determined by annular dark-field electron microscopy.

PubMed

Pennycook, Timothy J; Jones, Lewys; Pettersson, Henrik; Coelho, João; Canavan, Megan; Mendoza-Sanchez, Beatriz; Nicolosi, Valeria; Nellist, Peter D

2014-12-22

Dynamic processes, such as solid-state chemical reactions and phase changes, are ubiquitous in materials science, and developing a capability to observe the mechanisms of such processes on the atomic scale can offer new insights across a wide range of materials systems. Aberration correction in scanning transmission electron microscopy (STEM) has enabled atomic resolution imaging at significantly reduced beam energies and electron doses. It has also made possible the quantitative determination of the composition and occupancy of atomic columns using the atomic number (Z)-contrast annular dark-field (ADF) imaging available in STEM. Here we combine these benefits to record the motions and quantitative changes in the occupancy of individual atomic columns during a solid-state chemical reaction in manganese oxides. These oxides are of great interest for energy-storage applications such as for electrode materials in pseudocapacitors. We employ rapid scanning in STEM to both drive and directly observe the atomic scale dynamics behind the transformation of Mn3O4 into MnO. The results demonstrate we now have the experimental capability to understand the complex atomic mechanisms involved in phase changes and solid state chemical reactions.

Composition, Characterization and Antibacterial activity of Mn(II), Co(II),Ni(II), Cu(II) Zn(II) and Cd(II) mixed ligand complexes Schiff base derived from Trimethoprim with 8-Hydroxy quinoline

NASA Astrophysics Data System (ADS)

Numan, Ahmed T.; Atiyah, Eman M.; Al-Shemary, Rehab K.; Ulrazzaq, Sahira S. Abd

2018-05-01

New Schiff base ligand 2-((4-amino-5-(3, 4, 5-trimethoxybenzyl) pyrimidin-2-ylimino) (phenyl)methyl)benzoic acid] = [HL] was synthesized using microwave irradiation trimethoprim and 2-benzoyl benzoic acid. Mixed ligand complexes of Mn((II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) are reacted in ethanol with Schiff base ligand [HL] and 8-hydroxyquinoline [HQ] then reacted with metal salts in ethanol as a solvent in (1:1:1) ratio. The ligand [HL] is characterized by FTIR, UV-Vis, melting point, elemental microanalysis (C.H.N), 1H-NMR, 13C-NMR, and mass spectra. The mixed ligand complexes are characterized by infrared spectra, electronic spectra, (C.H.N), melting point, atomic absorption, molar conductance and magnetic moment measurements. These measurements indicate that the ligand [HL] coordinates with metal (II) ion in a tridentate manner through the oxygen and nitrogen atoms of the ligand, octahedral structures are suggested for these complexes. Antibacterial activity of the ligands [HL], [HQ] and their complexes are studied against (gram positive) and (gram negative) bacteria.

Microwave absorption properties of carbon nanocoils coated with highly controlled magnetic materials by atomic layer deposition.

PubMed

Wang, Guizhen; Gao, Zhe; Tang, Shiwei; Chen, Chaoqiu; Duan, Feifei; Zhao, Shichao; Lin, Shiwei; Feng, Yuhong; Zhou, Lei; Qin, Yong

2012-12-21

In this work, atomic layer deposition is applied to coat carbon nanocoils with magnetic Fe(3)O(4) or Ni. The coatings have a uniform and highly controlled thickness. The coated nanocoils with coaxial multilayer nanostructures exhibit remarkably improved microwave absorption properties compared to the pristine carbon nanocoils. The enhanced absorption ability arises from the efficient complementarity between complex permittivity and permeability, chiral morphology, and multilayer structure of the products. This method can be extended to exploit other composite materials benefiting from its convenient control of the impedance matching and combination of dielectric-magnetic multiple loss mechanisms for microwave absorption applications.

Radiation-induced segregation on defect clusters in single-phase concentrated solid-solution alloys

DOE PAGES

Lu, Chenyang; Yang, Taini; Jin, Ke; ...

2017-01-12

A group of single-phase concentrated solid-solution alloys (SP-CSAs), including NiFe, NiCoFe, NiCoFeCr, as well as a high entropy alloy NiCoFeCrMn, was irradiated with 3 MeV Ni 2+ ions at 773 K to a fluence of 5 10 16 ions/cm 2 for the study of radiation response with increasing compositional complexity. Advanced transmission electron microscopy (TEM) with electron energy loss spectroscopy (EELS) was used to characterize the dislocation loop distribution and radiation-induced segregation (RIS) on defect clusters in the SP-CSAs. The results show that a higher fraction of faulted loops exists in the more compositionally complex alloys, which indicate that increasingmore » compositional complexity can extend the incubation period and delay loop growth. The RIS behaviors of each element in the SP-CSAs were observed as follows: Ni and Co tend to enrich, but Cr, Fe and Mn prefer to deplete near the defect clusters. RIS level can be significantly suppressed by increasing compositional complexity due to the sluggish atom diffusion. According to molecular static (MS) simulations, disk like segregations may form near the faulted dislocation loops in the SP-CSAs. Segregated elements tend to distribute around the whole faulted loop as a disk rather than only around the edge of the loop.« less

Standard deviations of composition measurements in atom probe analyses. Part I conventional 1D atom probe.

PubMed

Danoix, F; Grancher, G; Bostel, A; Blavette, D

2007-09-01

Atom probe is a very powerful instrument to measure concentrations on a sub nanometric scale [M.K. Miller, G.D.W. Smith, Atom Probe Microanalysis, Principles and Applications to Materials Problems, Materials Research Society, Pittsburgh, 1989]. Atom probe is therefore a unique tool to study and characterise finely decomposed metallic materials. Composition profiles or 3D mapping can be realised by gathering elemental composition measurements. As the detector efficiency is generally not equal to 1, the measured compositions are only estimates of actual values. The variance of the estimates depends on which information is to be estimated. It can be calculated when the detection process is known. These two papers are devoted to give complete analytical derivation and expressions of the variance on composition measurements in several situations encountered when using atom probe. In the first paper, we will concentrate on the analytical derivation of the variance when estimation of compositions obtained from a conventional one dimension (1D) atom probe is considered. In particular, the existing expressions, and the basic hypotheses on which they rely, will be reconsidered, and complete analytical demonstrations established. In the second companion paper, the case of 3D atom probe will be treated, highlighting how the knowledge of the 3D position of detected ions modifies the analytical derivation of the variance of local composition data.

A script to highlight hydrophobicity and charge on protein surfaces

PubMed Central

Hagemans, Dominique; van Belzen, Ianthe A. E. M.; Morán Luengo, Tania; Rüdiger, Stefan G. D.

2015-01-01

The composition of protein surfaces determines both affinity and specificity of protein-protein interactions. Matching of hydrophobic contacts and charged groups on both sites of the interface are crucial to ensure specificity. Here, we propose a highlighting scheme, YRB, which highlights both hydrophobicity and charge in protein structures. YRB highlighting visualizes hydrophobicity by highlighting all carbon atoms that are not bound to nitrogen and oxygen atoms. The charged oxygens of glutamate and aspartate are highlighted red and the charged nitrogens of arginine and lysine are highlighted blue. For a set of representative examples, we demonstrate that YRB highlighting intuitively visualizes segments on protein surfaces that contribute to specificity in protein-protein interfaces, including Hsp90/co-chaperone complexes, the SNARE complex and a transmembrane domain. We provide YRB highlighting in form of a script that runs using the software PyMOL. PMID:26528483

Electronic and chemical structure of an organic light emitter embedded in an inorganic wide-bandgap semiconductor: Photoelectron spectroscopy of layered and composite structures of Ir(BPA) and ZnSe

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

Dimamay, Mariel; Laboratoire de Chimie des Polymères Organiques, CNRS, Université de Bordeaux, UMR 5629-16 Avenue Pey-Berland, 33607 Pessac; Mayer, Thomas

Luminescent organic phases embedded in conductive inorganic matrices are proposed for hybrid organic-inorganic light-emitting diodes. In this configuration, the organic dye acts as the radiative recombination site for charge carriers injected into the inorganic matrix. Our investigation is aimed at finding a material combination where the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the organic dye are situated in between the valence and conduction bands of the inorganic matrix in order to promote electron and hole transfer from the matrix to the dye. Bilayer and composite thin films of zinc selenide (ZnSe) and a redmore » iridium complex (Ir(BPA)) organic light emitter were prepared in situ via UHV thermal evaporation technique. The electronic and atomic structures were studied applying X-ray and ultraviolet photoelectron spectroscopies. The measured energy band alignments for the ZnSe/Ir(BPA) bilayer and ZnSe+Ir(BPA) composite reveal that the HOMO and LUMO of the organic dye are positioned in the ZnSe bandgap. For the initial steps of ZnSe deposition on a dye film to form Ir(BPA)/ZnSe bilayers, zinc atoms intercalate into the dye film leaving behind an excess of selenium at the interface that partly reacts with dye molecules. Photoelectron spectroscopy of the composites shows the same species suggesting a similar mechanism. This mechanism leads to composite films with increased content of amorphous phases in the inorganic matrix, thereby affecting its conductivity, as well as to the presence of nonradiative recombination sites provided by the intercalated Zn atoms.« less

Surface modification of cellulose fibers: towards wood composites by biomimetics.

PubMed

Gradwell, Sheila E; Renneckar, Scott; Esker, Alan R; Heinze, Thomas; Gatenholm, Paul; Vaca-Garcia, Carlos; Glasser, Wolfgang

2004-01-01

A biomimetic approach was taken for studying the adsorption of a model copolymer (pullulan abietate, DS 0.027), representing the lignin-carbohydrate complex, to a model surface for cellulose fibers (Langmuir-Blodgett thin films of regenerated cellulose). Adsorption results were assayed using surface plasmon resonance spectroscopy (SPR) and atomic force microscopy (AFM). Rapid, spontaneous, and desorption-resistant surface modification resulted. This effort is viewed as a critical first step towards the permanent surface modification of cellulose fibers with a layer of molecules amenable to either enzymatic crosslinking for improved wood composites or thermoplastic consolidation.

Synthesis and characterization of heterobimetallic molybdenum and nickel complexes derived from polyfunctional disalicylaldehyde oxaloyldihydrazone

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Borthakur, Rosmita; Koch, Angira; Chanu, Oinam B.; Choudhury, Sanjesh; Lemtur, Aka; Lal, Ram A.

2011-07-01

Heterobimetallic nickel and molybdenum complexes of the composition [Ni(L)MoO 2(A) 4]· nH 2O (A = H 2O (1), py (2), 2-pic (3), 3-pic (4), and 4-pic (5); n = 0, 2) and [Ni(L)(MoO 2)(BB) 2](BB = bpy (6) and (phen (7)) have been synthesized from the multidentate ligand disalicylaldehyde oxaloyldihydrazone (H 4L) in methanol. The composition of the complexes has been established based on data obtained from elemental analyses, thermoanalytical, mass spectral and molecular weight studies. The probable structures of the complexes have been discussed in the light of molar conductance, magnetic moment data and electronic, EPR and infrared spectral studies. In all of the complexes, the dihydrazone is present in enol form and coordinates to the metal centre as a tetrabasic hexadentate ligand. All of the complexes are normal paramagnetic to the extent of two unpaired electrons per nickel atom. The μeff values for the complexes lying in the region 2.87-3.07 B.M. are consistent with the octahedral stereochemistry of nickel(II) in the heterobimetallic complexes. The EPR and electronic spectral data also support the distorted octahedral stereochemistry of the nickel(II) centre. Both nickel and molybdenum have octahedral geometry in the complexes.

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

The Anh, Le, E-mail: letheanh@jaist.ac.jp; Lam, Pham Tien; Manoharan, Muruganathan

We present a first-principles study on the interstitial-mediated diffusion process of neutral phosphorus (P) atoms in a silicon crystal with the presence of mono-atomic hydrogen (H). By relaxing initial Si structures containing a P atom and an H atom, we derived four low-energy P-H-Si defect complexes whose formation energies are significantly lower than those of P-Si defect complexes. These four defect complexes are classified into two groups. In group A, an H atom is located near a Si atom, whereas in group B, an H atom is close to a P atom. We found that the H atom pairs withmore » P or Si atom and changes the nature bonding between P and Si atoms from out-of-phase conjugation to in-phase conjugation. This fact results in the lower formation energies compare to the cases without H atom. For the migration of defect complexes, we have found that P-H-Si defect complexes can migrate with low barrier energies if an H atom sticks to either P or Si atom. Group B complexes can migrate from one lattice site to another with an H atom staying close to a P atom. Group A complexes cannot migrate from one lattice site to another without a transfer of an H atom from one Si atom to another Si atom. A change in the structure of defect complexes between groups A and B during the migration results in a transfer of an H atom between P and Si atoms. The results for diffusion of group B complexes show that the presence of mono-atomic H significantly reduces the activation energy of P diffusion in a Si crystal, which is considered as a summation of formation energy and migration barrier energy, leading to the enhancement of diffusion of P atoms at low temperatures, which has been suggested by recent experimental studies.« less

The effect orientation of features in reconstructed atom probe data on the resolution and measured composition of T1 plates in an A2198 aluminium alloy.

PubMed

Mullin, Maria A; Araullo-Peters, Vicente J; Gault, Baptiste; Cairney, Julie M

2015-12-01

Artefacts in atom probe tomography can impact the compositional analysis of microstructure in atom probe studies. To determine the integrity of information obtained, it is essential to understand how the positioning of features influences compositional analysis. By investigating the influence of feature orientation within atom probe data on measured composition in microstructural features within an AA2198 Al alloy, this study shows differences in the composition of T1 (Al2CuLi) plates that indicates imperfections in atom probe reconstructions. The data fits a model of an exponentially-modified Gaussian that scales with the difference in evaporation field between solutes and matrix. This information provides a guide for obtaining the most accurate information possible. Copyright © 2015 Elsevier B.V. All rights reserved.

Thermal characteristics of carbon fiber reinforced epoxy containing multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lee, Jin-woo; Park, Soo-Jeong; Kim, Yun-hae; Riichi-Murakami

2018-06-01

The material with irregular atomic structures such as polymer material exhibits low thermal conductivity because of the complex structural properties. Even materials with same atomic configurations, thermal conductivity may be different based on their structural properties. It is expected that nanoparticles with conductivity will change non-conductive polymer base materials to electrical conductors, and improve the thermal conductivity even with extremely small filling amount. Nano-composite materials contain nanoparticles with a higher surface ratio which makes the higher interface percentage to the total surface of nanoparticles. Therefore, thermal resistance of the interface becomes a dominating factor determines the effective thermal conductivity in nano-composite materials. Carbon fiber has characteristic of resistance or magnetic induction and Also, Carbon nanotube (CNT) has electronic and thermal property. It can be applied for heating system. These characteristic are used as heating composite. In this research, the exothermic characteristics of Carbon fiber reinforced composite added CNT were evaluated depend on CNT length and particle size. It was found that the CNT dispersed in the resin reduces the resistance between the interfaces due to the decrease in the total resistance of the heating element due to the addition of CNTs. It is expected to improve the life and performance of the carbon fiber composite material as a result of the heating element resulting from this paper.

Zinc(II) complexes with potent cyclin-dependent kinase inhibitors derived from 6-benzylaminopurine: synthesis, characterization, X-ray structures and biological activity.

PubMed

Trávnícek, Zdenek; Krystof, Vladimír; Sipl, Michal

2006-02-01

The synthesis, characterization and biological activity of the first zinc(II) complexes with potent inhibitors of cyclin-dependent kinases (CDKs) derived from 6-benzylaminopurine are described. Based on the results following from elemental analyses, infrared, NMR and ES+MS (electrospray mass spectra in the positive ion mode) spectroscopies, conductivity data, thermal analysis and X-ray structures, the tetrahedral Zn(II) complexes of the compositions [Zn(Olo)Cl(2)](n) (1), [Zn(iprOlo)Cl(2)](n) (2), [Zn(BohH(+))Cl(3)] x H(2)O (3) and [Zn(iprOloH(+))Cl(3)] x H(2)O (4) have been prepared, where Olo=2-(2-hydroxyethylamino)-6-benzylamino-9-methylpurine (Olomoucine), iprOlo=2-(2-hydroxyethylamino)-6-benzylamino-9-isopropylpurine (i-propyl-Olomoucine), Boh=2-(3-hydroxypropylamino)-6-benzylamino-9-isopropylpurine (Bohemine). The 1D-polymeric chain structure for [Zn(Olo)Cl(2)](n) (1) as well as the monomeric one for [Zn(BohH(+))Cl(3)] x H(2)O (3) and [Zn(iprOloH(+))Cl(3)] x H(2)O (4) have been revealed unambiguously by single crystal X-ray analyses. The 1D-polymeric chain of 1 consists of Zn(Olo)Cl(2) monomeric units in which the Zn(II) ion is coordinated by two chlorine atoms and one oxygen atom of the 2-hydroxyethylamino group of Olomoucine. The next monomeric unit is bonded to Zn(II) through the N7 atom of a purine ring. Thus, each of Zn(II) ions is tetrahedrally coordinated and a ZnCl(2)NO chromophore occurs in the complex 1. The complexes 3 and 4 are mononuclear species with a distorted tetrahedral arrangement of donor atoms around the Zn(II) ion with a ZnCl(3)N chromophore. The corresponding CDK inhibitor, i.e., both Boh and iprOlo, is coordinated to Zn(II) via the N7 atom of the purine ring in 3 and 4. The cytotoxicity of the zinc(II) complexes against human melanoma, sarcoma, leukaemia and carcinoma cell lines has been determined as well as the inhibition of the CDK2/cyclin E kinase. A relationship between the structure and biological activity of the complexes is also discussed.

Preparation, characterization and stability of curcumin-loaded zein-shellac composite colloidal particles.

PubMed

Sun, Cuixia; Xu, Chenqi; Mao, Like; Wang, Di; Yang, Jie; Gao, Yanxiang

2017-08-01

Curcumin-loaded zein-shellac composite particles were prepared by the antisolvent co-precipitation method. The encapsulation efficiency of curcumin was significantly improved from 82.7% in zein particles to 93.2% in zein-shellac complex particles. The result of differential scanning calorimetry suggested that curcumin in the polymeric matrix was in an amorphous state. Fourier transform infrared spectroscopy analysis revealed that curcumin had non-covalently interacted with zein and shellac, mainly through hydrogen bonding and hydrophobic interaction. Aggregates in irregular shapes, with large sizes, were found by atomic force microscopy, and conglutination, integration or fusion of different entities into network structures occurred at a high level of shellac. At the mass ratio of zein to shellac of 1:1, curcumin in the complex particles exhibited improved photochemical and thermal stability. Curcumin-loaded zein-shellac complex particles allowed the controlled release of curcumin in both PBS medium and simulated gastrointestinal fluids. Copyright © 2017 Elsevier Ltd. All rights reserved.

New atom probe approaches to studying segregation in nanocrystalline materials.

PubMed

Samudrala, S K; Felfer, P J; Araullo-Peters, V J; Cao, Y; Liao, X Z; Cairney, J M

2013-09-01

Atom probe is a technique that is highly suited to the study of nanocrystalline materials. It can provide accurate atomic-scale information about the composition of grain boundaries in three dimensions. In this paper we have analysed the microstructure of a nanocrystalline super-duplex stainless steel prepared by high pressure torsion (HPT). Not all of the grain boundaries in this alloy display obvious segregation, making visualisation of the microstructure challenging. In addition, the grain boundaries present in the atom probe data acquired from this alloy have complex shapes that are curved at the scale of the dataset and the interfacial excess varies considerably over the boundaries, making the accurate characterisation of the distribution of solute challenging using existing analysis techniques. In this paper we present two new data treatment methods that allow the visualisation of boundaries with little or no segregation, the delineation of boundaries for further analysis and the quantitative analysis of Gibbsian interfacial excess at boundaries, including the capability of excess mapping. Copyright © 2013 Elsevier B.V. All rights reserved.

Hierarchical Model for the Analysis of Scattering Data of Complex Materials

DOE PAGES

Oyedele, Akinola; Mcnutt, Nicholas W.; Rios, Orlando; ...

2016-05-16

Interpreting the results of scattering data for complex materials with a hierarchical structure in which at least one phase is amorphous presents a significant challenge. Often the interpretation relies on the use of large-scale molecular dynamics (MD) simulations, in which a structure is hypothesized and from which a radial distribution function (RDF) can be extracted and directly compared against an experimental RDF. This computationally intensive approach presents a bottleneck in the efficient characterization of the atomic structure of new materials. Here, we propose and demonstrate an approach for a hierarchical decomposition of the RDF in which MD simulations are replacedmore » by a combination of tractable models and theory at the atomic scale and the mesoscale, which when combined yield the RDF. We apply the procedure to a carbon composite, in which graphitic nanocrystallites are distributed in an amorphous domain. We compare the model with the RDF from both MD simulation and neutron scattering data. Ultimately, this procedure is applicable for understanding the fundamental processing-structure-property relationships in complex magnetic materials.« less

Method for reducing NOx during combustion of coal in a burner

DOEpatents

Zhou, Bing [Cranbury, NJ; Parasher, Sukesh [Lawrenceville, NJ; Hare, Jeffrey J [Provo, UT; Harding, N Stanley [North Salt Lake, UT; Black, Stephanie E [Sandy, UT; Johnson, Kenneth R [Highland, UT

2008-04-15

An organically complexed nanocatalyst composition is applied to or mixed with coal prior to or upon introducing the coal into a coal burner in order to catalyze the removal of coal nitrogen from the coal and its conversion into nitrogen gas prior to combustion of the coal. This process leads to reduced NOx production during coal combustion. The nanocatalyst compositions include a nanoparticle catalyst that is made using a dispersing agent that can bond with the catalyst atoms. The dispersing agent forms stable, dispersed, nano-sized catalyst particles. The catalyst composition can be formed as a stable suspension to facilitate storage, transportation and application of the catalyst nanoparticles to a coal material. The catalyst composition can be applied before or after pulverizing the coal material or it may be injected directly into the coal burner together with pulverized coal.

Atomic scale chemical tomography of human bone

NASA Astrophysics Data System (ADS)

Langelier, Brian; Wang, Xiaoyue; Grandfield, Kathryn

2017-01-01

Human bone is a complex hierarchical material. Understanding bone structure and its corresponding composition at the nanometer scale is critical for elucidating mechanisms of biomineralization under healthy and pathological states. However, the three-dimensional structure and chemical nature of bone remains largely unexplored at the nanometer scale due to the challenges associated with characterizing both the structural and chemical integrity of bone simultaneously. Here, we use correlative transmission electron microscopy and atom probe tomography for the first time, to our knowledge, to reveal structures in human bone at the atomic level. This approach provides an overlaying chemical map of the organic and inorganic constituents of bone on its structure. This first use of atom probe tomography on human bone reveals local gradients, trace element detection of Mg, and the co-localization of Na with the inorganic-organic interface of bone mineral and collagen fibrils, suggesting the important role of Na-rich organics in the structural connection between mineral and collagen. Our findings provide the first insights into the hierarchical organization and chemical heterogeneity in human bone in three-dimensions at its smallest length scale - the atomic level. We demonstrate that atom probe tomography shows potential for new insights in biomineralization research on bone.

Synergic effect of atomic oxygen and outgassing phenomena on Carbon/SiC composites for space applications

NASA Astrophysics Data System (ADS)

Albano, Marta

The space environment is one of the most critical for space structures. The low earth orbit (LEO) space environment includes hazards such as atomic oxygen, UV radiation, ionizing radiation (electrons, protons), high vacuum, plasma, micrometeoroids and debris, as well as severe temperature cycles. Exposure of composites to the space environment may result in different detrimental effects via modification of their chemical, electrical, thermal, optical and mechanical properties as well as surface erosion. The high vacuum induces material outgassing (e.g. low-molecular weight residues, plasticizers and additives) and consequent contamination of nearby surfaces. At LEO altitudes the neutral atmosphere consists primarily of ATOX (˜80%) and nitrogen molecules (˜20%). ATOX, which is formed by photo-dissociation of molecular oxygen in the upper atmosphere, is a severe hazard for composites. The number density of ATOX at about 300 km altitude is ˜2 × 109 to 8 × 109 atoms/cm3, for minimum and maximum solar activity, respectively. Front surfaces (ram direction) of space vehicles orbiting at a velocity of about 8 km/s collide with the ATOX species with impingement kinetic energy of approximately 5 eV. The ATOX flux is determined by such parameters as altitude, orbital inclination, solar activity and time of day. A nominal range of values for LEO is 1014-1015 atoms/cm2 s. The Low Earth Orbit is a complex and dynamic environment where constituents vary with position, local time, season and solar activity. Effects of different constituents of the space environment on spacecraft materials play an important role in determining the system function, reliability and lifetime. This is more crucial if the structure has to be used for the re-entry as thermal protection systems for example. In this case the integrity of the surface and its coating is crucial for the success of the entire mission. During the re-entry, resistance of materials is hard tested by fast chemical reactions so that sublimation and ablation easily can take place. The key role played by carbon composites in re-entry environment is due to their high stability at high temperature, preserving their mechanical properties. However, most of these applications involve extended time periods in oxidizing environments where carbon reacts rapidly with oxygen at temperatures as low as 770K and the composites are subjected to oxidation degradation. For these reasons coated C/C and C/SiC composites are the most promising materials for the exposed surface of a thermal protection system. The modern approaches to a design of such materials assume broad application of mathematical and physical simulation methods. But mathematical simulation is impossible if there is no true information available on the characteristics (properties) of objects analyzed. In the majority of cases in practice the direct measurement of materials thermo physical properties, especially of complex composition, is impossible. There is only one way which permits to overcome these complexities - the indirect measurement. Mathematically, such an approach is usually formulated as a solution of the inverse problem: through direct measurements of system's state (temperature, component concentration, etc.) define the properties of a system analyzed, for example, the materials thermophysical characteristics. Violation of cause-and-effect relations in the statement of these problems results in their correctness in mathematical sense (i.e., the absence of existence and/or uniqueness and/or stability of the solution). Hence to solve such problems special methods are developed usually called regularized. In order to guarantee the success of a space structure there is the necessity to study the synergic effects of all the challenges that the harsh space environment place to the structure. For this reason here is presented a joint experimental study on synergic effects on C/SiC composites. Outgassing and atomic oxygen corrosion are investigated by experimental tests. A correlation between these two phenomena and the variation in thermal properties of the C/SiC composites is studied by the means of the inverse method and SEM analysis.

Semiconductor composition containing iron, dysprosium, and terbium

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

Pooser, Raphael C.; Lawrie, Benjamin J.; Baddorf, Arthur P.

An amorphous semiconductor composition includes 1 to 70 atomic percent iron, 15 to 65 atomic percent dysprosium, 15 to 35 atomic percent terbium, balance X, wherein X is at least one of an oxidizing element and a reducing element. The composition has an essentially amorphous microstructure, an optical transmittance of at least 50% in at least the visible spectrum and semiconductor electrical properties.

Doppler effects on 3-D non-LTE radiation transport and emission spectra.

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

Giuliani, J. L.; Davis, J.; DasGupta, A.

2010-10-01

Spatially and temporally resolved X-ray emission lines contain information about temperatures, densities, velocities, and the gradients in a plasma. Extracting this information from optically thick lines emitted from complex ions in dynamic, three-dimensional, non-LTE plasmas requires self-consistent accounting for both non-LTE atomic physics and non-local radiative transfer. We present a brief description of a hybrid-structure spectroscopic atomic model coupled to an iterative tabular on-the-spot treatment of radiative transfer that can be applied to plasmas of arbitrary material composition, conditions, and geometries. The effects of Doppler line shifts on the self-consistent radiative transfer within the plasma and the emergent emission andmore » absorption spectra are included in the model. Sample calculations for a two-level atom in a uniform cylindrical plasma are given, showing reasonable agreement with more sophisticated transport models and illustrating the potential complexity - or richness - of radially resolved emission lines from an imploding cylindrical plasma. Also presented is a comparison of modeled L- and K-shell spectra to temporally and radially resolved emission data from a Cu:Ni plasma. Finally, some shortcomings of the model and possible paths for improvement are discussed.« less

Investigation of iron adsorption on composite transition metal carbides in steel by first-principles calculation

NASA Astrophysics Data System (ADS)

Xiong, Hui-Hui; Gan, Lei; Tong, Zhi-Fang; Zhang, Heng-Hua; Zhou, Yang

2018-05-01

The nucleation potential of transition metal (TM) carbides formed in steel can be predicted by the behavior of iron adsorption on their surface. Therefore, Fe adsorption on the (001) surface of (A1-xmx)C (A = Nb, Ti, m = Mo, V) was investigated by the first-principles method to reveal the initialization of Fe nucleation. The Mulliken population and partial density of state (PDOS) were also calculated and analyzed in this work. The results show that Fe adsorption depends on the composition and configuration of the composite carbides. The adsorption energy (Wads) of Fe on most of (A1-xmx)C is larger than that of Fe on pure TiC or NbC. The maximum Wads is found for Fe on (Nb0.5Mo0.5)C complex carbide, indicating that this carbide has the high nucleation capacity at early stage. The Fe adsorption could be improved by the segregation of Cr and Mn atoms on the surfaces of (Nb0.5Mo0.5)C and (Ti0.5Mo0.5)C. The PDOS analysis of (Cr, Mn)-doped systems further explains the strong interactions between Fe and Cr or Mn atoms.

A systematic composite service design modeling method using graph-based theory.

PubMed

Elhag, Arafat Abdulgader Mohammed; Mohamad, Radziah; Aziz, Muhammad Waqar; Zeshan, Furkh

2015-01-01

The composite service design modeling is an essential process of the service-oriented software development life cycle, where the candidate services, composite services, operations and their dependencies are required to be identified and specified before their design. However, a systematic service-oriented design modeling method for composite services is still in its infancy as most of the existing approaches provide the modeling of atomic services only. For these reasons, a new method (ComSDM) is proposed in this work for modeling the concept of service-oriented design to increase the reusability and decrease the complexity of system while keeping the service composition considerations in mind. Furthermore, the ComSDM method provides the mathematical representation of the components of service-oriented design using the graph-based theoryto facilitate the design quality measurement. To demonstrate that the ComSDM method is also suitable for composite service design modeling of distributed embedded real-time systems along with enterprise software development, it is implemented in the case study of a smart home. The results of the case study not only check the applicability of ComSDM, but can also be used to validate the complexity and reusability of ComSDM. This also guides the future research towards the design quality measurement such as using the ComSDM method to measure the quality of composite service design in service-oriented software system.

A Systematic Composite Service Design Modeling Method Using Graph-Based Theory

PubMed Central

Elhag, Arafat Abdulgader Mohammed; Mohamad, Radziah; Aziz, Muhammad Waqar; Zeshan, Furkh

2015-01-01

The composite service design modeling is an essential process of the service-oriented software development life cycle, where the candidate services, composite services, operations and their dependencies are required to be identified and specified before their design. However, a systematic service-oriented design modeling method for composite services is still in its infancy as most of the existing approaches provide the modeling of atomic services only. For these reasons, a new method (ComSDM) is proposed in this work for modeling the concept of service-oriented design to increase the reusability and decrease the complexity of system while keeping the service composition considerations in mind. Furthermore, the ComSDM method provides the mathematical representation of the components of service-oriented design using the graph-based theoryto facilitate the design quality measurement. To demonstrate that the ComSDM method is also suitable for composite service design modeling of distributed embedded real-time systems along with enterprise software development, it is implemented in the case study of a smart home. The results of the case study not only check the applicability of ComSDM, but can also be used to validate the complexity and reusability of ComSDM. This also guides the future research towards the design quality measurement such as using the ComSDM method to measure the quality of composite service design in service-oriented software system. PMID:25928358

Atomic-Scale Characterization of Oxide Interfaces and Superlattices Using Scanning Transmission Electron Microscopy

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

Spurgeon, Steven R.; Chambers, Scott A.

Scanning transmission electron microscopy (STEM) has become one of the fundamental tools to characterize oxide interfaces and superlattices. Atomic-scale structure, chemistry, and composition mapping can now be conducted on a wide variety of materials systems thanks to the development of aberration-correctors and advanced detectors. STEM imaging and diffraction, coupled with electron energy loss (EELS) and energy-dispersive X-ray (EDS) spectroscopies, offer unparalleled, high-resolution analysis of structure-property relationships. In this chapter we highlight investigations into key phenomena, including interfacial conductivity in oxide superlattices, charge screening effects in magnetoelectric heterostructures, the design of high-quality iron oxide interfaces, and the complex physics governing atomic-scalemore » chemical mapping. These studies illustrate how unique insights from STEM characterization can be integrated with other techniques and first-principles calculations to develop better models for the behavior of functional oxides.« less

Copernicus, Epicurus, Galileo, and Gassendi.

PubMed

LoLordo, Antonia

2015-06-01

In his Letters on the motion impressed by a moving mover, the theory of the motion of composite bodies put forth by Gassendi is strikingly similar to Galileo's. In other of his writings, however, his description of the motion of individual atoms is understood very differently. In those places, he holds (1) that individual atoms are always in motion, even when the body that contains them is at rest, (2) that atomic motion is discontinuous although the motion of composite bodies is at least apparently continuous, and (3) that atomic motion is grounded in an intrinsic vis motrix, motive power. In contrast, composite bodies simply persist in their state of motion or rest in the absence of outside interference. Unfortunately, Gassendi neglects to explain how his accounts of atomic and composite motion fit together, and it is difficult to see how they could possibly be integrated. My goal is to explain, given this difficulty, why he accepted both the Galilean theory of the motion of composite bodies and the Epicurean theory of atomic motion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis, spectral and electrochemical studies of binuclear Ru(III) complexes containing dithiosemicarbazone ligand

NASA Astrophysics Data System (ADS)

Kanchana Devi, A.; Ramesh, R.

2014-01-01

Synthesis of several new octahedral binuclear ruthenium(III) complexes of the general composition [(EPh3)2(X)Ru-L-Ru(X)(EPh3)2] containing benzene dithiosemicarbazone ligands (where E = P or As; X = Cl or Br; L = binucleating ligands) is presented. All the complexes have been fully characterized by elemental analysis, FT-IR, UV-vis and EPR spectroscopy together with magnetic susceptibility measurements. IR study shows that the dithiosemicarbazone ligands behave as dianionic tridentate ligands coordinating through the oxygen atom of the deprotonated phenolic group, nitrogen atom of the azomethine group and thiolate sulphur. In DMF solution, all the complexes exhibit intense d-d transition and ligand-to-metal charge transfer (LMCT) transition in the visible region. The magnetic moment values of the complexes are in the range 1.78-1.82 BM, which reveals the presence of one unpaired electron on each metal ion. The EPR spectra of the liquid samples at LNT show the presence of three different 'g' values (gx ≠ gy ≠ gz) indicate a rhombic distortion around the ruthenium ion. All the complexes exhibit two quasi-reversible one electron oxidation responses (RuIII-RuIII/RuIII-RuIV; RuIII-RuIV/RuIV-RuIV) within the E1/2 range of 0.61-0.74 V and 0.93-0.98 V respectively, versus Ag/AgCl.

Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals

DOEpatents

Farmer, Joseph C.; Wong, Frank M.G.; Haslam, Jeffery J.; Yang, Nancy; Lavernia, Enrique J.; Blue, Craig A.; Graeve, Olivia A.; Bayles, Robert; Perepezko, John H.; Kaufman, Larry; Schoenung, Julie; Ajdelsztajn, Leo

2014-07-15

A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).

Corrosion resistant amorphous metals and methods of forming corrosion resistant amorphous metals

DOEpatents

Farmer, Joseph C [Tracy, CA; Wong, Frank M. G. [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Yang, Nancy [Lafayette, CA; Lavernia, Enrique J [Davis, CA; Blue, Craig A [Knoxville, TN; Graeve, Olivia A [Reno, NV; Bayles, Robert [Annandale, VA; Perepezko, John H [Madison, WI; Kaufman, Larry [Brookline, MA; Schoenung, Julie [Davis, CA; Ajdelsztajn, Leo [Walnut Creek, CA

2009-11-17

A system for coating a surface comprises providing a source of amorphous metal, providing ceramic particles, and applying the amorphous metal and the ceramic particles to the surface by a spray. The coating comprises a composite material made of amorphous metal that contains one or more of the following elements in the specified range of composition: yttrium (.gtoreq.1 atomic %), chromium (14 to 18 atomic %), molybdenum (.gtoreq.7 atomic %), tungsten (.gtoreq.1 atomic %), boron (.ltoreq.5 atomic %), or carbon (.gtoreq.4 atomic %).

A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: ionic composition in a wide range of cryolite ratios.

PubMed

Nazmutdinov, Renat R; Zinkicheva, Tamara T; Vassiliev, Sergey Yu; Glukhov, Dmitri V; Tsirlina, Galina A; Probst, Michael

2010-04-01

The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms ("dimers") was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition. Copyright 2010. Published by Elsevier B.V.

Graph-Based Semantic Web Service Composition for Healthcare Data Integration.

PubMed

Arch-Int, Ngamnij; Arch-Int, Somjit; Sonsilphong, Suphachoke; Wanchai, Paweena

2017-01-01

Within the numerous and heterogeneous web services offered through different sources, automatic web services composition is the most convenient method for building complex business processes that permit invocation of multiple existing atomic services. The current solutions in functional web services composition lack autonomous queries of semantic matches within the parameters of web services, which are necessary in the composition of large-scale related services. In this paper, we propose a graph-based Semantic Web Services composition system consisting of two subsystems: management time and run time. The management-time subsystem is responsible for dependency graph preparation in which a dependency graph of related services is generated automatically according to the proposed semantic matchmaking rules. The run-time subsystem is responsible for discovering the potential web services and nonredundant web services composition of a user's query using a graph-based searching algorithm. The proposed approach was applied to healthcare data integration in different health organizations and was evaluated according to two aspects: execution time measurement and correctness measurement.

Graph-Based Semantic Web Service Composition for Healthcare Data Integration

PubMed Central

2017-01-01

Within the numerous and heterogeneous web services offered through different sources, automatic web services composition is the most convenient method for building complex business processes that permit invocation of multiple existing atomic services. The current solutions in functional web services composition lack autonomous queries of semantic matches within the parameters of web services, which are necessary in the composition of large-scale related services. In this paper, we propose a graph-based Semantic Web Services composition system consisting of two subsystems: management time and run time. The management-time subsystem is responsible for dependency graph preparation in which a dependency graph of related services is generated automatically according to the proposed semantic matchmaking rules. The run-time subsystem is responsible for discovering the potential web services and nonredundant web services composition of a user's query using a graph-based searching algorithm. The proposed approach was applied to healthcare data integration in different health organizations and was evaluated according to two aspects: execution time measurement and correctness measurement. PMID:29065602

Compositional modulated atomic layer stacking and uniaxial magnetocrystalline anisotropy of CoPt alloy sputtered films with close-packed plane orientation

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

Saito, Shin, E-mail: ssaito@ecei.tohoku.ac.jp; Nozawa, Naoki; Hinata, Shintaro

An atomic layer stacking structure in hexagonal close packed (hcp) Co{sub 100−x}Pt{sub x} alloy films with c-plane sheet texture was directly observed by a high-angle annular dark-field imaging scanning transmission electron microscopy. The analysis of sequential and/or compositional atomic layer stacking structure and uniaxial magnetocrystalline anisotropy (K{sub u} = K{sub u1} + K{sub u2}) revealed that (1) integrated intensity of the superlattice diffraction takes the maximum at x = 20 at. % and shows broadening feature against x for the film fabricated under the substrate temperature (T{sub sub}) of 400 °C. (2) Compositional separation structure in atomic layers is formed for the films fabricated under T{sub sub} = 400 °C.more » A sequential alternative stacking of atomic layers with different compositions is hardly formed in the film with x = 50 at. %, whereas easily formed in the film with x = 20 at. %. This peculiar atomic layer stacking structure consists of in-plane-disordered Pt-rich and Pt-poor layers, which is completely different from the so-called atomic site ordered structure. (3) A face centered cubic atomic layer stacking as faults appeared in the host hcp atomic layer stacking exists in accompanies with irregularities for the periodicity of the compositional modulation atomic layers. (4) K{sub u1} takes the maximum of 1.4 × 10{sup 7 }erg/cm{sup 3} at around x = 20 at. %, whereas K{sub u2} takes the maximum of 0.7 × 10{sup 7 }erg/cm{sup 3} at around x = 40 at. %, which results in the maximum of 1.8 × 10{sup 7 }erg/cm{sup 3} of K{sub u} at x = 30 at. % and a shoulder in compositional dependence of K{sub u} in the range of x = 30–60 at. %. Not only compositional separation of atomic layers but also sequential alternative stacking of different compositional layers is quite important to improve essential uniaxial magnetocrystalline anisotropy.« less

Local mechanical and electromechanical properties of the P(VDF-TrFE)-graphene oxide thin films

NASA Astrophysics Data System (ADS)

Silibin, M. V.; Bystrov, V. S.; Karpinsky, D. V.; Nasani, N.; Goncalves, G.; Gavrilin, I. M.; Solnyshkin, A. V.; Marques, P. A. A. P.; Singh, Budhendra; Bdikin, I. K.

2017-11-01

Recently, many organic materials, including carbon materials such as carbon nanotubes (CNTs) and graphene (single-walled carbon sheet structure) were studied in order to improve their mechanical and electrical properties. In particular, copolymers of poly (vinylidene fluoride) and poly trifluoroethylene [P(VDF-TrFE)] are promising materials, which can be used as probes, sensors, actuators, etc. Composite thin film of the copolymer P(VDF-TrFE) with graphene oxide (GO) were prepared by spin coating. The obtained films were investigated using piezoresponse force microscopy (PFM). The switching behavior, piezoelectric response, dielectric permittivity and mechanical properties of the films were found to depend on the presence of GO. For understanding the mechanism of piezoresponse evolution of the composite we used models of PVDF chain, its behavior in electrical field and computed the data for piezoelectric coefficients using HyperChem software. The summarized models of graphene oxide based on graphene layer from 96 carbon atoms C: with oxygen and OH groups and with COOH groups arranged by hydrogen were used for PVDF/Graphene oxide complex: 1) with H-side (hydrogen atom) connected from PVDF to graphene oxide, 2) with F-side (fluorine atom) connected from PVDF graphene oxide and 3) Graphene Oxide/PVDF with both sides (sandwich type). Experimental results qualitatively correlate with those obtained in the calculations.

Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.

PubMed

Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

2014-01-25

To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution. Copyright © 2013 Elsevier B.V. All rights reserved.

Quantitative composition determination at the atomic level using model-based high-angle annular dark field scanning transmission electron microscopy.

PubMed

Martinez, G T; Rosenauer, A; De Backer, A; Verbeeck, J; Van Aert, S

2014-02-01

High angle annular dark field scanning transmission electron microscopy (HAADF STEM) images provide sample information which is sensitive to the chemical composition. The image intensities indeed scale with the mean atomic number Z. To some extent, chemically different atomic column types can therefore be visually distinguished. However, in order to quantify the atomic column composition with high accuracy and precision, model-based methods are necessary. Therefore, an empirical incoherent parametric imaging model can be used of which the unknown parameters are determined using statistical parameter estimation theory (Van Aert et al., 2009, [1]). In this paper, it will be shown how this method can be combined with frozen lattice multislice simulations in order to evolve from a relative toward an absolute quantification of the composition of single atomic columns with mixed atom types. Furthermore, the validity of the model assumptions are explored and discussed. © 2013 Published by Elsevier B.V. All rights reserved.

Determination of atomic-scale chemical composition at semiconductor heteroepitaxial interfaces by high-resolution transmission electron microscopy.

PubMed

Wen, C; Ma, Y J

2018-03-01

The determination of atomic structures and further quantitative information such as chemical compositions at atomic scale for semiconductor defects or heteroepitaxial interfaces can provide direct evidence to understand their formation, modification, and/or effects on the properties of semiconductor films. The commonly used method, high-resolution transmission electron microscopy (HRTEM), suffers from difficulty in acquiring images that correctly show the crystal structure at atomic resolution, because of the limitation in microscope resolution or deviation from the Scherzer-defocus conditions. In this study, an image processing method, image deconvolution, was used to achieve atomic-resolution (∼1.0 Å) structure images of small lattice-mismatch (∼1.0%) AlN/6H-SiC (0001) and large lattice-mismatch (∼8.5%) AlSb/GaAs (001) heteroepitaxial interfaces using simulated HRTEM images of a conventional 300-kV field-emission-gun transmission electron microscope under non-Scherzer-defocus conditions. Then, atomic-scale chemical compositions at the interface were determined for the atomic intermixing and Lomer dislocation with an atomic step by analyzing the deconvoluted image contrast. Furthermore, the effect of dynamical scattering on contrast analysis was also evaluated for differently weighted atomic columns in the compositions. Copyright © 2018 Elsevier Ltd. All rights reserved.

[DNA complexes, formed on aqueous phase surfaces: new planar polymeric and composite nanostructures].

PubMed

Antipina, M N; Gaĭnutdinov, R V; Rakhnianskaia, A A; Sergeev-Cherenkov, A N; Tolstikhina, A L; Iurova, T V; Kislov, V V; Khomutov, G B

2003-01-01

The formation of DNA complexes with Langmuir monolayers of the cationic lipid octadecylamine (ODA) and the new amphiphilic polycation poly-4-vinylpyridine with 16% of cetylpyridinium groups (PVP-16) on the surface of an aqueous solution of native DNA of low ionic strength was studied. Topographic images of Langmuir-Blodgett films of DNA/ODA and DNA/PVP-16 complexes applied to micaceous substrates were investigated by the method of atomic force microscopy. It was found that films of the amphiphilic polycation have an ordered planar polycrystalline structure. The morphology of planar DNA complexes with the amphiphilic cation substantially depended on the incubation time and the phase state of the monolayer on the surface of the aqueous DNA solution. Complex structures and individual DNA molecules were observed on the surface of the amphiphilic monolayer. Along with quasi-linear individual bound DNA molecules, characteristic extended net-like structures and quasi-circular toroidal condensed conformations of planar DNA complexes were detected. Mono- and multilayer films of DNA/PVP-16 complexes were used as templates and nanoreactors for the synthesis of inorganic nanostructures via the binding of metal cations from the solution and subsequent generation of the inorganic phase. As a result, ultrathin polymeric composite films with integrated DNA building blocks and quasi-linear arrays of inorganic semiconductor (CdS) and iron oxide nanoparticles and nanowires were obtained. The nanostructures obtained were characterized by scanning probe microscopy and transmission electron microscopy techniques. The methods developed are promising for investigating the mechanisms of structural organization and transformation in DNA and polyelectrolyte complexes at the gas-liquid interface and for the design of new extremely thin highly ordered planar polymeric and composite materials, films, and coatings with controlled ultrastructure for applications in nanoelectronics and nanobiotechnology.

Workflow Design Using Fragment Composition

NASA Astrophysics Data System (ADS)

Mosser, Sébastien; Blay-Fornarino, Mireille; France, Robert

The Service-Oriented Architecture (Soa) paradigm supports the assembly of atomic services to create applications that implement complex business processes. Assembly can be accomplished by service orchestrations defined by Soa architects. The Adore method allows Soa architects to model complex orchestrations of services by composing models of smaller orchestrations called orchestration fragments. The Adore method can also be used to weave fragments that address new concerns into existing application models. In this paper we illustrate how the Adore method can be used to separate and compose process aspects in a Soa design of the Car Crash Crisis Management System. The paper also includes a discussion of the benefits and limitations of the Adore method.

Composite pulses for interferometry in a thermal cold atom cloud

NASA Astrophysics Data System (ADS)

Dunning, Alexander; Gregory, Rachel; Bateman, James; Cooper, Nathan; Himsworth, Matthew; Jones, Jonathan A.; Freegarde, Tim

2014-09-01

Atom interferometric sensors and quantum information processors must maintain coherence while the evolving quantum wave function is split, transformed, and recombined, but suffer from experimental inhomogeneities and uncertainties in the speeds and paths of these operations. Several error-correction techniques have been proposed to isolate the variable of interest. Here we apply composite pulse methods to velocity-sensitive Raman state manipulation in a freely expanding thermal atom cloud. We compare several established pulse sequences, and follow the state evolution within them. The agreement between measurements and simple predictions shows the underlying coherence of the atom ensemble, and the inversion infidelity in a ˜80μK atom cloud is halved. Composite pulse techniques, especially if tailored for atom interferometric applications, should allow greater interferometer areas, larger atomic samples, and longer interaction times, and hence improve the sensitivity of quantum technologies from inertial sensing and clocks to quantum information processors and tests of fundamental physics.

Atom probe tomography (APT) of carbonate minerals.

PubMed

Pérez-Huerta, Alberto; Laiginhas, Fernando; Reinhard, David A; Prosa, Ty J; Martens, Rich L

2016-01-01

Atom probe tomography (APT) combines the highest spatial resolution with chemical data at atomic scale for the analysis of materials. For geological specimens, the process of field evaporation and molecular ion formation and interpretation is not yet entirely understood. The objective of this study is to determine the best conditions for the preparation and analysis by APT of carbonate minerals, of great importance in the interpretation of geological processes, focusing on the bulk chemical composition. Results show that the complexity of the mass spectrum is different for calcite and dolomite and relates to dissimilarities in crystalochemical parameters. In addition, APT bulk chemistry of calcite closely matches the expected stoichiometry but fails to provide accurate atomic percentages for elements in dolomite under the experimental conditions evaluated in this work. For both calcite and dolomite, APT underestimates the amount of oxygen based on their chemical formula, whereas it is able to detect small percentages of elemental substitutions in crystal lattices. Overall, our results demonstrate that APT of carbonate minerals is possible, but further optimization of the experimental parameters are required to improve the use of atom probe tomography for the correct interpretation of mineral geochemistry. Copyright © 2015 Elsevier Ltd. All rights reserved.

Trithiocyanurate complexes of iron, manganese and nickel and their anticholinesterase activity.

PubMed

Kopel, Pavel; Dolezal, Karel; Langer, Vratislav; Jun, Daniel; Adam, Vojtech; Kuca, Kamil; Kizek, Rene

2014-04-08

The complexes of Fe(II), Mn(II) and Ni(II) with a combination of a Schiff base, nitrogen-donor ligand or macrocyclic ligand and trithiocyanuric acid (ttcH3) were prepared and characterized by elemental analysis and spectroscopies. Crystal and molecular structures of the iron complex of composition [Fe(L1)](ttcH2)(ClO4)·EtOH·H2O (1), where L1 is Schiff base derived from tris(2-aminoethyl)amine and 2-pyridinecarboxaldehyde, were solved. It was found that the Schiff base is coordinated to the central iron atom by six nitrogens forming deformed octahedral arrangement, whereas trithiocyanurate(1-) anion, perchlorate and solvent molecules are not coordinated. The X-ray structure of the Schiff base sodium salt is also presented and compared with the iron complex. The anticholinesterase activity of the complexes was also studied.

Space environmental effects on polymer composites: Research needs and opportunities

NASA Technical Reports Server (NTRS)

Jang, Bor Z.; Bianchi, J.; Liu, Y. M.; Chang, C. P.

1993-01-01

The long-term performance of polymer-based composites in the space environment is discussed. Both thermoset and thermoplastic matrix composites are included in this discussion. Previous efforts on the space environmental effects on composites are briefly reviewed. Focus of this review is placed on the effects of hygrothermal stresses, atomic oxygen, ultraviolet (UV), and space debris/micrometeoroid impacts along with the potential synergism. Potential approaches to estimating the residual strength of polymer composites after exposure to atomic oxygen erosion or space debris/micrometeoroid impact are evaluated. New ground-based data are then utilized to illustrate the effects of atomic oxygen and thermal cycling on the failure behavior of polymer composites. Finally, research needs, challenges, and opportunities in the field of space environmental effects on composite materials are highlighted.

Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide bromine atom complexes with alcohols

NASA Astrophysics Data System (ADS)

Sumiyoshi, Takashi; Fujiyoshi, Ryoko; Katagiri, Miho; Sawamura, Sadashi

2007-05-01

Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10 9 M -1 s -1 and 6300 M -1 cm -1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl 3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ˜10 8 M -1 s -1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ˜ 10 7 M -1 s -1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes.

Complex Stoichiometry reordering of PTCDA on Ag(111) upon K Intercalation

NASA Astrophysics Data System (ADS)

Brivio, G. P.; Baby, A.; Zwick, C.; Gruenewald, M.; Forker, R.; Fritz, T.; Fratesi, G.; Hofmann, O. T.; Zojer, E.

Alkali metal atoms are a simple yet efficient n-type dopant of organic semiconductors. However, the molecular crystal structures need be controlled and well understood in order to optimize the electronic properties (charge carrier density and mobility) of the target material. Here, we report that potassium intercalation into PTCDA monolayer domains on a Ag(111) substrate induces distinct stoichiometry-dependent structural reordering processes, resulting in highly ordered and large KxPTCDA domains. The emerging structures are analyzed by low temperature scanning tunneling microscopy (STM), scanning tunneling hydrogen microscopy (STHM), and low-energy electron diffraction (LEED) as a function of the stoichiometry and by density functional theory (DFT) calculations. Large stable monolayer domains are found for x=2,4. The epitaxy types for all intercalated stages are determined as point-on-line. The K atoms adsorb in the vicinity of the oxygen atoms of the PTCDA molecules, and their positions are determined with sub-Angstrom precision. This is a crucial prerequisite for the prospective assessment of the electronic properties of such composite films, as they depend on the mutual alignment between donor atoms and acceptor molecules.

Isotopic composition of a sample enriched in 93Zr

DOE PAGES

Fujii, Toshiyuki; Hori, Jun-ichi; Du, Miting; ...

2015-10-22

A project to determine the neutron-capture cross section of long lived fission products and minor actinides has been started by using a beam-line at Japan Proton Accelerator Research Complex (J-PARC). We prepared one of the target nuclides is Zr-93, which in Oak Ridge National Laboratory. Qualitative and quantitative analyses on the sample were performed at Kyoto University. The isotopic composition of (m) Zr (m 90, 91, 92, 93, 94, and 96) was precisely determined by multi-collector thermal ionization mass spectrometry with < 0.1 % of 2 sigma uncertainty. We determined that the atomic abundance of Zr-93 in the sample tomore » be 18.86 ± A 0.05 %.« less

Composite material reinforced with atomized quasicrystalline particles and method of making same

DOEpatents

Biner, S.B.; Sordelet, D.J.; Lograsso, B.K.; Anderson, I.E.

1998-12-22

A composite material comprises an aluminum or aluminum alloy matrix having generally spherical, atomized quasicrystalline aluminum-transition metal alloy reinforcement particles disposed in the matrix to improve mechanical properties. A composite article can be made by consolidating generally spherical, atomized quasicrystalline aluminum-transition metal alloy particles and aluminum or aluminum alloy particles to form a body that is cold and/or hot reduced to form composite products, such as composite plate or sheet, with interfacial bonding between the quasicrystalline particles and the aluminum or aluminum alloy matrix without damage (e.g. cracking or shape change) of the reinforcement particles. The cold and/or hot worked composite exhibits substantially improved yield strength, tensile strength, Young`s modulus (stiffness). 3 figs.

Melting phenomena: effect of composition for 55-atom Ag-Pd bimetallic clusters.

PubMed

Cheng, Daojian; Wang, Wenchuan; Huang, Shiping

2008-05-14

Understanding the composition effect on the melting processes of bimetallic clusters is important for their applications. Here, we report the relationship between the melting point and the metal composition for the 55-atom icosahedral Ag-Pd bimetallic clusters by canonical Monte Carlo simulations, using the second-moment approximation of the tight-binding potentials (TB-SMA) for the metal-metal interactions. Abnormal melting phenomena for the systems of interest are found. Our simulation results reveal that the dependence of the melting point on the composition is not a monotonic change, but experiences three different stages. The melting temperatures of the Ag-Pd bimetallic clusters increase monotonically with the concentration of the Ag atoms first. Then, they reach a plateau presenting almost a constant value. Finally, they decrease sharply at a specific composition. The main reason for this change can be explained in terms of the relative stability of the Ag-Pd bimetallic clusters at different compositions. The results suggest that the more stable the cluster, the higher the melting point for the 55-atom icosahedral Ag-Pd bimetallic clusters at different compositions.

Alkyl phospholipid antihypertensive agents in method of lowering blood pressure

DOEpatents

Snyder, Fred L.; Blank, Merle L.; Muirhead, Ernest E.; Leach, deceased, Byron E.; Byers, Lawrence W.

1988-01-01

The composition of this invention is 1-O-alkyl-2-acetoyl-sn-glycero-3-phosphocholine, having the ionic structural formula; ##STR1## wherein R is saturated alkyl having 9-21 carbon atoms, or salts or hydrates of the composition. Preferably R has 13-19 carbon atoms and most preferably R has 15 carbon atoms. The composition of this invention is useful for reducing hypertension in warm-blooded animals, including humans, when administered either orally or by injection or innoculation, e.g., intravenous injection. The composition can be prepared from naturally occurring lipids or synthetically from commercially available material.

Metastability and structural polymorphism in noble metals: the role of composition and metal atom coordination in mono- and bimetallic nanoclusters.

PubMed

Sanchez, Sergio I; Small, Matthew W; Bozin, Emil S; Wen, Jian-Guo; Zuo, Jian-Min; Nuzzo, Ralph G

2013-02-26

This study examines structural variations found in the atomic ordering of different transition metal nanoparticles synthesized via a common, kinetically controlled protocol: reduction of an aqueous solution of metal precursor salt(s) with NaBH₄ at 273 K in the presence of a capping polymer ligand. These noble metal nanoparticles were characterized at the atomic scale using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM). It was found for monometallic samples that the third row, face-centered-cubic (fcc), transition metal [(3M)-Ir, Pt, and Au] particles exhibited more coherently ordered geometries than their second row, fcc, transition metal [(2M)-Rh, Pd, and Ag] analogues. The former exhibit growth habits favoring crystalline phases with specific facet structures while the latter samples are dominated by more disordered atomic arrangements that include complex systems of facets and twinning. Atomic pair distribution function (PDF) measurements further confirmed these observations, establishing that the 3M clusters exhibit longer ranged ordering than their 2M counterparts. The assembly of intracolumn bimetallic nanoparticles (Au-Ag, Pt-Pd, and Ir-Rh) using the same experimental conditions showed a strong tendency for the 3M atoms to template long-ranged, crystalline growth of 2M metal atoms extending up to over 8 nm beyond the 3M core.

Effects of ultrasonic treatment on amylose-lipid complex formation and properties of sweet potato starch-based films.

PubMed

Liu, Pengfei; Wang, Rui; Kang, Xuemin; Cui, Bo; Yu, Bin

2018-06-01

To investigate the effect of ultrasonic treatment on the properties of sweet potato starch and sweet potato starch-based films, the complexing index, thermograms and diffractograms of the sweet potato starch-lauric acid composite were tested, and light transmission, microstructure, and mechanical and moisture barrier properties of the films were measured. The results indicated that the low power density ultrasound was beneficial to the formation of an inclusion complex. In thermograms, the gelatinization enthalpies of the ultrasonically treated starches were lower than those of the untreated sample. With the ultrasonic amplitude increased from 40% to 70%, the melting enthalpy (ΔH) of the inclusion complex gradually decreased. X-ray diffraction revealed that the diffraction intensity of the untreated samples was weaker than that of the ultrasonically treated samples. When the ultrasonic amplitude was above 40%, the diffraction intensity and relative crystallinity of inclusion complex gradually decreased. The scanning electronic microscope showed that the surface of the composite films became smooth after being treated by ultrasonication. Ultrasonication led to a reduction in film surface roughness under atomic force microscopy analysis. The films with ultrasonic treatment exhibited higher light transmission, lower elongation at break, higher tensile strength and better moisture barrier property than those without ultrasonic treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Experimental design, modeling and optimization of polyplex formation between DNA oligonucleotides and branched polyethylenimine.

PubMed

Clima, Lilia; Ursu, Elena L; Cojocaru, Corneliu; Rotaru, Alexandru; Barboiu, Mihail; Pinteala, Mariana

2015-09-28

The complexes formed by DNA and polycations have received great attention owing to their potential application in gene therapy. In this study, the binding efficiency between double-stranded oligonucleotides (dsDNA) and branched polyethylenimine (B-PEI) has been quantified by processing of the images captured from the gel electrophoresis assays. The central composite experimental design has been employed to investigate the effects of controllable factors on the binding efficiency. On the basis of experimental data and the response surface methodology, a multivariate regression model has been constructed and statistically validated. The model has enabled us to predict the binding efficiency depending on experimental factors, such as concentrations of dsDNA and B-PEI as well as the initial pH of solution. The optimization of the binding process has been performed using simplex and gradient methods. The optimal conditions determined for polyplex formation have yielded a maximal binding efficiency close to 100%. In order to reveal the mechanism of complex formation at the atomic-scale, a molecular dynamic simulation has been carried out. According to the computation results, B-PEI amine hydrogen atoms have interacted with oxygen atoms from dsDNA phosphate groups. These interactions have led to the formation of hydrogen bonds between macromolecules, stabilizing the polyplex structure.

Composite material reinforced with atomized quasicrystalline particles and method of making same

DOEpatents

Biner, Suleyman B.; Sordelet, Daniel J.; Lograsso, Barbara K.; Anderson, Iver E.

1998-12-22

A composite material comprises an aluminum or aluminum alloy matrix having generally spherical, atomized quasicrystalline aluminum-transition metal alloy reinforcement particles disposed in the matrix to improve mechanical properties. A composite article can be made by consolidating generally spherical, atomized quaiscrystalline aluminum-transition metal alloy particles and aluminum or aluminum alloy particles to form a body that is cold and/or hot reduced to form composite products, such as composite plate or sheet, with interfacial bonding between the quasicrystalline particles and the aluminum or aluminum alloy matrix without damage (e.g. cracking or shape change) of the reinforcement particles. The cold and/or hot worked compositehibits substantially improved yield strength, tensile strength, Young's modulus (stiffness).

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

NASA Astrophysics Data System (ADS)

Gunasekera, K.; Boolchand, P.; Micoulaut, M.

2014-04-01

Amorphous GexSixTe1-2x glasses are studied as a function of composition by a combination of experimental and theoretical methods, allowing for a full description of the network structure in relationship with physico-chemical properties. Calorimetric and thermal measurements reveal that such glasses display an anomalous behavior across a range of compositions xc1=7.5% and

Atom-scale compositional distribution in InAlAsSb-based triple junction solar cells by atom probe tomography.

PubMed

Hernández-Saz, J; Herrera, M; Delgado, F J; Duguay, S; Philippe, T; Gonzalez, M; Abell, J; Walters, R J; Molina, S I

2016-07-29

The analysis by atom probe tomography (APT) of InAlAsSb layers with applications in triple junction solar cells (TJSCs) has shown the existence of In- and Sb-rich regions in the material. The composition variation found is not evident from the direct observation of the 3D atomic distribution and because of this a statistical analysis has been required. From previous analysis of these samples, it is shown that the small compositional fluctuations determined have a strong effect on the optical properties of the material and ultimately on the performance of TJSCs.

A motif for infinite metal atom wires.

PubMed

Yin, Xi; Warren, Steven A; Pan, Yung-Tin; Tsao, Kai-Chieh; Gray, Danielle L; Bertke, Jeffery; Yang, Hong

2014-12-15

A new motif for infinite metal atom wires with tunable compositions and properties is developed based on the connection between metal paddlewheel and square planar complex moieties. Two infinite Pd chain compounds, [Pd4(CO)4(OAc)4Pd(acac)2] 1 and [Pd4(CO)4(TFA)4Pd(acac)2] 2, and an infinite Pd-Pt heterometallic chain compound, [Pd4(CO)4(OAc)4Pt(acac)2] 3, are identified by single-crystal X-ray diffraction analysis. In these new structures, the paddlewheel moiety is a Pd four-membered ring coordinated by bridging carboxylic ligands and μ2 carbonyl ligands. The planar moiety is either Pd(acac)2 or Pt(acac)2 (acac = acetylacetonate). These moieties are connected by metallophilic interactions. The results showed that these one-dimensional metal wire compounds have photoluminescent properties that are tunable by changing ligands and metal ions. 3 can also serve as a single source precursor for making Pd4Pt bimetallic nanostructures with precise control of metal composition. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

2015-05-01

The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader's quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN (1Σ) and hydrideisocyanidezinc HZnNC (1Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]+ composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn+ (2Σ) and HCNZn+ (2Σ).

Extended X-ray absorption fine structure investigation of Sn local environment in strained and relaxed epitaxial Ge{sub 1−x}Sn{sub x} films

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

Gencarelli, F., E-mail: federica.gencarelli@imec.be; Heyns, M.; Department of Metallurgy and Materials Engineering, KU Leuven, Kasteelpark Arenberg 44, B-3001 Leuven

2015-03-07

We present an extended X-ray absorption fine structure investigation of the local environment of Sn atoms in strained and relaxed Ge{sub 1−x}Sn{sub x} layers with different compositions. We show that the preferred configuration for the incorporation of Sn atoms in these Ge{sub 1−x}Sn{sub x} layers is that of a α-Sn defect, with each Sn atom covalently bonded to four Ge atoms in a classic tetrahedral configuration. Sn interstitials, Sn-split vacancy complexes, or Sn dimers, if present at all, are not expected to involve more than 2.5% of the total Sn atoms. This finding, along with a relative increase of Snmore » atoms in the second atomic shell around a central Sn atom in Ge{sub 1−x}Sn{sub x} layers with increasing Sn concentrations, suggests that the investigated materials are homogeneous random substitutional alloys. Within the accuracy of the measurements, the degree of strain relaxation of the Ge{sub 1−x}Sn{sub x} layers does not have a significant impact on the local atomic surrounding of the Sn atoms. Finally, the calculated topological rigidity parameter a** = 0.69 ± 0.29 indicates that the strain due to alloying in Ge{sub 1−x}Sn{sub x} is accommodated via bond stretching and bond bending, with a slight predominance of the latter, in agreement with ab initio calculations reported in literature.« less

Synthesis, photophysical properties and structures of organotin-Schiff bases utilizing aromatic amino acid from the chiral pool and evaluation of the biological perspective of a triphenyltin compound.

PubMed

Basu Baul, Tushar S; Kehie, Pelesakuo; Duthie, Andrew; Guchhait, Nikhil; Raviprakash, Nune; Mokhamatam, Raveendra B; Manna, Sunil K; Armata, Nerina; Scopelliti, Michelangelo; Wang, Ruimin; Englert, Ulli

2017-03-01

Five new organotin(IV) complexes of compositions [Me 2 SnL 1 ] (1), [Me 2 SnL 2 ] n (2), [Me 2 SnL 3 ] (3), [Ph 3 SnL 1 H] n (4) and [Ph 3 SnL 3 H] (5) (where L 1 =(2S)-2-((E)-((Z)-4-hydroxypent-3-en-2-ylidene)amino)-3-(1H-indol-3-yl)propanoate, L 2 =(2S)-(E)-2-((2-hydroxybenzylidene)amino)-3-(1H-indol-3-yl)propanoate and L 3 =(2S)-(E)-2-((1-(2-hydroxyphenyl)ethylidene)amino)-3-(1H-indol-3-yl)propanoate were synthesized and spectroscopically characterized. The crystal structures of 1-4 were determined. For the dimethyltin derivative 2, a polymeric chain structure was observed as a result of a long Sn∙∙∙O contact involving the exocyclic carbonyl oxygen-atom from the tridentate ligand of a neighboring Sn-complex unit. The tin atom in this complex has a distorted octahedral coordination geometry, in which the long Sn-O bond is almost trans to the tridentate ligand nitrogen-atom. In contrast, the dimethyltin(IV) complexes 1 and 3 displayed discrete monomeric structures where the tin atom has distorted trigonal-bipyramidal geometry with the two coordinating L oxygen atoms defining the axial positions. On the other hand, 4 is a chain polymer in the solid state. The ligand-bridged Sn atoms adopt a trans-Ph 3 SnO 2 trigonal-bipyramidal configuration with equatorial phenyl groups. A carboxylato oxygen atom from one and the hydroxyl oxygen of the successive ligand in the chain occupy the axial positions. The solution structures were predicted by the use of 119 Sn NMR chemical shifts. The photophysical properties of the complexes were investigated in the solid and in solution. The triphenyltin(IV) compound 4 was tested in detail ex vivo against A375 (human melanoma) cell line, exhibiting an IC 50 value of 261nM to induce cell death as assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay without significant alteration of cytolysis as determined by lactate dehydrogenase (LDH) assay. Compound 4-mediated potent cell death was also determined by Live and Dead assay and caspase-mediated cleavage of poly-ADP ribose polymerase (PARP). Potent cell death activity was not observed in primary cells, like blood-derived peripheral mononuclear cells (PBMC). Compound 4 inhibited the diphenyl hexatriene (DPH) binding to cells and decreased the micro viscosity in a dose-dependent manner. Additionally, the ability of 4 and cyclodextrin (CD) to interact was determined by molecular modelling. Copyright © 2016 Elsevier Inc. All rights reserved.

Observation of CO2 in Comet C/2012 K5 LINEAR

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Chanover, Nancy

2012-12-01

The study of cometary composition is important to understanding the formation and evolution of our solar system. Comets have undergone very little thermal evolution in their lifetimes, which results in their near pristine composition. The nucleus of a comet is very rarely detected directly. Instead, we observe the coma that surrounds the nucleus. Physical and chemical processes in the coma affect its composition, and therefore coma composition is not a direct representation of nuclear composition. An important trend is the observed variation of coma composition with heliocentric distance, most likely influenced by the volatility of the main surface ices, H2O, CO2, and CO. Infrared studies of these molecules are complicated by telluric features, so often daughter molecules of these species such as OH are observed instead. A potentially effective tracer for these primary ices is atomic oxygen in the coma. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comet C/2012 K5 LINEAR. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and observations of H2O at Keck. These near simultaneous observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of these primary volatiles and aid our understanding of the variation in coma composition as a function of heliocentric distance, and therefore the composition of the nucleus and how our solar system was formed.

Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

DOE PAGES

Coplen, Tyler B.; Holden, Norman E.

2016-01-01

Abstract The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Anymore » desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.« less

Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Holden, Norman E.

2016-01-01

The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Any desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.

Evaluation of atomic oxygen resistant protective coatings for fiberglass-epoxy composites in LEO

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Paulsen, Phillip E.; Brady, Joyce A.

1989-01-01

Fiberglass-epoxy composite masts are the prime structural members for the Space Station Freedom solar array. At the altitude where Space Station Freedom will operate, atomic oxygen atoms are the most predominant species. Atomic oxygen is highly reactive and has been shown to oxidize organic and some metallic materials. Tests with random and directed atomic oxygen exposure have shown that the epoxy is removed from the composite exposing brittle glass fibers which could be easily removed from the surface where they could contaminate Space Station Freedom Systems. Protection or fiber containment systems; inorganic based paints, aluminum braid, and a metal coating; were evaluated for resistance to atomic oxygen, vacuum ultraviolet radiation, thermal cycling, and mechanical flexing. All appeared to protect well against atomic oxygen and provide fiber containment except for the single aluminum braid covering. UV radiation resistance was acceptable and in general, thermal cycling and flexure had little to no effect on the mass loss rate for most coatings.

Origin of organic matter in the protosolar nebula and in comets

NASA Technical Reports Server (NTRS)

Greenberg, J. M.; Shalabiea, O. M.; Mendoza-Gomez, C. X.; Schutte, W.; Gerakines, P. A.

1994-01-01

Comet organics are traced to their origin in interstellar space. Possible sources of comet organics from solar nebula chemistry are briefly discussed. The infrared spectra of interstellar dust are compared with spectra of solar (space) irradiated laboratory organic residues and with meteorites. The spectra compare very favorably. The atomic composition of first generation laboratory organic residues compares favorably with that of comet Halley organics if divided into approrpriate 'volatile' (less refreactory) and 'refractory' (more refractory) complex organics.

Study of the composition, structure, and optical properties of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket films erbium doped from the Er(pd){sub 3} complex compound

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

Kudoyarova, V. Kh., E-mail: kudoyarova@mail.ioffe.ru; Tolmachev, V. A.; Gushchina, E. V.

2013-03-15

Rutherford backscattering, IR spectroscopy, ellipsometry, and atomic-force microscopy are used to perform an integrated study of the composition, structure and optical properties of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films. The technique employed to obtain the a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films includes the high-frequency decomposition of a mixture of gases, (SiH{sub 4}){sub a} + (CH{sub 4}){sub b}, and the simultaneous thermal evaporation of a complex compound, Er(pd){sub 3}. It is demonstrated that raising the amount of CH{sub 4} in the gas mixture results in an increase in the carbon content of the films under study andmore » an increase in the optical gap E{sub g}{sup opt} from 1.75 to 2.2 eV. Changes in the composition of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films, accompanied, in turn, by changes in the optical constants, are observed in the IR spectra. The ellipsometric spectra obtained are analyzed in terms of multiple-parameter models. The conclusion is made on the basis of this analysis that the experimental and calculated spectra coincide well when variation in the composition of the amorphous films with that of the gas mixture is taken into account. The existence of a thin (6-8 nm) silicon-oxide layer on the surface of the films under study and the validity of using the double-layer model in ellipsometric calculations is confirmed by the results of structural analyses by atomic-force microscopy.« less

Standard deviations of composition measurements in atom probe analyses-Part II: 3D atom probe.

PubMed

Danoix, F; Grancher, G; Bostel, A; Blavette, D

2007-09-01

In a companion paper [F. Danoix, G. Grancher, A. Bostel, D. Blavette, Surf. Interface Anal. this issue (previous paper).], the derivation of variances of the estimates of measured composition, and the underlying hypotheses, have been revisited in the the case of conventional one dimensional (1D) atom probes. In this second paper, we will concentrate on the analytical derivation of the variance when the estimate of composition is obtained from a 3D atom probe. As will be discussed, when the position information is available, compositions can be derived either from constant number of atoms, or from constant volume, blocks. The analytical treatment in the first case is identical to the one developed for conventional 1D instruments, and will not be discussed further in this paper. Conversely, in the second case, the analytical treatment is different, as well as the formula of the variance. In particular, it will be shown that the detection efficiency plays an important role in the determination of the variance.

Analysis of Complex Carbohydrate Composition in Plant Cell Wall Using Fourier Transformed Mid-Infrared Spectroscopy (FT-IR).

PubMed

Badhan, Ajay; Wang, Yuxi; McAllister, Tim A

2017-01-01

Fourier transformed mid-infrared spectroscopy (FTIR) is a powerful tool for compositional analysis of plant cell walls (Acebes et al., Front Plant Sci 5:303, 2014; Badhan et al., Biotechnol Biofuels 7:1-15, 2014; Badhan et al., BioMed Res Int 2015: 562952, 2015; Roach et al., Plant Physiol 156:1351-1363, 2011). The infrared spectrum generates a fingerprint of a sample with absorption peaks corresponding to the frequency of vibrations between the bonds of the atoms making up the material. Here, we describe a method focused on the use of FTIR in combination with principal component analysis (PCA) to characterize the composition of the plant cell wall. This method has been successfully used to study complex enzyme saccharification processes like rumen digestion to identify recalcitrant moieties in low-quality forage which resist rumen digestion (Badhan et al., BioMed Res Int 2015: 562952, 2015), as well as to characterize cell wall mutant lines or transgenic lines expressing exogenous hydrolases (Badhan et al., Biotechnol Biofuels 7:1-15, 2014; Roach et al., Plant Physiol 156:1351-1363, 2011). The FTIR method described here facilitates high-throughput identification of the major compositional differences across a large set of samples in a low cost and nondestructive manner.

Bombardment-induced segregation and redistribution

NASA Astrophysics Data System (ADS)

Lam, N. Q.; Wiedersich, H.

During ion bombardment, a number of processes can alter the compositional distribution and microstructure in near-surface regions of alloys. The relative importance of each process depends principally on the target composition, temperature, and ion characteristics. In addition to displacement mixing leading to a randomization of atomic locations, and preferential loss of alloying elements by sputtering, which are dominant at relatively low temperatures, several thermally-activated processes, including radiation-enhanced diffusion, radiation-induced segregation and Gibbsian adsorption, also play important roles. At elevated temperatures, nonequilibrium point defects induced by ion impacts become mobile and tend to anneal out by recombination and diffusion to extended sinks, such as dislocations, grain boundaries and free surfaces. The high defect concentrations, far exceeding the thermodynamic equilibrium values, can enhance diffusion-controlled processes, while persistent defect fluxes, originating from the spatial non-uniformity in defect production and annihilation, give rise to local redistribution of alloy constituents because of radiation-induced segregation. Moreover, when the alloy is maintained at high temperature, Gibbsian adsorption, driven by the reduction in free energy of the system, occurs even without irradiation; it involves a compositional perturbation in a few atom layers near the alloy surface. The combination of these processes leads to the complex development of a compositionally-modified layer in the subsurface region. Considerable progress has been made recently in identifying and understanding the relative contributions from the individual processes under various irradiation conditions. In the present paper, selected examples of these different phenomena and their synergistic effects on the evolution of the near-surface compositions of alloys during sputtering and ion implantation at elevated temperatures are discussed.

Toward a better determination of dairy powders surface composition through XPS matrices development.

PubMed

Nikolova, Y; Petit, J; Sanders, C; Gianfrancesco, A; Scher, J; Gaiani, C

2015-01-01

The surface composition of dairy powders prepared by mixing various amounts of micellar casein (MC), whey proteins isolate (WPI), lactose, and anhydrous milk fat (AMF) was investigated by XPS measurements. The use of matrices are generally accepted to transform surface atomic composition (i.e., C, O, N contents) into surface component composition (i.e., lactose, proteins, lipids). These atomic-based matrices were revisited and two new matrices based on the surface bond composition were developed. Surface compositions obtained from atomic and bond-based matrices were compared. A successful matrix allowing good correlations between XPS predicted and theoretical surface composition for powders free from fat was identified. Nevertheless, samples containing milk fat were found to present a possible segregation of components owing to the AMF overrepresentation on the surface. Supplementary analyses (FTIR, SEM) were carried out in order to investigate the homogeneity of the mixtures. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and crystal structures of nitratocobaltates Na2[Co(NO3)4], K2[Co(NO3)4], and Ag[Co(NO3)3] and potassium nitratonickelate K2[Ni(NO3)4

NASA Astrophysics Data System (ADS)

Morozov, I. V.; Fedorova, A. A.; Albov, D. V.; Kuznetsova, N. R.; Romanov, I. A.; Rybakov, V. B.; Troyanov, S. I.

2008-03-01

The cobalt(II) and nickel(II) nitrate complexes with an island structure (Na2[Co(NO3)4] ( I) and K2[Co(NO3)4] ( II)] and a chain structure [Ag[Co(NO3)3] ( III) and K2[Ni(NO3)4] ( IV)] are synthesized and investigated using X-ray diffraction. In the anionic complex [Co(NO3)4]2- of the crystal structure of compound I, the Co coordination polyhedron is a twisted tetragonal prism formed by the O atoms of four asymmetric bidentate nitrate groups. In the anion [Co(NO3)4]2- of the crystal structure of compound II, one of the four NO3 groups is monodentate and the other NO3 groups are bidentate (the coordination number of the cobalt atom is equal to seven, and the cobalt coordination polyhedron is a monocapped trigonal prism). The crystal structures of compounds III and IV contain infinite chains of the compositions [Co(NO3)2(NO3)2/2]- and [Ni(NO3)3(NO3)2/2]2-, respectively. In the crystal structure of compound III, seven oxygen atoms of one monodentate and three bidentate nitrate groups form a dodecahedron with an unoccupied vertex of the A type around the Co atom. In the crystal structure of compound IV, the octahedral polyhedron of the Ni atom is formed by five nitrate groups, one of which is terminal bidentate. The data on the structure of Co(II) coordination polyhedra in the known nitratocobaltates are generalized.

Nanoscale Charge-Balancing Mechanism in Alkali-Substituted Calcium-Silicate-Hydrate Gels.

PubMed

Özçelik, V Ongun; White, Claire E

2016-12-15

Alkali-activated materials and related alternative cementitious systems are sustainable technologies that have the potential to substantially lower the CO 2 emissions associated with the construction industry. However, these systems have augmented chemical compositions as compared to ordinary Portland cement (OPC), which may impact the evolution of the hydrate phases. In particular, calcium-silicate-hydrate (C-S-H) gel, the main hydrate phase in OPC, is likely to be altered at the atomic scale due to changes in the bulk chemical composition, specifically via the addition of alkalis (i.e., Na or K) and aluminum. Here, via density functional theory calculations, we reveal the presence of a charge balancing mechanism at the molecular level in C-S-H gel (as modeled using crystalline 14 Å tobermorite) when alkalis and aluminum atoms are introduced into the structure. Different structural representations are obtained depending on the level of substitution and the degree of charge balancing incorporated in the structures. The impact of these substitutional and charge balancing effects on the structures is assessed by analyzing the formation energies, local bonding environments, diffusion barriers and mechanical properties. The results of this computational study provide information on the phase stability of alkali/aluminum containing C-S-H gels, shedding light on the fundamental atomic level mechanisms that play a crucial role in these complex disordered materials.

Organic solvent soluble oxide supported hydrogenation catalyst precursors

DOEpatents

Edlund, David J.; Finke, Richard G.; Saxton, Robert J.

1992-01-01

The present invention discloses two polyoxoanion supported metal complexes found to be useful in olefin hydrogenation. The complexes are novel compositions of matter which are soluble in organic solvents. In particular, the compositions of matter comprise A.sub.x [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.15 M'.sub.3 O.sub.62 ].sup.x- and A.sub.y [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.9 M'.sub.3 O.sub.40 ].sup.y- where L is a ligand preferably chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L; X is a "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M is either W or Mo; M' is preferably Nb or V but Ti, Zr, Ta, Hf are also useful; and A is a countercation preferably selected from tetrabutyl ammonium and alkali metal ions.

PEG and mPEG-anthracene induce DNA condensation and particle formation.

PubMed

Froehlich, E; Mandeville, J S; Arnold, D; Kreplak, L; Tajmir-Riahi, H A

2011-08-18

In this study, we investigated the binding of DNA with poly(ethylene glycol) (PEG) of different sizes and compositions such as PEG 3350, PEG 6000, and mPEG-anthracene in aqueous solution at physiological conditions. The effects of size and composition on DNA aggregation and condensation as well as conformation were determined using Fourier transform infrared (FTIR), UV-visible, CD, fluorescence spectroscopic methods and atomic force microscopy (AFM). Structural analysis showed moderate complex formation for PEG 3350 and PEG 6000 and weaker interaction for mPE-anthracene-DNA adducts with both hydrophilic and hydrophobic contacts. The order of ± stability of the complexes formed is K(PEG 6000) = 1.5 (±0.4) × 10(4) M(-1) > K(PEG 3350) = 7.9 (±1) × 10(3) M(-1) > K(m(PEG-anthracene))= 3.6 (±0.8) × 10(3) M(-1) with nearly 1 bound PEG molecule per DNA. No B-DNA conformational changes were observed, while DNA condensation and particle formation occurred at high PEG concentration.

Effects of optical dopants and laser wavelength on atom probe tomography analyses of borosilicate glasses

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

Lu, Xiaonan; Schreiber, Daniel K.; Neeway, James J.

Atom probe tomography (APT) is a novel analytical microscopy method that provides three dimensional elemental mapping with sub-nanometer spatial resolution and has only recently been applied to insulating glass and ceramic samples. In this paper, we have studied the influence of the optical absorption in glass samples on APT characterization by introducing different transition metal optical dopants to a model borosilicate nuclear waste glass (international simple glass). A systematic comparison is presented of the glass optical properties and the resulting APT data quality in terms of compositional accuracy and the mass spectra quality for two APT systems: one with amore » green laser (532 nm, LEAP 3000X HR) and one with a UV laser (355 nm, LEAP 4000X HR). These data were also compared to the study of a more complex borosilicate glass (SON68). The results show that the analysis data quality such as compositional accuracy and total ions collected, was clearly linked to optical absorption when using a green laser, while for the UV laser optical doping aided in improving data yield but did not have a significant effect on compositional accuracy. Comparisons of data between the LEAP systems suggest that the smaller laser spot size of the LEAP 4000X HR played a more critical role for optimum performance than the optical dopants themselves. The smaller spot size resulted in more accurate composition measurements due to a reduced background level independent of the material’s optical properties.« less

Nano is the next big thing: Revealing geochemical processes with atom probe microscopy

NASA Astrophysics Data System (ADS)

Reddy, Steven; Saxey, David; Rickard, William; Fougerouse, Denis; Peterman, Emily; van Riessen, Arie; Johnson, Tim

2017-04-01

Characterizing compositional variations in minerals at the nanometre scale has the potential to yield fundamental insights into a range of geological processes associated with nucleation and mineral growth and the subsequent modification of mineral compositions by processes such as diffusion, deformation and recrystallization. However, there are few techniques that allow the quantitative measurement of low abundance trace elements and isotopes signatures at the nanometre scale. Atom probe microscopy is one such technique that has been widely used in the study of metals and, in the last decade, semiconductors. However, the development and application of atom probe microscopy to minerals is in its infancy and only a handful of published studies exist in the literature. Here, we provide an introduction to atom probe microscopy and its potential use in geological studies using two examples from both undeformed and deformed zircon (ZrSiO4). In the first example, we use atom probe microscopy to show that discordant data from the core of an undeformed 2.1 Ga zircon, metamorphosed at granulite facies conditions 150 Myr ago, contains distinct Pb reservoirs that represent both the crystallisation and metamorphic 207Pb/206Pb ages. Crystallisation ages are preserved within ˜10 nm diameter dislocation loops that formed during annealing of radiation-damaged zircon during the prograde path of the metamorphic event. The results highlight the potential for resolving the chronology of multiple, distinct Pb reservoirs within isotopically complex zircon and provide an explanation for varying amounts of discordance within individual zircon grains. In the second example, we illustrate complex trace element distributions associated with near-instantaneous deformation of a shocked zircon during the ˜1.17 Ga Stac Fada bolide impact. Substitutional and interstitial ions show correlated segregation, indicating coupling between different mobility mechanisms associated with the rapid formation and migration of oxygen vacancies and dislocations into low energy configurations. The results of these two studies show how quantification of elemental and isotopic variations at the nanoscale may reveal fundamental new insights into geochemical processes that underpin the interpretation of geochemical data collected at the microscale. Furthermore, these new data highlight the important role of crystal defects, even in undeformed zircon, in the chemical modification of zircon, and allow the interplay amongst radiation damage, recrystallization and deformation to be assessed.

Application of composite dictionary multi-atom matching in gear fault diagnosis.

PubMed

Cui, Lingli; Kang, Chenhui; Wang, Huaqing; Chen, Peng

2011-01-01

The sparse decomposition based on matching pursuit is an adaptive sparse expression method for signals. This paper proposes an idea concerning a composite dictionary multi-atom matching decomposition and reconstruction algorithm, and the introduction of threshold de-noising in the reconstruction algorithm. Based on the structural characteristics of gear fault signals, a composite dictionary combining the impulse time-frequency dictionary and the Fourier dictionary was constituted, and a genetic algorithm was applied to search for the best matching atom. The analysis results of gear fault simulation signals indicated the effectiveness of the hard threshold, and the impulse or harmonic characteristic components could be separately extracted. Meanwhile, the robustness of the composite dictionary multi-atom matching algorithm at different noise levels was investigated. Aiming at the effects of data lengths on the calculation efficiency of the algorithm, an improved segmented decomposition and reconstruction algorithm was proposed, and the calculation efficiency of the decomposition algorithm was significantly enhanced. In addition it is shown that the multi-atom matching algorithm was superior to the single-atom matching algorithm in both calculation efficiency and algorithm robustness. Finally, the above algorithm was applied to gear fault engineering signals, and achieved good results.

On stoichiometry and intermixing at the spinel/perovskite interface in CoFe2O4/BaTiO3 thin films.

PubMed

Tileli, Vasiliki; Duchamp, Martial; Axelsson, Anna-Karin; Valant, Matjaz; Dunin-Borkowski, Rafal E; Alford, Neil McN

2015-01-07

The performance of complex oxide heterostructures depends primarily on the interfacial coupling of the two component structures. This interface character inherently varies with the synthesis method and conditions used since even small composition variations can alter the electronic, ferroelectric, or magnetic functional properties of the system. The focus of this article is placed on the interface character of a pulsed laser deposited CoFe2O4/BaTiO3 thin film. Using a range of state-of-the-art transmission electron microscopy methodologies, the roles of substrate morphology, interface stoichiometry, and cation intermixing are determined on the atomic level. The results reveal a surprisingly uneven BaTiO3 substrate surface formed after the film deposition and Fe atom incorporation in the top few monolayers inside the unit cell of the BaTiO3 crystal. Towards the CoFe2O4 side, a disordered region extending several nanometers from the interface was revealed and both Ba and Ti from the substrate were found to diffuse into the spinel layer. The analysis also shows that within this somehow incompatible composite interface, a different phase is formed corresponding to the compound Ba2Fe3Ti5O15, which belongs to the ilmenite crystal structure of FeTiO3 type. The results suggest a chemical activity between these two oxides, which could lead to the synthesis of complex engineered interfaces.

Statistical analysis of dimer formation in supersaturated metal vapor based on molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Korenchenko, Anna E.; Vorontsov, Alexander G.; Gelchinski, Boris R.; Sannikov, Grigorii P.

2018-04-01

We discuss the problem of dimer formation during the homogeneous nucleation of atomic metal vapor in an inert gas environment. We simulated nucleation with molecular dynamics and carried out the statistical analysis of double- and triple-atomic collisions as the two ways of long-lived diatomic complex formation. Close pair of atoms with lifetime greater than the mean time interval between atom-atom collisions is called a long-lived diatomic complex. We found that double- and triple-atomic collisions gave approximately the same probabilities of long-lived diatomic complex formation, but internal energy of the resulted state was essentially lower in the second case. Some diatomic complexes formed in three-particle collisions are stable enough to be a critical nucleus.

Method for continuous control of composition and doping of pulsed laser deposited films

DOEpatents

Lowndes, Douglas H.; McCamy, James W.

1995-01-01

A method for growing a deposit upon a substrate of semiconductor material involves the utilization of pulsed laser deposition techniques within a low-pressure gas environment. The substrate and a target of a first material are positioned within a deposition chamber and a low-pressure gas atmosphere is developed within the chamber. The substrate is then heated, and the target is irradiated, so that atoms of the target material are ablated from the remainder of the target, while atoms of the gas simultaneously are adsorbed on the substrate/film surface. The ablated atoms build up upon the substrate, together with the adsorbed gas atoms to form the thin-film deposit on the substrate. By controlling the pressure of the gas of the chamber atmosphere, the composition of the formed deposit can be controlled, and films of continuously variable composition or doping can be grown from a single target of fixed composition.

Method for continuous control of composition and doping of pulsed laser deposited films by pressure control

DOEpatents

Lowndes, Douglas H.; McCamy, James W.

1996-01-01

A method for growing a deposit upon a substrate of semiconductor material involves the utilization of pulsed laser deposition techniques within a low-pressure gas environment. The substrate and a target of a first material are positioned within a deposition chamber and a low-pressure gas atmosphere is developed within the chamber. The substrate is then heated, and the target is irradiated, so that atoms of the target material are ablated from the remainder of the target, while atoms of the gas simultaneously are adsorbed on the substrate/film surface. The ablated atoms build up upon the substrate, together with the adsorbed gas atoms to form the thin-film deposit on the substrate. By controlling the pressure of the gas of the chamber atmosphere, the composition of the formed deposit can be controlled, and films of continuously variable composition or doping can be grown from a single target of fixed composition.

Large moments in bcc FexCoyMnz ternary alloy thin films

NASA Astrophysics Data System (ADS)

Snow, R. J.; Bhatkar, H.; N'Diaye, A. T.; Arenholz, E.; Idzerda, Y. U.

2018-02-01

The elemental magnetic moments and the average atomic moment of 10-20 nm thick single crystal bcc (bct) FexCoyMnz films deposited on MgO(001) have been determined as a function of a broad range of compositions. Thin film epitaxy stabilized the bcc structure for 80% of the available ternary compositional space compared to only a 23% stability region for the bulk. The films that display ferromagnetism represent 60% of the available compositional possibilities compared to 25% for the bulk. A maximum average atomic moment of 3.25 ± 0.3 μB/atom was observed for a bcc Fe9Co62Mn29 film (well above the limit of the Slater-Pauling binary alloy curve of 2.45 μB/atom). The FexCoyMnz ternary alloys that exhibit high moments can only be synthesized as ultrathin films since the bcc structure is not stable in the bulk for those compositions.

Prediction of a New Phase of Cu x S near Stoichiometric Composition

DOE PAGES

Khatri, Prashant; Huda, Muhammad N.

2015-01-01

Cumore » 2 S is known to be a promising solar absorber material due to its suitable band gap and the abundance of its constituent elements. 2 S is known to have complex phase structures depending on the concentration of vacancies. Its instability of phases is due to favorable formation of vacancies and the mobility of atoms within the crystal. Understanding its phase structures is of crucial important for its application as solar absorber material. In this paper, we have predicted a new crystal phase of copper sulfide ( x S) around chemical composition of x = 1.98 by utilizing crystal database search and density functional theory. We have shown that this new crystal phase of x S is more favorable than low chalcocite structure even at stoichiometric composition of x = 2 . However, vacancy formation probability was found to be higher in this new phase than the low chalcocite structure.« less

Remote laser evaporative molecular absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hughes, Gary B.; Lubin, Philip; Cohen, Alexander; Madajian, Jonathan; Kulkarni, Neeraj; Zhang, Qicheng; Griswold, Janelle; Brashears, Travis

2016-09-01

We describe a novel method for probing bulk molecular and atomic composition of solid targets from a distant vantage. A laser is used to melt and vaporize a spot on the target. With sufficient flux, the spot temperature rises rapidly, and evaporation of surface materials occurs. The melted spot creates a high-temperature blackbody source, and ejected material creates a plume of surface materials in front of the spot. Molecular and atomic absorption occurs as the blackbody radiation passes through the ejected plume. Bulk molecular and atomic composition of the surface material is investigated by using a spectrometer to view the heated spot through the ejected plume. The proposed method is distinct from current stand-off approaches to composition analysis, such as Laser-Induced Breakdown Spectroscopy (LIBS), which atomizes and ionizes target material and observes emission spectra to determine bulk atomic composition. Initial simulations of absorption profiles with laser heating show great promise for Remote Laser-Evaporative Molecular Absorption (R-LEMA) spectroscopy. The method is well-suited for exploration of cold solar system targets—asteroids, comets, planets, moons—such as from a spacecraft orbiting the target. Spatial composition maps could be created by scanning the surface. Applying the beam to a single spot continuously produces a borehole or trench, and shallow subsurface composition profiling is possible. This paper describes system concepts for implementing the proposed method to probe the bulk molecular composition of an asteroid from an orbiting spacecraft, including laser array, photovoltaic power, heating and ablation, plume characteristics, absorption, spectrometry and data management.

Icosahedral and decagonal quasicrystals of intermetallic compounds are multiple twins of cubic or orthorhombic crystals composed of very large atomic complexes with icosahedral point-group symmetry in cubic close packing or body-centered packing: Structure of decagonal Al6Pd

PubMed Central

Pauling, Linus

1989-01-01

A doubly icosahedral complex involves roughly spherical clusters of atoms with icosahedral point-group symmetry, which are themselves, in parallel orientation, icosahedrally packed. These complexes may form cubic crystallites; three structures of this sort have been identified. Analysis of electron diffraction photographs of the decagonal quasicrystal Al6Pd has led to its description as involving pentagonal twinning of an orthorhombic crystal with a = 51.6 Å, b = 37.6 Å, and c = 33.24 Å, with about 4202 atoms in the unit, comprising two 1980-atom doubly icosahedral complexes, each involving icosahedral packing of 45 44-atom icosahedral complexes (at 0 0 0 and 1/2 1/2 1/2) and 242 interstitial atoms. The complexes and clusters are oriented with one of their fivefold axes in the c-axis direction. Images PMID:16594092

Icosahedral and decagonal quasicrystals of intermetallic compounds are multiple twins of cubic or orthorhombic crystals composed of very large atomic complexes with icosahedral point-group symmetry in cubic close packing or body-centered packing: Structure of decagonal Al(6)Pd.

PubMed

Pauling, L

1989-12-01

A doubly icosahedral complex involves roughly spherical clusters of atoms with icosahedral point-group symmetry, which are themselves, in parallel orientation, icosahedrally packed. These complexes may form cubic crystallites; three structures of this sort have been identified. Analysis of electron diffraction photographs of the decagonal quasicrystal Al(6)Pd has led to its description as involving pentagonal twinning of an orthorhombic crystal with a = 51.6 A, b = 37.6 A, and c = 33.24 A, with about 4202 atoms in the unit, comprising two 1980-atom doubly icosahedral complexes, each involving icosahedral packing of 45 44-atom icosahedral complexes (at 0 0 0 and 1/2 1/2 1/2) and 242 interstitial atoms. The complexes and clusters are oriented with one of their fivefold axes in the c-axis direction.

Quinary metallic glass alloys

DOEpatents

Lin, Xianghong; Johnson, William L.

1998-01-01

At least quinary alloys form metallic glass upon cooling below the glass transition temperature at a rate less than 10.sup.3 K/s. Such alloys comprise zirconium and/or hafnium in the range of 45 to 65 atomic percent, titanium and/or niobium in the range of 4 to 7.5 atomic percent, and aluminum and/or zinc in the range of 5 to 15 atomic percent. The balance of the alloy compositions comprise copper, iron, and cobalt and/or nickel. The composition is constrained such that the atomic percentage of iron is less than 10 percent. Further, the ratio of copper to nickel and/or cobalt is in the range of from 1:2 to 2:1. The alloy composition formula is: (Zr,Hf).sub.a (Al,Zn).sub.b (Ti,Nb).sub.c (Cu.sub.x Fe.sub.y (Ni,Co).sub.z).sub.d wherein the constraints upon the formula are: a ranges from 45 to 65 atomic percent, b ranges from 5 to 15 atomic percent, c ranges from 4 to 7.5 atomic percent, d comprises the balance, d.multidot.y is less than 10 atomic percent, and x/z ranges from 0.5 to 2.

Quinary metallic glass alloys

DOEpatents

Lin, X.; Johnson, W.L.

1998-04-07

At least quinary alloys form metallic glass upon cooling below the glass transition temperature at a rate less than 10{sup 3}K/s. Such alloys comprise zirconium and/or hafnium in the range of 45 to 65 atomic percent, titanium and/or niobium in the range of 4 to 7.5 atomic percent, and aluminum and/or zinc in the range of 5 to 15 atomic percent. The balance of the alloy compositions comprise copper, iron, and cobalt and/or nickel. The composition is constrained such that the atomic percentage of iron is less than 10 percent. Further, the ratio of copper to nickel and/or cobalt is in the range of from 1:2 to 2:1. The alloy composition formula is: (Zr,Hf){sub a}(Al,Zn){sub b}(Ti,Nb){sub c}(Cu{sub x}Fe{sub y}(Ni,Co){sub z}){sub d} wherein the constraints upon the formula are: a ranges from 45 to 65 atomic percent, b ranges from 5 to 15 atomic percent, c ranges from 4 to 7.5 atomic percent, d comprises the balance, d{hor_ellipsis}y is less than 10 atomic percent, and x/z ranges from 0.5 to 2.

Three-dimensional atom probe tomography of oxide, anion, and alkanethiolate coatings on gold.

PubMed

Zhang, Yi; Hillier, Andrew C

2010-07-15

We have used three-dimensional atom probe tomography to analyze several nanometer-thick and monomolecular films on gold surfaces. High-purity gold wire was etched by electropolishing to create a sharp tip suitable for field evaporation with a radius of curvature of <100 nm. The near-surface region of a freshly etched gold tip was examined with the atom probe at subnanometer spatial resolution and with atom-level composition accuracy. A thin contaminant layer, primarily consisting of water and atmospheric gases, was observed on a fresh tip. This sample exhibited crystalline lattice spacings consistent with the interlayer spacing of {200} lattice planes of bulk gold. A thin oxide layer was created on the gold surface via plasma oxidation, and the thickness and composition of this layer was measured. Clear evidence of a nanometer-thick oxide layer was seen coating the gold tip, and the atomic composition of the oxide layer was consistent with the expected stoichiometry for gold oxide. Monomolecular anions layers of Br(-) and I(-) were created via adsorption from aqueous solutions onto the gold. Atom probe data verified the presence of the monomolecular anion layers on the gold surface, with ion density values consistent with literature values. A hexanethiolate monolayer was coated onto the gold tip, and atom probe analysis revealed a thin film whose ion fragments were consistent with the molecular composition of the monolayer and a surface coverage similar to that expected from literature. Details of the various coating compositions and structures are presented, along with discussion of the reconstruction issues associated with properly analyzing these thin-film systems.

Mechanical gate control for atom-by-atom cluster assembly with scanning probe microscopy.

PubMed

Sugimoto, Yoshiaki; Yurtsever, Ayhan; Hirayama, Naoki; Abe, Masayuki; Morita, Seizo

2014-07-11

Nanoclusters supported on substrates are of great importance in physics and chemistry as well as in technical applications, such as single-electron transistors and nanocatalysts. The properties of nanoclusters differ significantly from those of either the constituent atoms or the bulk solid, and are highly sensitive to size and chemical composition. Here we propose a novel atom gating technique to assemble various atom clusters composed of a defined number of atoms at room temperature. The present gating operation is based on the transfer of single diffusing atoms among nanospaces governed by gates, which can be opened in response to the chemical interaction force with a scanning probe microscope tip. This method provides an alternative way to create pre-designed atom clusters with different chemical compositions and to evaluate their chemical stabilities, thus enabling investigation into the influence that a single dopant atom incorporated into the host clusters has on a given cluster stability.

Perfluorinated Polyalkylether Based Lubricant Composition.

DTIC Science & Technology

phosphorus atoms are substituted by aromatic groups and the carbon atom is substituted by a perfluoroalkyl or perfluoroalkylether moiety. (Author)...A lubricant composition comprising a perfluorinated polyalkylether base fluid and a minor amount of a diphospha-s-triazine in which the two

Experimental methods of molecular matter-wave optics.

PubMed

Juffmann, Thomas; Ulbricht, Hendrik; Arndt, Markus

2013-08-01

We describe the state of the art in preparing, manipulating and detecting coherent molecular matter. We focus on experimental methods for handling the quantum motion of compound systems from diatomic molecules to clusters or biomolecules.Molecular quantum optics offers many challenges and innovative prospects: already the combination of two atoms into one molecule takes several well-established methods from atomic physics, such as for instance laser cooling, to their limits. The enormous internal complexity that arises when hundreds or thousands of atoms are bound in a single organic molecule, cluster or nanocrystal provides a richness that can only be tackled by combining methods from atomic physics, chemistry, cluster physics, nanotechnology and the life sciences.We review various molecular beam sources and their suitability for matter-wave experiments. We discuss numerous molecular detection schemes and give an overview over diffraction and interference experiments that have already been performed with molecules or clusters.Applications of de Broglie studies with composite systems range from fundamental tests of physics up to quantum-enhanced metrology in physical chemistry, biophysics and the surface sciences.Nanoparticle quantum optics is a growing field, which will intrigue researchers still for many years to come. This review can, therefore, only be a snapshot of a very dynamical process.

Negative Ion Photoelectron Spectroscopy Reveals Remarkable Noninnocence of Ligands in Nickel Bis(dithiolene) Complexes [Ni(dddt) 2 ] - and [Ni(edo) 2 ] -

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

Liu, Xing; Hou, Gao-Lei; Wang, Xuefeng

2016-04-21

[Ni(dddt) 2] – (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) and [Ni(edo) 2] – (edo = 5,6-dihydro-1,4-dioxine-2,3-dithiolate) are two donor-type nickel bis(dithiolene) complexes, with the tendency of donating low binding energy electrons. These two structurally similar complexes differ only with respect to the outer atoms in the ligand framework where the former has four S atoms while the latter has four O atoms. Herein, we report a negative ion photoelectron spectroscopy (NIPES) study on these two complexes to probe electronic structures of the anions and their corresponding neutrals. The NIPE spectra exhibit the adiabatic electron detachment energy (ADE) or, equivalently, the electron affinity (EA)more » of the neutral [Ni(L) 2] 0 to be relatively low for this type complexes, 2.780 and 2.375 eV for L = dddt and edo, respectively. The 0.4 eV difference in ADEs shows significant substitution effect for sulfur in dddt by oxygen in edo, i.e., noninnocence of the ligands, which has decreased the electronic stability of [Ni(edo) 2] – by lowering its electron binding energy by ~0.4 eV. The observed substitution effect on gas-phase EA values correlates well with the measured redox potentials for [Ni(dddt) 2] –/0 and [Ni(edo) 2] –/0 in solutions. The singlet-triplet splitting (ΔE ST) of [Ni(dddt) 2] 0 and [Ni(edo) 2] 0 is also determined from the spectra to be 0.57 and 0.53 eV, respectively. Accompanying DFT calculations and molecular orbital (MO) composition analyses show significant ligand contributions to the redox MOs and allow the components of the orbitals involved in each electronic transition and spectral assignments to be identified.« less

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

Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Baulin, V. E.; Ivanova, I. S.

The coordination compounds of Er{sup 3+} with 1-(methoxydiphenylphosphoryl)-2-diphenylphosphorylbenzene [ErL{sub 2}{sup 1}(NO{sub 3}){sub 2}]{sub 2}[Er(NO{sub 3}){sub 2}(H{sub 2}O){sub 5}]{sub 0.333}(NO{sub 3}){sub 2.333} · 2.833H{sub 2}O (I) and its ethyl substituted derivative [ErL{sub 2}{sup 2}(NO{sub 3}){sub 2}][Er(NO{sub 3}){sub 5}]{sub 0.5} · 0.5H{sub 2}O (II) are synthesized and their crystal structures are studied. I and II contain [ErL{sub 2}(NO{sub 3}){sub 2}]{sup +} complex cations of identical composition and close structure. The eight-vertex polyhedron of the Er atom in the shape of a distorted octahedron with two split trans vertices is formed by the O atoms of the phosphoryl groups of L ligands andmore » nitrate anions. L ligands close nine-membered metallocycles. The structures contain spacious channels which are populated differently, namely, by disordered [Er(NO{sub 3}){sub 2}(H{sub 2}O){sub 5}]{sup +} complex cations, NO{sub 3}{sup −} anions, and crystallization water molecules in I and disordered [Er(NO{sub 3}){sub 5}]{sup 2−} complex anions and crystallization water molecules in II. The IR spectra of I and II are studied.« less

Infrared spectra of some acetone—magnesium adducts

NASA Astrophysics Data System (ADS)

Hisatsune, I. C.

Co-deposition of atomic magnesium with excess acetone at liquid-nitrogen temperature produces an unstable charge-transfer complex with a characteristic carbonyl infrared band at 1595 cm -1 and stable acetone adducts in which the metal atom bridges the carbonyl bond (π-complex) or coordinates to the oxygen atom (σ-complex). Infrared spectra of these complexes with (CH 3) 2CO and (CD 3) 2CO have been obtained. Corroborations for these adducts were obtained from infrared studies of acetone matrices with atomic copper and acetaldehyde matrices with atomic magnesium and with atomic copper. Infrared spectra of an acetone adduct and a dimethyl ether adduct of the Grignard reagent CH 3MgI have also been obtained. Hydrolysis of a σ-adduct gives acetone but isopropyl alcohol is obtained from hydrolysis of the π-adduct.

Free Surface Flows and Extensional Rheology of Polymer Solutions

NASA Astrophysics Data System (ADS)

Dinic, Jelena; Jimenez, Leidy Nallely; Biagioli, Madeleine; Estrada, Alexandro; Sharma, Vivek

Free-surface flows - jetting, spraying, atomization during fuel injection, roller-coating, gravure printing, several microfluidic drop/particle formation techniques, and screen-printing - all involve the formation of axisymmetric fluid elements that spontaneously break into droplets by a surface-tension-driven instability. The growth of the capillary-driven instability and pinch-off dynamics are dictated by a complex interplay of inertial, viscous and capillary stresses for simple fluids. Additional contributions by elasticity, extensibility and extensional viscosity play a role for complex fluids. We show that visualization and analysis of capillary-driven thinning and pinch-off dynamics of the columnar neck in an asymmetric liquid bridge created by dripping-onto-substrate (DoS) can be used for characterizing the extensional rheology of complex fluids. Using a wide variety of complex fluids, we show the measurement of the extensional relaxation time, extensional viscosity, power-law index and shear viscosity. Lastly, we elucidate how polymer composition, flexibility, and molecular weight determine the thinning and pinch-off dynamics of polymeric complex fluids.

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements

DOE PAGES

Bonamici, Chloë E.; Hervig, Richard L.; Kinman, William S.

2017-08-25

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. By using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclidesmore » generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Moreover, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.« less

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements

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

Bonamici, Chloë E.; Hervig, Richard L.; Kinman, William S.

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. By using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclidesmore » generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Moreover, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.« less

Tracking Radionuclide Fractionation in the First Atomic Explosion Using Stable Elements.

PubMed

Bonamici, Chloë E; Hervig, Richard L; Kinman, William S

2017-09-19

Compositional analysis of postdetonation fallout is a tool for forensic identification of nuclear devices. However, the relationship between device composition and fallout composition is difficult to interpret because of the complex combination of physical mixing, nuclear reactions, and chemical fractionations that occur in the chaotic nuclear fireball. Using a combination of in situ microanalytical techniques (electron microprobe analysis and secondary ion mass spectrometry), we show that some heavy stable elements (Rb, Sr, Zr, Ba, Cs, Ba, La, Ce, Nd, Sm, Dy, Lu, U, Th) in glassy fallout from the first nuclear test, Trinity, are reliable chemical proxies for radionuclides generated during the explosion. Stable-element proxies show that radionuclides from the Trinity device were chemically, but not isotopically, fractionated by condensation. Furthermore, stable-element proxies delineate chemical fractionation trends that can be used to connect present-day fallout composition to past fireball composition. Stable-element proxies therefore offer a novel approach for elucidating the phenomenology of the nuclear fireball as it relates to the formation of debris and the fixation of device materials within debris.

Atomic layer deposition of (K,Na)(Nb,Ta)O{sub 3} thin films

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

Sønsteby, Henrik Hovde, E-mail: henrik.sonsteby@kjemi.iuio.no; Nilsen, Ola; Fjellvåg, Helmer

2016-07-15

Thin films of complex alkali oxides are frequently investigated due to the large range of electric effects that are found in this class of materials. Their piezo- and ferroelectric properties also place them as sustainable lead free alternatives in optoelectronic devices. Fully gas-based routes for deposition of such compounds are required for integration into microelectronic devices that need conformal thin films with high control of thickness- and composition. The authors here present a route for deposition of materials in the (K,Na)(Nb,Ta)O{sub 3}-system, including the four end members NaNbO{sub 3}, KNbO{sub 3}, NaTaO{sub 3}, and KTaO{sub 3}, using atomic layer depositionmore » with emphasis on control of stoichiometry in such mixed quaternary and quinary compunds.« less

Monte Carlo simulations of mixtures involving ketones and aldehydes by a direct bubble pressure calculation.

PubMed

Ferrando, Nicolas; Lachet, Véronique; Boutin, Anne

2010-07-08

Ketone and aldehyde molecules are involved in a large variety of industrial applications. Because they are mainly present mixed with other compounds, the prediction of phase equilibrium of mixtures involving these classes of molecules is of first interest particularly to design and optimize separation processes. The main goal of this work is to propose a transferable force field for ketones and aldehydes that allows accurate molecular simulations of not only pure compounds but also complex mixtures. The proposed force field is based on the anisotropic united-atoms AUA4 potential developed for hydrocarbons, and it introduces only one new atom, the carbonyl oxygen. The Lennard-Jones parameters of this oxygen atom have been adjusted on saturated thermodynamic properties of both acetone and acetaldehyde. To simulate mixtures, Monte Carlo simulations are carried out in a specific pseudoensemble which allows a direct calculation of the bubble pressure. For polar mixtures involved in this study, we show that this approach is an interesting alternative to classical calculations in the isothermal-isobaric Gibbs ensemble. The pressure-composition diagrams of polar + polar and polar + nonpolar binary mixtures are well reproduced. Mutual solubilities as well as azeotrope location, if present, are accurately predicted without any empirical binary interaction parameters or readjustment. Such result highlights the transferability of the proposed force field, which is an essential feature toward the simulation of complex oxygenated mixtures of industrial interest.

Composite Structural Motifs of Binding Sites for Delineating Biological Functions of Proteins

PubMed Central

Kinjo, Akira R.; Nakamura, Haruki

2012-01-01

Most biological processes are described as a series of interactions between proteins and other molecules, and interactions are in turn described in terms of atomic structures. To annotate protein functions as sets of interaction states at atomic resolution, and thereby to better understand the relation between protein interactions and biological functions, we conducted exhaustive all-against-all atomic structure comparisons of all known binding sites for ligands including small molecules, proteins and nucleic acids, and identified recurring elementary motifs. By integrating the elementary motifs associated with each subunit, we defined composite motifs that represent context-dependent combinations of elementary motifs. It is demonstrated that function similarity can be better inferred from composite motif similarity compared to the similarity of protein sequences or of individual binding sites. By integrating the composite motifs associated with each protein function, we define meta-composite motifs each of which is regarded as a time-independent diagrammatic representation of a biological process. It is shown that meta-composite motifs provide richer annotations of biological processes than sequence clusters. The present results serve as a basis for bridging atomic structures to higher-order biological phenomena by classification and integration of binding site structures. PMID:22347478

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

NASA Astrophysics Data System (ADS)

Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

2008-09-01

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Evaluation of the laser-induced breakdown spectroscopy technique for determination of the chemical composition of copper concentrates

NASA Astrophysics Data System (ADS)

Łazarek, Łukasz; Antończak, Arkadiusz J.; Wójcik, Michał R.; Drzymała, Jan; Abramski, Krzysztof M.

2014-07-01

Laser-induced breakdown spectroscopy (LIBS), like many other spectroscopic techniques, is a comparative method. Typically, in qualitative analysis, synthetic certified standard with a well-known elemental composition is used to calibrate the system. Nevertheless, in all laser-induced techniques, such calibration can affect the accuracy through differences in the overall composition of the chosen standard. There are also some intermediate factors, which can cause imprecision in measurements, such as optical absorption, surface structure and thermal conductivity. In this work the calibration performed for the LIBS technique utilizes pellets made directly from the tested materials (old well-characterized samples). This choice produces a considerable improvement in the accuracy of the method. This technique was adopted for the determination of trace elements in industrial copper concentrates, standardized by conventional atomic absorption spectroscopy with a flame atomizer. A series of copper flotation concentrate samples was analyzed for three elements: silver, cobalt and vanadium. We also proposed a method of post-processing the measurement data to minimize matrix effects and permit reliable analysis. It has been shown that the described technique can be used in qualitative and quantitative analyses of complex inorganic materials, such as copper flotation concentrates. It was noted that the final validation of such methodology is limited mainly by the accuracy of the characterization of the standards.

Diamond growth on copper rods from polymer composite nanofibres

NASA Astrophysics Data System (ADS)

Varga, M.; Potocky, S.; Tesarek, P.; Babchenko, O.; Davydova, M.; Kromka, A.

2014-09-01

The potential uses of diamond films can be found in a diverse range of industrial applications. However, deposition of diamond films onto some foreign materials is still not a simple task. Here we present the growth of adherent diamond films on copper rods with the focus on substrate pre-treatment by polyvinyl alcohol composite nanofibres. The primary role of the polymer fibres substantially act as a carbon source which enhances the diamond nucleation and accelerates a homogenous CVD growth. Diamond growth was carried out in pulsed linear antenna microwave chemical vapour deposition system, which is characterized by cold plasma due to larger distance of hot plasma region from the substrate, at various gas compositions. The large distance between plasma source and the substrate holder also allows the uniform deposition of diamond on a large number of substrates with complex geometry (3D objects) as well as for the vertically positioned substrates. Moreover, the inhomogeneity in diamond film thickness deposited on vertically positioned substrates was suppressed by using polyvinyl alcohol nanofibre textile. Combination of PVA polymer fibres use together with this unique deposition system leads to a successful overcoating of the copper rods by continuous diamond film without the film cracking or delamination. We propose that the sequence of plasma-chemical reactions enhances the transformation of certain number of carbon atoms into the sp3-bonded form which further are stabilized by atomic hydrogen coming from plasma.

Composition measurement in substitutionally disordered materials by atomic resolution energy dispersive X-ray spectroscopy in scanning transmission electron microscopy.

PubMed

Chen, Z; Taplin, D J; Weyland, M; Allen, L J; Findlay, S D

2017-05-01

The increasing use of energy dispersive X-ray spectroscopy in atomic resolution scanning transmission electron microscopy invites the question of whether its success in precision composition determination at lower magnifications can be replicated in the atomic resolution regime. In this paper, we explore, through simulation, the prospects for composition measurement via the model system of Al x Ga 1-x As, discussing the approximations used in the modelling, the variability in the signal due to changes in configuration at constant composition, and the ability to distinguish between different compositions. Results are presented in such a way that the number of X-ray counts, and thus the expected variation due to counting statistics, can be gauged for a range of operating conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Statistical analysis of atom probe data: detecting the early stages of solute clustering and/or co-segregation.

PubMed

Hyde, J M; Cerezo, A; Williams, T J

2009-04-01

Statistical analysis of atom probe data has improved dramatically in the last decade and it is now possible to determine the size, the number density and the composition of individual clusters or precipitates such as those formed in reactor pressure vessel (RPV) steels during irradiation. However, the characterisation of the onset of clustering or co-segregation is more difficult and has traditionally focused on the use of composition frequency distributions (for detecting clustering) and contingency tables (for detecting co-segregation). In this work, the authors investigate the possibility of directly examining the neighbourhood of each individual solute atom as a means of identifying the onset of solute clustering and/or co-segregation. The methodology involves comparing the mean observed composition around a particular type of solute with that expected from the overall composition of the material. The methodology has been applied to atom probe data obtained from several irradiated RPV steels. The results show that the new approach is more sensitive to fine scale clustering and co-segregation than that achievable using composition frequency distribution and contingency table analyses.

Synthesis and Spectral Characterization of Antifungal Sensitive Schiff Base Transition Metal Complexes

PubMed Central

Sakthivel, A.; Rajasekaran, K.

2007-01-01

New N2O2 donor type Schiff base has been designed and synthesized by condensing acetoacetanilido-4-aminoantipyrine with 2-aminobenzoic acid in ethanol. Solid metal complexes of the Schiff base with Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) metal ions were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conduction, fast atom bombardment (FAB) mass, IR, UV-Vis, and 1H NMR spectral studies. The data show that the complexes have the composition of ML type. The UV-Vis. and magnetic susceptibility data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The in vitro antifungal activities of the compounds were tested against fungi such as Aspergillus niger, Aspergillus flavus, Rhizopus stolonifer, Candida albicans, Rhizoctonia bataicola and Trichoderma harizanum. All the metal complexes showed stronger antifungal activities than the free ligand. The minimum inhibitory concentrations (MIC) of the metal complexes were found in the range of 10~31 µg/ml. PMID:24015086

Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

NASA Astrophysics Data System (ADS)

Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

2016-03-01

A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

Two Series of Homodinuclear Lanthanide Complexes: Greatly Enhancing Energy Barriers through Tuning Terminal Solvent Ligands in Dy2 Single-Molecule Magnets.

PubMed

Qin, Yaru; Zhang, Haifeng; Sun, Hao; Pan, Yangdan; Ge, Yu; Li, Yahong; Zhang, Yi-Quan

2017-11-02

The utilization of 2-ethoxy-6-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol (H 2 L) as a chelating ligand, in combination with the employment of alcohols (EtOH and MeOH) as auxiliary ligands, in 4 f-metal chemistry afforded two series of dinuclear lanthanide complexes of compositions [Ln 2 L 2 (NO 3 ) 2 (EtOH) 2 ] (Ln=Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7)) and [Ln 2 L 2 (NO 3 ) 2 (MeOH) 2 ] (Ln=Sm (8), Eu (9), Gd (10), Tb (11), Dy (12), Ho (13), Er (14)). The structures of 1-14 were determined by single-crystal X-ray crystallography. Complexes 1-7 are isomorphous. The two lanthanide(III) ions in 1-7 are doubly bridged by two deprotonated aminophenoxide oxygen atoms of two μ 2 :η 0 :η 1 :η 2 :η 1 :η 1 :η 0 -L 2- ligands. One nitrogen atom, two oxygen atoms of the NO 3 - anion, two methoxide oxygen atoms of two ligand sets, and one oxygen atom of the terminally coordinated EtOH molecule complete the distorted dodecahedron geometry of each lanthanide(III) ion. Compounds 8-14 are isomorphous and their structures are similar to those of 1-7. The slight difference between 1-7 and 8-14 stems from purposefully replacing the EtOH ligands in 1-7 with MeOH in 8-14. Direct-current magnetic susceptibility studies in the 2-300 K range reveal weak antiferromagnetic interactions for 3, 4, 7, 10, 11, and 14, and ferromagnetic interactions at low temperature for 5, 6, 12, and 13. Complexes 5 and 12 exhibit single-molecule magnet (SMM) behavior with energy barriers of 131.3 K for 5 and 198.8 K for 12. The energy barrier is significantly enhanced by dexterously regulating the terminal ligands. To rationalize the observed difference in the magnetic behavior, complete-active-space self-consistent field (CASSCF) calculations were performed on two Dy 2 complexes. Subtle variation in the angle between the magnetic axes and the vector connecting two dysprosium(III) ions results in a weaker influence on the tunneling gap of individual dysprosium(III) ions by the dipolar field in 12. This work proposes an efficient strategy for synthesizing Dy 2 SMMs with high energy barriers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Stoichiometric Analysis of a High-Temperature Superconductor by Atom Probe Tomography.

PubMed

Pedrazzini, Stella; London, Andrew J; Gault, Baptiste; Saxey, David; Speller, Susannah; Grovenor, Chris R M; Danaie, Mohsen; Moody, Michael P; Edmondson, Philip D; Bagot, Paul A J

2017-04-01

The functional properties of the high-temperature superconductor Y1Ba2Cu3O7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y7.7Ba15.3Cu23O54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of the experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y7.9Ba10.4Cu24.4O57.2.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II)

NASA Astrophysics Data System (ADS)

Singh, Bibhesh K.; Jetley, Umesh K.; Sharma, Rakesh K.; Garg, Bhagwan S.

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML 2 composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II).

PubMed

Singh, Bibhesh K; Jetley, Umesh K; Sharma, Rakesh K; Garg, Bhagwan S

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML(2) composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Structures of nitrato-(2-hydroxybenzaldehydo) (2,2 Prime -bipyridyl)copper and nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2 Prime -bipyridyl)copper

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

Chumakov, Yu. M.; Paladi, L. G.; Antosyak, B. Ya.

2011-03-15

Nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2 Prime -bipyridyl)copper (I) and nitrato-(2-hydroxybenzaldehydo)(2,2 Prime -bipyridyl)copper (II) were synthesized and characterized by X-ray diffraction. The coordination polyhedron of the central copper atom in complex I can be described as a distorted tetragonal pyramid whose base is formed by the phenol and carbonyl oxygen atoms of the monodeprotonated 2-hydroxy-5nitrobenzaldehyde molecule and the nitrogen atoms of the 2,2 Prime -bipyridyl ligand and whose apex is occupied by the oxygen atom of the nitrato group. In the crystal structure, complexes I are linked by the acido ligands and the NO{sub 2} groups of the aldehyde molecule into infinite chains. In complexmore » II, the central copper atom is coordinated by 2-hydroxybenzaldehyde, 2,2 Prime -bipyridyl, and the nitrato group, resulting in the formation of centrosymmetric dimers. The coordination polyhedron of the central copper atom can be described as a bipyramid (4 + 1 + 1) with the same base as in complex I. The axial vertices of the bipyramid are occupied by the oxygen atom of the nitrato group and the bridging phenol oxygen atom of the adjacent complex related to the initial complex by a center of symmetry. In the crystal structure, complexes II are hydrogen bonded into infinite chains.« less

Virtual interface substructure synthesis method for normal mode analysis of super-large molecular complexes at atomic resolution.

PubMed

Chen, Xuehui; Sun, Yunxiang; An, Xiongbo; Ming, Dengming

2011-10-14

Normal mode analysis of large biomolecular complexes at atomic resolution remains challenging in computational structure biology due to the requirement of large amount of memory space and central processing unit time. In this paper, we present a method called virtual interface substructure synthesis method or VISSM to calculate approximate normal modes of large biomolecular complexes at atomic resolution. VISSM introduces the subunit interfaces as independent substructures that join contacting molecules so as to keep the integrity of the system. Compared with other approximate methods, VISSM delivers atomic modes with no need of a coarse-graining-then-projection procedure. The method was examined for 54 protein-complexes with the conventional all-atom normal mode analysis using CHARMM simulation program and the overlap of the first 100 low-frequency modes is greater than 0.7 for 49 complexes, indicating its accuracy and reliability. We then applied VISSM to the satellite panicum mosaic virus (SPMV, 78,300 atoms) and to F-actin filament structures of up to 39-mer, 228,813 atoms and found that VISSM calculations capture functionally important conformational changes accessible to these structures at atomic resolution. Our results support the idea that the dynamics of a large biomolecular complex might be understood based on the motions of its component subunits and the way in which subunits bind one another. © 2011 American Institute of Physics

Evidence for the Formation of Nitrogen-Rich Platinum and Palladium Nitride Nanoparticles

DOE PAGES

Veith, Gabriel M.; Lupini, Andrew R.; Baggetto, Loïc; ...

2013-12-03

Here, we report evidence for the formation of nitrogen-rich precious metal nanoparticles (Pt, Pd) prepared by reactive sputtering of the pure metal in a N 2 plasma. The composition of the nanoparticles varies as a function of particle size and growth conditions. For the smallest particles the nitrogen content appears to be as high as 6.7 N atoms for each Pd atom or 5.9 N atoms for each Pt atom whereas bulk films have nominal compositions of Pt 7.3N and Pd 2.5N. The nanoparticles are metastable in air and moisture, slowly decomposing over several years. This paper describes the synthesismore » of these materials along with experimental evidence of the composition, oxidation state, and growth modes. Moreover, the catalytic properties of these N-rich nanoparticles were accessed by rotating disk electrode electrochemical studies, the liquid phase oxidation of benzyl alcohol and gas phase CO oxidation and support the experimental evidence for the materials composition.« less

Templated synthesis of metal nanorods in silica nanotubes

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

Yin, Yadong; Gao, Chuanbo

A method of preparing a metal nanorod. The method includes seeding a metal nanoparticle within the lumen of a nanotube, and growing a metal nanorod from the seeded metal nanoparticle to form a metal nanorod-nanotube composite. In some cases, the nanotube includes metal binding ligands attached to the inner surface. Growing of the metal nanorod includes incubating the seeded nanotube in a solution that includes: a metal source for the metal in the metal nanorod, the metal source including an ion of the metal; a coordinating ligand that forms a stable complex with the metal ion; a reducing agent formore » reducing the metal ion, and a capping agent that stabilizes atomic monomers of the metal. Compositions derived from the method are also provided.« less

Statistical clumped isotope signatures

PubMed Central

Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

2016-01-01

High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

Ball bearings comprising nickel-titanium and methods of manufacture thereof

NASA Technical Reports Server (NTRS)

DellaCorte, Christopher (Inventor); Glennon, Glenn N. (Inventor)

2012-01-01

Disclosed herein is a friction reducing nickel-titanium composition. The nickel-titanium composition includes a first phase that comprises nickel and titanium in an atomic ratio of about 0.45:0.55 to about 0.55:0.45; a second phase that comprises nickel and titanium in an atomic ratio of about 0.70:0.30 to about 0.80:0.20; and a third phase that comprises nickel and titanium in an atomic ratio of about 0.52:0.48 to about 0.62:0.38. A bearing for reducing friction comprising a nickel-titanium composition comprising a first phase that comprises nickel and titanium in an atomic ratio of about 0.45:0.55 to about 0.55:0.45; a second phase that comprises nickel and titanium in an atomic ratio of about 0.70:0.30 to about 0.80:0.20; and a third phase that comprises nickel and titanium in an atomic ratio of about 0.52:0.48 to about 0.62:0.38; where the bearing is free from voids and pinholes.

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

Kaur, Sandeep, E-mail: sipusukhn@gmail.com; Sharma, Amrish; Mudahar, Isha, E-mail: isha@pbi.ac.in

First principle calculations based on density functional theory were performed to calculate the structural and electronic properties of C{sub 20}-N{sub m}@C{sub n} dimer complexes. The calculated binding energies of the complexes formed are comparable to C{sub 60} dimer which ensures their stability. The bond lengths of these dimer complexes were found to be nearly same as pure complexes C{sub 20}-C{sub n}. Further, nitrogen (N) atoms were encapsulated inside the secondary cage (C{sub n}) of dimer complexes and the number of N atoms depends on diameter of the cage. The HOMO-LUMO gaps of new proposed complexes indicate the increase in gapmore » as compared to pure complexes. Mulliken charge analysis of these complexes has been studied which shows the significant charge transfer from the N atoms to the secondary cage of these complexes. The study propose the formation of the new dimer complexes which are stable and are able to encapsulate atoms which are otherwise reactive in free space.« less

AtomicChargeCalculator: interactive web-based calculation of atomic charges in large biomolecular complexes and drug-like molecules.

PubMed

Ionescu, Crina-Maria; Sehnal, David; Falginella, Francesco L; Pant, Purbaj; Pravda, Lukáš; Bouchal, Tomáš; Svobodová Vařeková, Radka; Geidl, Stanislav; Koča, Jaroslav

2015-01-01

Partial atomic charges are a well-established concept, useful in understanding and modeling the chemical behavior of molecules, from simple compounds, to large biomolecular complexes with many reactive sites. This paper introduces AtomicChargeCalculator (ACC), a web-based application for the calculation and analysis of atomic charges which respond to changes in molecular conformation and chemical environment. ACC relies on an empirical method to rapidly compute atomic charges with accuracy comparable to quantum mechanical approaches. Due to its efficient implementation, ACC can handle any type of molecular system, regardless of size and chemical complexity, from drug-like molecules to biomacromolecular complexes with hundreds of thousands of atoms. ACC writes out atomic charges into common molecular structure files, and offers interactive facilities for statistical analysis and comparison of the results, in both tabular and graphical form. Due to high customizability and speed, easy streamlining and the unified platform for calculation and analysis, ACC caters to all fields of life sciences, from drug design to nanocarriers. ACC is freely available via the Internet at http://ncbr.muni.cz/ACC.

Atomic structure solution of the complex quasicrystal approximant Al77Rh15Ru8 from electron diffraction data.

PubMed

Samuha, Shmuel; Mugnaioli, Enrico; Grushko, Benjamin; Kolb, Ute; Meshi, Louisa

2014-12-01

The crystal structure of the novel Al77Rh15Ru8 phase (which is an approximant of decagonal quasicrystals) was determined using modern direct methods (MDM) applied to automated electron diffraction tomography (ADT) data. The Al77Rh15Ru8 E-phase is orthorhombic [Pbma, a = 23.40 (5), b = 16.20 (4) and c = 20.00 (5) Å] and has one of the most complicated intermetallic structures solved solely by electron diffraction methods. Its structural model consists of 78 unique atomic positions in the unit cell (19 Rh/Ru and 59 Al). Precession electron diffraction (PED) patterns and high-resolution electron microscopy (HRTEM) images were used for the validation of the proposed atomic model. The structure of the E-phase is described using hierarchical packing of polyhedra and a single type of tiling in the form of a parallelogram. Based on this description, the structure of the E-phase is compared with that of the ε6-phase formed in Al-Rh-Ru at close compositions.

Atomic-scale study of stacking faults in Zr hydrides and implications on hydride formation.

PubMed

Besson, Remy; Thuinet, L; Louchez, Marc-Antoine

2018-06-25

We performed atomic-scale ab initio calculations to investigate the stacking fault (SF) properties of the metastable zeta-Zr2H zirconium hydride. The effect of H near the SF was found to entail the existence of negative SF energies, showing that the zeta compound is probably unstable with respect to shearing in the basal plane. The effect of temperature on SFs was investigated by means of free energy calculations in the quasiharmonic approximation. This evidenced unexpectedly large temperature effects, confirming the main conclusions drawn at 0 K, in particular the zeta mechanical instability. The complex behaviour of H atoms during the shear process suggested zeta-hcp --> Zr2H[111]-fcc as a plausible shear path leading to an fcc compound with same composition as zeta. Finally, as shown by an analysis based on microelasticity, this Zr2H[111]-fcc intermediate compound may be relevant for better interpreting the currently intricate issue of hydride habit planes in zirconium. © 2018 IOP Publishing Ltd.

Production and study of radionuclides at the research institute of atomic reactors (NIIAR)

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

Karelin, E.A.; Gordeev, Y.N.; Filimonov, V.T.

1995-01-01

The main works of the Radionuclide Sources and Preparations Department (ORIP) of the Research Institute of Atomic Reactors (NIIAR) are summarized. The major activity of the Radionuclide Sources and Preparations Department (ORIP) is aimed at production of radioactive preparations of trans-plutonium elements (TPE) and also of lighter elements (from P to Ir), manufacture of ionizing radiation sources thereof, and scientific research to develop new technologies. One of the radionuclides that recently has received major attention is gadolinium-153. Photon sources based on it are used in densimeters for diagnostics of bone deseases. The procedure for separating gadolinium and europium, which ismore » currently used at the Research Institute of Atomic Reactors (NILAR), is based on europium cementation with the use of sodium amalgam. The method, though efficient, did not until recently permit an exhaustive removal of radioactive europium from {sup 153}Gd. The authors have thoroughly studied the separation process in semi-countercurrent mode, using citrate solutions. A special attention was given to the composition of europium complex species.« less

A posteriori operation detection in evolving software models

PubMed Central

Langer, Philip; Wimmer, Manuel; Brosch, Petra; Herrmannsdörfer, Markus; Seidl, Martina; Wieland, Konrad; Kappel, Gerti

2013-01-01

As every software artifact, also software models are subject to continuous evolution. The operations applied between two successive versions of a model are crucial for understanding its evolution. Generic approaches for detecting operations a posteriori identify atomic operations, but neglect composite operations, such as refactorings, which leads to cluttered difference reports. To tackle this limitation, we present an orthogonal extension of existing atomic operation detection approaches for detecting also composite operations. Our approach searches for occurrences of composite operations within a set of detected atomic operations in a post-processing manner. One major benefit is the reuse of specifications available for executing composite operations also for detecting applications of them. We evaluate the accuracy of the approach in a real-world case study and investigate the scalability of our implementation in an experiment. PMID:23471366

Synthesis and structural characterization of two half-sandwich nickel(II) complexes with the scorpionate ligands

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

Wang, G.-F., E-mail: wgf1979@126.com, E-mail: s-shuwen@163.com; Zhang, X., E-mail: zhangx@hit.edu.cn; Sun, S.-W.

The synthesis and characterization of two new halfsandwich mononuclear nickel(II) complexes with the scorpionate ligands, [k{sup 3}-N, N',N''-Tp{sup t-Bu}, {sup Me}NiI] (1) and [k{sup 3}-N,N',N''-Tp{sup t-Bu}, {sup Me}NiNO{sub 3}] (2), are reported. These complexes have been fully characterized by elemental analyses and infrared spectra. Their molecular structures were determined by single crystal X-ray diffraction. The nickel(II) ion of complex 1 is in a four-coordinate environment, in which the donor atoms are provided by three nitrogen atoms of a hydrotris(pyrazolyl) borate ligand and one iodide atom, while that of complex 2 is in a five-coordinate environment with three nitrogen atoms frommore » a hydrotris(pyrazolyl)borate ligand and two oxygen atoms from a nitrate ion.« less

Characterization of dilute species within CVD-grown silicon nanowires doped using trimethylboron: protected lift-out specimen preparation for atom probe tomography.

PubMed

Prosa, T J; Alvis, R; Tsakalakos, L; Smentkowski, V S

2010-08-01

Three-dimensional quantitative compositional analysis of nanowires is a challenge for standard techniques such as secondary ion mass spectrometry because of specimen size and geometry considerations; however, it is precisely the size and geometry of nanowires that makes them attractive candidates for analysis via atom probe tomography. The resulting boron composition of various trimethylboron vapour-liquid-solid grown silicon nanowires were measured both with time-of-flight secondary ion mass spectrometry and pulsed-laser atom probe tomography. Both characterization techniques yielded similar results for relative composition. Specialized specimen preparation for pulsed-laser atom probe tomography was utilized and is described in detail whereby individual silicon nanowires are first protected, then lifted out, trimmed, and finally wet etched to remove the protective layer for subsequent three-dimensional analysis.

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.

Sensor-Based Vibration Signal Feature Extraction Using an Improved Composite Dictionary Matching Pursuit Algorithm

PubMed Central

Cui, Lingli; Wu, Na; Wang, Wenjing; Kang, Chenhui

2014-01-01

This paper presents a new method for a composite dictionary matching pursuit algorithm, which is applied to vibration sensor signal feature extraction and fault diagnosis of a gearbox. Three advantages are highlighted in the new method. First, the composite dictionary in the algorithm has been changed from multi-atom matching to single-atom matching. Compared to non-composite dictionary single-atom matching, the original composite dictionary multi-atom matching pursuit (CD-MaMP) algorithm can achieve noise reduction in the reconstruction stage, but it cannot dramatically reduce the computational cost and improve the efficiency in the decomposition stage. Therefore, the optimized composite dictionary single-atom matching algorithm (CD-SaMP) is proposed. Second, the termination condition of iteration based on the attenuation coefficient is put forward to improve the sparsity and efficiency of the algorithm, which adjusts the parameters of the termination condition constantly in the process of decomposition to avoid noise. Third, composite dictionaries are enriched with the modulation dictionary, which is one of the important structural characteristics of gear fault signals. Meanwhile, the termination condition of iteration settings, sub-feature dictionary selections and operation efficiency between CD-MaMP and CD-SaMP are discussed, aiming at gear simulation vibration signals with noise. The simulation sensor-based vibration signal results show that the termination condition of iteration based on the attenuation coefficient enhances decomposition sparsity greatly and achieves a good effect of noise reduction. Furthermore, the modulation dictionary achieves a better matching effect compared to the Fourier dictionary, and CD-SaMP has a great advantage of sparsity and efficiency compared with the CD-MaMP. The sensor-based vibration signals measured from practical engineering gearbox analyses have further shown that the CD-SaMP decomposition and reconstruction algorithm is feasible and effective. PMID:25207870

Sensor-based vibration signal feature extraction using an improved composite dictionary matching pursuit algorithm.

PubMed

Cui, Lingli; Wu, Na; Wang, Wenjing; Kang, Chenhui

2014-09-09

This paper presents a new method for a composite dictionary matching pursuit algorithm, which is applied to vibration sensor signal feature extraction and fault diagnosis of a gearbox. Three advantages are highlighted in the new method. First, the composite dictionary in the algorithm has been changed from multi-atom matching to single-atom matching. Compared to non-composite dictionary single-atom matching, the original composite dictionary multi-atom matching pursuit (CD-MaMP) algorithm can achieve noise reduction in the reconstruction stage, but it cannot dramatically reduce the computational cost and improve the efficiency in the decomposition stage. Therefore, the optimized composite dictionary single-atom matching algorithm (CD-SaMP) is proposed. Second, the termination condition of iteration based on the attenuation coefficient is put forward to improve the sparsity and efficiency of the algorithm, which adjusts the parameters of the termination condition constantly in the process of decomposition to avoid noise. Third, composite dictionaries are enriched with the modulation dictionary, which is one of the important structural characteristics of gear fault signals. Meanwhile, the termination condition of iteration settings, sub-feature dictionary selections and operation efficiency between CD-MaMP and CD-SaMP are discussed, aiming at gear simulation vibration signals with noise. The simulation sensor-based vibration signal results show that the termination condition of iteration based on the attenuation coefficient enhances decomposition sparsity greatly and achieves a good effect of noise reduction. Furthermore, the modulation dictionary achieves a better matching effect compared to the Fourier dictionary, and CD-SaMP has a great advantage of sparsity and efficiency compared with the CD-MaMP. The sensor-based vibration signals measured from practical engineering gearbox analyses have further shown that the CD-SaMP decomposition and reconstruction algorithm is feasible and effective.

Oxidation and protection of fiberglass-epoxy composite masts for photovoltaic arrays in the low Earth orbital environment

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Paulsen, Phillip E.; Brady, Joyce A.; Ciancone, Michael L.

1988-01-01

Fiberglass-epoxy composites are considered for use as structural members for the mast of the space station solar array panel. The low Earth orbital environment in which space station is to operate is composed mainly of atomic oxygen, which has been shown to cause erosion of many organic materials and some metals. Ground based testing in a plasma asher was performed to determine the extent of degradation of fiberglass-epoxy composites when exposed to a simulated atomic oxygen environment. During exposure, the epoxy at the surface of the composite was oxidized, exposing individual glass fibers which could easily be removed. Several methods of protecting the composite were evaluated in an atomic oxygen environment and with thermal cycling and flexing. The protection techniques evaluated to date include an aluminum braid covering, an indium-tin eutectic and a silicone based paint. The open aluminum braid offered little protection while the CV-1144 coating offered some initial protection against atomic oxygen, but appears to develop cracks which accelerate degradation when flexed. Coatings such as the In-Sn eutectic may provide adequate protection by containing the glass fibers even though mass loss still occurs.

Atomic force microscopy of adsorbed proteoglycan mimetic nanoparticles: Toward new glycocalyx-mimetic model surfaces.

PubMed

Hedayati, Mohammadhasan; Kipper, Matt J

2018-06-15

Blood vessels present a dense, non-uniform, polysaccharide-rich layer, called the endothelial glycocalyx. The polysaccharides in the glycocalyx include polyanionic glycosaminoglycans (GAGs). This polysaccharide-rich surface has excellent and unique blood compatibility. We report new methods for preparing and characterizing dense GAG surfaces that can serve as models of the vascular endothelial glycocalyx. The GAG-rich surfaces are prepared by adsorbing heparin or chondroitin sulfate-containing polyelectrolyte complex nanoparticles (PCNs) to chitosan-hyaluronan polyelectrolyte multilayers (PEMs). The surfaces are characterized by PeakForce tapping atomic force microscopy, both in air and in aqueous pH 7.4 buffer, and by PeakForce quantitative nanomechanics (PF-QNM) mode with high spatial resolution. These new surfaces provide access to heparin-rich or chondroitin sulfate-rich coatings that mimic both composition and nanoscale structural features of the vascular endothelial glycocalyx. Copyright © 2018. Published by Elsevier Ltd.

Crystal Graph Convolutional Neural Networks for an Accurate and Interpretable Prediction of Material Properties

NASA Astrophysics Data System (ADS)

Xie, Tian; Grossman, Jeffrey C.

2018-04-01

The use of machine learning methods for accelerating the design of crystalline materials usually requires manually constructed feature vectors or complex transformation of atom coordinates to input the crystal structure, which either constrains the model to certain crystal types or makes it difficult to provide chemical insights. Here, we develop a crystal graph convolutional neural networks framework to directly learn material properties from the connection of atoms in the crystal, providing a universal and interpretable representation of crystalline materials. Our method provides a highly accurate prediction of density functional theory calculated properties for eight different properties of crystals with various structure types and compositions after being trained with 1 04 data points. Further, our framework is interpretable because one can extract the contributions from local chemical environments to global properties. Using an example of perovskites, we show how this information can be utilized to discover empirical rules for materials design.

Faradaurate-940: Synthesis, Mass Spectrometry, STEM, PDF, and SAXS Study of Au~940(SR)~160 Nanocrystals

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

Kumara, Chanaka; Zuo, Xiaobing; Cullen, David A

2014-01-01

Obtaining monodisperse nanocrystals, and determining its composition to the atomic level and its atomic structure is highly desirable, but is generally lacking. Here, we report the discovery and comprehensive characterization of a 3-nm plasmonic nanocrystal with a composition of Au940 20(SCH2CH2Ph)160 4, which is, the largest mass spectrometrically characterized gold thiolate nanoparticle produced to date. The compositional assignment has been made using electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) mass spectrometry (MS). The MS results show an unprecedented size monodispersity, where the number of Au atoms vary by only 40 atoms (940 20). The mass spectrometrically-determined sizemore » and composition are supported by aberration-corrected scanning transmission electron microscopy (STEM) and synchrotron-based methods such as atomic pair distribution function (PDF) and small angle X-ray scattering (SAXS). Lower resolution STEM images show an ensemble of particles 1000 s per frame visually demonstrating monodispersity. Modelling of SAXS on statistically significant nanoparticle population approximately 1012 individual nanoparticles - shows that the diameter is 3.0 0.2nm, supporting mass spectrometry and electron microscopy results on monodispersity. Atomic PDF based on high energy X-ray diffraction experiments show decent match with either a Marks decahedral or truncated octrahedral structure. Atomic resolution STEM images of single particles and its FFT suggest face-centered cubic (fcc) arrangement. UV-visible spectroscopy data shows that the 940-atom size supports a surface plasmon resonance peak at 505 nm. These monodisperse plasmonic nanoparticles minimize averaging effects and has potential application in solar cells, nano-optical devices, catalysis and drug delivery.« less

Ion energy/momentum effects during ion assisted growth of niobium nitride films

NASA Astrophysics Data System (ADS)

Klingenberg, Melissa L.

The research described herein was performed to better understand and discern ion energy vs. ion momentum effects during ion beam assisted (IBAD) film growth and their effects on residual stress, crystalline structure, morphology, and composition, which influence film tribological properties. NbxN y was chosen for this research because it is a refractory material that can possess a large number of crystalline structures, and it has been found to have good tribological properties. To separate the effects of momentum transfer per arriving atom (p/a), which considers bombarding species mass, energy, and ion-to-atom transport ratio, from those of energy deposition per arriving atom (E/a), a mass independent parameter, different inert ion beams (krypton, argon, and neon) were used to create a matrix of coatings formed using similar energy deposition, but different momentum transfer and vice versa. Deposition was conducted in a research-scale IBAD system using electron beam evaporation, a radio frequency ion source, and a neutral nitrogen gas backfill. Films were characterized using x-ray diffraction, atomic force microscopy, Rutherford backscattering spectrometry, and residual stress analysis. Direct and quantifiable effects of bombardment were observed; however, energy deposition and momentum transfer effects could not be completely separated, confirming that thin film processes are complex. Complexities arose from ion-specific interactions (ion size, recoil energy, per cent reflected neutrals, Penning ionization, etc.) and chemistry effects that are not considered by the simple models. Overall, it can be stated that bombardment promoted nitride formation, nanocrystallinity, and compressive stress formation; influenced morphology (which influenced post-deposition oxygen uptake) and stress evolution; increased lattice parameter; modified crystalline phase and texture; and led to inert gas incorporation. High stress levels correlated strongly with material disorder and closed-structured morphologies.

Close contacts at the interface: Experimental-computational synergies for solving complexity problems

NASA Astrophysics Data System (ADS)

Torras, Juan; Zanuy, David; Bertran, Oscar; Alemán, Carlos; Puiggalí, Jordi; Turón, Pau; Revilla-López, Guillem

2018-02-01

The study of material science has been long devoted to the disentanglement of bulk structures which mainly entails finding the inner structure of materials. That structure is accountable for a major portion of materials' properties. Yet, as our knowledge of these "backbones" enlarged so did the interest for the materials' boundaries properties which means the properties at the frontier with the surrounding environment that is called interface. The interface is thus to be understood as the sum of the material's surface plus the surrounding environment be it in solid, liquid or gas phase. The study of phenomena at this interface requires both the use of experimental and theoretical techniques and, above all, a wise combination of them in order to shed light over the most intimate details at atomic, molecular and mesostructure levels. Here, we report several cases to be used as proof of concept of the results achieved when studying interface phenomena by combining a myriad of experimental and theoretical tools to overcome the usual limitation regardind atomic detail, size and time scales and systems of complex composition. Real world examples of the combined experimental-theoretical work and new tools, software, is offered to the readers.

Corrigendum to “Atom probe tomography characterization of neutron irradiated surveillance samples from the R.E. Ginna reactor pressure vessel”

DOE PAGES

Edmondson, Philip D.; Miller, Michael K.; Powers, K. A.; ...

2017-03-24

In our recent paper entitled “Atom probe tomography characterization of neutron irradiated surveillance samples from the R. E. Ginna reactor pressure vessel”, we make reference to a table within the article as providing the average compositions of the precipitates, when in fact the bulk compositions were given. In this correction, we present the average precipitate compositions for the data presented in Ref. [1]. These correct compositions are provided for information and do not alter the conclusions of the original manuscript.

Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir Branko

2010-04-06

The present invention relates to particle and nanoparticle composites useful as oxygen-reduction electrocatalysts. The particle composites are composed of a palladium or palladium-alloy particle or nanoparticle substrate coated with an atomic submonolayer, monolayer, bilayer, or trilayer of zerovalent platinum atoms. The invention also relates to a catalyst and a fuel cell containing the particle or nanoparticle composites of the invention. The invention additionally includes methods for oxygen reduction and production of electrical energy by using the particle and nanoparticle composites of the invention.

Enhanced plastic deformations of nanofibrillated cellulose film by adsorbed moisture and protein-mediated interactions.

PubMed

Malho, Jani-Markus; Ouellet-Plamondon, Claudiane; Rüggeberg, Markus; Laaksonen, Päivi; Ikkala, Olli; Burgert, Ingo; Linder, Markus B

2015-01-12

Biological composites are typically based on an adhesive matrix that interlocks rigid reinforcing elements in fiber composite or brick-and-mortar assemblies. In nature, the adhesive matrix is often made up of proteins, which are also interesting model systems, as they are unique among polymers in that we know how to engineer their structures with atomic detail and to select protein elements for specific interactions with other components. Here we studied how fusion proteins that consist of cellulose binding proteins linked to proteins that show a natural tendency to form multimer complexes act as an adhesive matrix in combination with nanofibrillated cellulose. We found that the fusion proteins are retained with the cellulose and that the proteins mainly affect the plastic yield behavior of the cellulose material as a function of water content. Interestingly, the proteins increased the moisture absorption of the composite, but the well-known plastifying effect of water was clearly decreased. The work helps to understand the functional basis of nanocellulose composites as materials and aims toward building model systems for molecular biomimetic materials.

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

Datta, Kaustuv; Neder, Reinhard B.; Chen, Jun

Revelation of unequivocal structural information at the atomic level for complex systems is uniquely important for deeper and generic understanding of the structure property connections and a key challenge in materials science. Here in this paper we report an experimental study of the local structure by applying total elastic scattering and Raman scattering analyses to an important non-relaxor ferroelectric solid solution exhibiting the so-called composition-induced morphotropic phase boundary (MPB), where concomitant enhancement of physical properties have been detected. The powerful combination of static and dynamic structural probes enabled us to derive direct correspondence between the atomic-level structural correlations and reportedmore » properties. The atomic pair distribution functions obtained from the neutron total scattering experiments were analysed through big-box atom-modelling implementing reverse Monte Carlo method, from which distributions of magnitudes and directions of off-centred cationic displacements were extracted. We found that an enhanced randomness of the displacement-directions for all ferroelectrically active cations combined with a strong dynamical coupling between the A- and B-site cations of the perovskite structure, can explain the abrupt amplification of piezoelectric response of the system near MPB. Finally, altogether this provides a more fundamental basis in inferring structure-property connections in similar systems including important implications in designing novel and bespoke materials.« less

The deflection of carbon composite carbon nanotube / graphene using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Kolesnikova, A. S.; Kirillova, I. V.; Kossovich, L. U.

2018-02-01

For the first time, the dependence of the bending force on the transverse displacement of atoms in the center of the composite material consisting of graphene and parallel oriented zigzag nanotubes was studied. Mathematical modeling of the action of the needle of the atomic force microscope was carried out using the single-layer armchair carbon nanotube. Armchair nanotubes are convenient for using them as a needle of an atomic force microscope, because their edges are not sharpened (unlike zigzag tubes). Consequently, armchair nanotubes will cause minimal damage upon contact with the investigation object. The geometric parameters of the composite was revealed under the action of the bending force of 6μN.

Atomic substitutions in synthetic apatite; Insights from solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Vaughn, John S.

Apatite, Ca5(PO4)3X (where X = F, Cl, or OH), is a unique mineral group capable of atomic substitutions for cations and anions of varied size and charge. Accommodation of differing substituents requires some kind of structural adaptation, e.g. new atomic positions, vacancies, or coupled substitutions. These structural adaptations often give rise to important physicochemical properties relevant to a range of scientific disciplines. Examples include volatile trapping during apatite crystallization, substitution for large radionuclides for long-term storage of nuclear fission waste, substitution for fluoride to improve acid resistivity in dental enamel composed dominantly of hydroxylapatite, and the development of novel biomaterials with enhanced biocompatibility. Despite the importance and ubiquity of atomic substitutions in apatite materials, many of the mechanisms by which these reactions occur are poorly understood. Presence of substituents at dilute concentration and occupancy of disordered atomic positions hinder detection by bulk characterization methods such as X-ray diffraction (XRD) and infrared (IR) spectroscopy. Solid-state nuclear magnetic resonance (NMR) spectroscopy is an isotope-specific structural characterization technique that does not require ordered atomic arrangements, and is therefore well suited to investigate atomic substitutions and structural adaptations in apatite. In the present work, solid-state NMR is utilized to investigate structural adaptations in three different types of apatite materials; a series of near-binary F, Cl apatite, carbonate-hydroxylapatite compositions prepared under various synthesis conditions, and a heat-treated hydroxylapatite enriched in 17O. The results indicate that hydroxyl groups in low-H, near binary F,Cl apatite facilitate solid-solution between F and Cl via column reversals, which result in average hexagonal symmetry despite very dilute OH concentration ( 2 mol percent). In addition, 19F NMR spectra indicate that fluorine occupies a complex distribution of atomic positions, which give rise to complex 19F peak shapes owing to varied F-Ca distance. 13C NMR analysis of carbonate-hydroxylapatite indicates that AB-type carbonate hydroxylapatite can be prepared without the presence of sodium or heat treatment. Isotopic 17O enrichment of hydroxylapatite and 17O NMR analysis reveals distinct signals corresponding to phosphate and hydroxyl oxygens, and heat treatment under vacuum results in loss of hydroxyl signal due to decomposition to tricalcium phosphate, which was observed by powder X-Ray diffraction (PXRD).

Organic molecules, ions, and rare isotopologues in the remnant of the stellar-merger candidate, CK Vulpeculae (Nova 1670)

NASA Astrophysics Data System (ADS)

Kamiński, T.; Menten, K. M.; Tylenda, R.; Karakas, A.; Belloche, A.; Patel, N. A.

2017-11-01

Context. CK Vulpeculae (CK Vul) is an enigmatic star whose outburst was observed in 1670-72. A stellar-merger event was proposed to explain its ancient eruption. Aims: We aim to investigate the composition of the molecular gas recently discovered in the remnant of CK Vul. Deriving the chemical, elemental, and isotopic composition is crucial for identifying the nature of the object and obtaining clues on its progenitor(s). Methods: We observed millimeter and submillimeter-wave spectra of CK Vul using the IRAM 30 m and APEX telescopes. Radiative-transfer modeling of the observed molecular features was performed to yield isotopic ratios for various elements. Results: The spectra of CK Vul reveal a very rich molecular environment of low excitation (Tex ≲ 12 K). Atomic carbon and twenty-seven different molecules, including two ions, were identified. They range from simple diatomic to complex polyatomic species of up to seven atoms large. The chemical composition of the molecular gas is indicative of carbon and nitrogen-driven chemistry but oxides are also present. Additionally, the abundance of fluorine may be enhanced. The spectra are rich in isotopologues that are very rare in most known sources. All stable isotopes of C, N, O, Si, and S are observed and their isotopic ratios are derived. Conclusions: The composition of the remnant's molecular gas is most peculiar and gives rise to a very unique millimeter and submillimeter spectrum. The observation of ions and complex molecules suggests the presence of a photoionizing source but its nature (a central star or shocks) remains unknown. The elemental and isotopic composition of the gas cannot be easily reconciled with standard stellar nucleosynthesis but processing in hot CNO cycles and partial helium burning can explain most of the chemical peculiarities. The isotopic ratios of CK Vul are remarkably close to those of presolar "nova grains" but the link of Nova 1670 to objects responsible for these grains is unclear. The accuracy of isotopic ratios can be improved by future observations at higher angular resolutions and with realistic models of the kinematical structure of the remnant. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/607/A78

Atomic Structure of Au 329(SR) 84 Faradaurate Plasmonic Nanomolecules

DOE PAGES

Kumara, Chanaka; Zuo, Xiaobing; Ilavsky, Jan; ...

2015-04-03

To design novel nanomaterials, it is important to precisely control the composition, determine the atomic structure, and manipulate the structure to tune the materials property. Here we present a comprehensive characterization of the material whose composition is Au 329(SR) 84 precisely, therefore referred to as a nanomolecule. The size homogeneity was shown by electron microscopy, solution X-ray scattering, and mass spectrometry. We proposed its atomic structure to contain the Au 260 core using experiments and modeling of a total-scattering-based atomic-pair distribution functional analysis. HAADF-STEM images shows fcc-like 2.0 ± 0.1 nm diameter nanomolecules.

Computer-aided design of polymers and composites

NASA Technical Reports Server (NTRS)

Kaelble, D. H.

1985-01-01

This book on computer-aided design of polymers and composites introduces and discusses the subject from the viewpoint of atomic and molecular models. Thus, the origins of stiffness, strength, extensibility, and fracture toughness in composite materials can be analyzed directly in terms of chemical composition and molecular structure. Aspects of polymer composite reliability are considered along with characterization techniques for composite reliability, relations between atomic and molecular properties, computer aided design and manufacture, polymer CAD/CAM models, and composite CAD/CAM models. Attention is given to multiphase structural adhesives, fibrous composite reliability, metal joint reliability, polymer physical states and transitions, chemical quality assurance, processability testing, cure monitoring and management, nondestructive evaluation (NDE), surface NDE, elementary properties, ionic-covalent bonding, molecular analysis, acid-base interactions, the manufacturing science, and peel mechanics.

Characterization of ternary bivalent metal complexes with bis(2-hydroxyethyl)iminotris(hydroxymethy)methane (Bis?Tris) and the comparison of five crystal structures of Bis?Tris complexes*1

NASA Astrophysics Data System (ADS)

Inomata, Yoshie; Gochou, Yoshihiro; Nogami, Masanobu; Howell, F. Scott; Takeuchi, Toshio

2004-09-01

Eleven bivalent metal complexes with bis(2-hydroxyethyl)iminotris(hydroxymethy)methane (Bis-Tris:hihm): [M(hihm)(H 2O)]SO 4· nH 2O (M: Co, Ni, Cu, Zn), [MCl(hihm)]Cl· nH 2O (M: Co, Ni, Cu), and [M(HCOO)(hihm)](HCOO) (M: Co, Ni, Cu, Zn) have been prepared and characterized by using their infrared absorption and powder diffuse reflection spectra, magnetic susceptibility, thermal analysis and powder X-ray diffraction analysis. The crystal structures of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2), [Cu(hihm)(H 2O)]SO 4 ( 3), [NiCl(hihm)]Cl·H 2O ( 6), [CuCl(hihm)]Cl ( 7) and [Co(HCOO)(hihm)](HCOO) ( 8) have been determined by single crystal X-ray diffraction analysis. The crystals of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2) and [Cu(hihm)(H 2O)]SO 4 ( 3) are each orthorhombic with the space group P2 12 12 1 and Pna2 1. For both complexes, the metal atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and a water molecule. [NiCl(hihm)]Cl·H 2O ( 6) is monoclinic with the space group P2 1/ n. For complex ( 6), the nickel atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and a chloride ion. [CuCl(hihm)]Cl ( 7) is orthorhombic with the space group P2 12 12 1. Although in this copper(II) complex the copper atom is ligated by six atoms, it is more reasonable to think that the copper atom is in a trigonal bipyramidal geometry coordinated with five atoms: three hydroxyl oxygen atoms, a nitrogen atom and a chloride ion if the bond distances and angles surrounding the copper atom are taken into consideration. [Co(HCOO)(hihm)](HCOO) ( 8) is monoclinic with the space group P2 1. In cobalt(II) complex ( 8), the cobalt atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and an oxygen atom of a formate ion. The structure of complex ( 8) is the same as the structure of [NiCl(hihm)]Cl·H 2O ( 6) except for the formate ion coordinating instead of the chloride ion. [M(hihm)(H 2O)]SO 4·H 2O (M: Co, Zn) ( 1, 4), [CoCl(hihm)]Cl·H 2O ( 5) and [M(HCOO)(hihm)](HCOO) (M: Ni, Cu, Zn) ( 9- 11) seem to have the same structures as the structures of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2), [NiCl(hihm)]Cl·H 2O ( 6) and [Co(HCOO)(hihm)](HCOO) ( 8), respectively, judging by the results of IR and powder diffuse reflection spectra and powder X-ray diffraction analysis. Bis-Tris has coordinated to the metal atoms as a pentadentate ligand in all complexes of which the structures have been determined by single crystal X-ray diffraction analysis in this work.

Low-temperature synthesis of homogeneous solid solutions of scheelite-structured Ca 1-xSr xWO 4 and Sr 1-xBa xWO 4 nanocrystals

DOE PAGES

Culver, Sean P.; Greaney, Matthew J.; Tinoco, Antonio; ...

2015-07-24

Here, a series of compositionally complex scheelite-structured nanocrystals of the formula A 1-xA’ xWO 4 (A = Ca, Sr, Ba) have been prepared under benign synthesis conditions using the vapor diffusion sol–gel method. Discrete nanocrystals with sub-20 nm mean diameters were obtained after kinetically controlled hydro- lysis and polycondensation at room temperature, followed by composition-dependent thermal aging at or below 60 °C. Rietveld analysis of X-ray diffraction data and Raman spectroscopy verified the synthesis of continuous and phase-pure nanocrystal solid solutions across the entire composition space for A 1-xA’ xWO 4, where 0 ≤ x ≤ 1. Elemental analysis bymore » X-ray photoelectron and inductively coupled plasma- atomic emission spectroscopies demonstrated excellent agreement between the nominal and experi- mentally determined elemental stoichiometries, while energy dispersive X-ray spectroscopy illustrated good spatial elemental homogeneity within these nanocrystals synthesized under benign conditions.« less

125Te NMR chemical-shift trends in PbTe–GeTe and PbTe–SnTe alloys

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

Njegic, Bosiljka; Levin, Evgenii M.; Schmidt-Rohr, Klaus

2013-10-08

Complex tellurides, such as doped PbTe, GeTe, and their alloys, are among the best thermoelectric materials. Knowledge of the change in 125Te NMR chemical shift due to bonding to dopant or “solute” atoms is useful for determination of phase composition, peak assignment, and analysis of local bonding. We have measured the 125Te NMR chemical shifts in PbTe-based alloys, Pb 1-xGe xTe and Pb 1-xSn xTe, which have a rocksalt-like structure, and analyzed their trends. For low x, several peaks are resolved in the 22-kHz MAS 125Te NMR spectra. A simple linear trend in chemical shifts with the number of Pbmore » neighbors is observed. No evidence of a proposed ferroelectric displacement of Ge atoms in a cubic PbTe matrix is detected at low Ge concentrations. The observed chemical shift trends are compared with the results of DFT calculations, which confirm the linear dependence on the composition of the first-neighbor shell. The data enable determination of the composition of various phases in multiphase telluride materials. They also provide estimates of the 125Te chemical shifts of GeTe and SnTe (+970 and +400±150 ppm, respectively, from PbTe), which are otherwise difficult to access due to Knight shifts of many hundreds of ppm in neat GeTe and SnTe.« less

Tungsten oxide--fly ash oxide composites in adsorption and photocatalysis.

PubMed

Visa, Maria; Bogatu, Cristina; Duta, Anca

2015-05-30

A novel composite based on tungsten oxide and fly ash was hydrothermally synthetized to be used as substrate in the advanced treatment of wastewaters with complex load resulted from the textile industry. The proposed treatment consists of one single step process combining photocatalysis and adsorption. The composite's crystalline structure was investigated by X-ray diffraction and FTIR, while atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to analyze the morphology. The adsorption capacity and photocatalytic properties of the material were tested on mono- and multi-pollutants systems containing two dyes (Bemacid Blau - BB and Bemacid Rot - BR) and one heavy metal ion-Cu(2+), and the optimized process conditions were identified. The results indicate better removal efficiencies using the novel composite material in the combined adsorption and photocatalysis, as compared to the separated processes. Dyes removal was significantly enhanced in the photocatalytic process by adding hydrogen peroxide and the mechanism was presented and discussed. The pseudo second order kinetics model best fitted the experimental data, both in the adsorption and in the combined processes. The kinetic parameters were calculated and correlated with the properties of the composite substrate. Copyright © 2015 Elsevier B.V. All rights reserved.

Consistent structures and interactions by density functional theory with small atomic orbital basis sets.

PubMed

Grimme, Stefan; Brandenburg, Jan Gerit; Bannwarth, Christoph; Hansen, Andreas

2015-08-07

A density functional theory (DFT) based composite electronic structure approach is proposed to efficiently compute structures and interaction energies in large chemical systems. It is based on the well-known and numerically robust Perdew-Burke-Ernzerhoff (PBE) generalized-gradient-approximation in a modified global hybrid functional with a relatively large amount of non-local Fock-exchange. The orbitals are expanded in Ahlrichs-type valence-double zeta atomic orbital (AO) Gaussian basis sets, which are available for many elements. In order to correct for the basis set superposition error (BSSE) and to account for the important long-range London dispersion effects, our well-established atom-pairwise potentials are used. In the design of the new method, particular attention has been paid to an accurate description of structural parameters in various covalent and non-covalent bonding situations as well as in periodic systems. Together with the recently proposed three-fold corrected (3c) Hartree-Fock method, the new composite scheme (termed PBEh-3c) represents the next member in a hierarchy of "low-cost" electronic structure approaches. They are mainly free of BSSE and account for most interactions in a physically sound and asymptotically correct manner. PBEh-3c yields good results for thermochemical properties in the huge GMTKN30 energy database. Furthermore, the method shows excellent performance for non-covalent interaction energies in small and large complexes. For evaluating its performance on equilibrium structures, a new compilation of standard test sets is suggested. These consist of small (light) molecules, partially flexible, medium-sized organic molecules, molecules comprising heavy main group elements, larger systems with long bonds, 3d-transition metal systems, non-covalently bound complexes (S22 and S66×8 sets), and peptide conformations. For these sets, overall deviations from accurate reference data are smaller than for various other tested DFT methods and reach that of triple-zeta AO basis set second-order perturbation theory (MP2/TZ) level at a tiny fraction of computational effort. Periodic calculations conducted for molecular crystals to test structures (including cell volumes) and sublimation enthalpies indicate very good accuracy competitive to computationally more involved plane-wave based calculations. PBEh-3c can be applied routinely to several hundreds of atoms on a single processor and it is suggested as a robust "high-speed" computational tool in theoretical chemistry and physics.

Electromagnetic interference shielding and microwave absorption properties of cobalt ferrite CoFe2O4/polyaniline composite

NASA Astrophysics Data System (ADS)

Ismail, Mukhils M.; Rafeeq, Sewench N.; Sulaiman, Jameel M. A.; Mandal, Avinandan

2018-05-01

Improvement of microwave-absorbing materials (MAMs) is the most important research area in various applications, such as in communication, radiation medical exposure, electronic warfare, air defense, and different civilian applications. Conducting polymer, polyaniline doped with para toluene sulphonic acid (PANI-PTSA) as well as cobalt ferrite (CoFe2O4) is synthesized by sol-gel method and intensely blends in different ratios. The characterization of the composite materials, CoFe2O4/PANI-PTSA (CFP1, CFP2, CFP3 and CFP4), was performed by X-ray diffraction (XRD), atomic force microscopy (AFM) and vibrating sample magnetometry (VSM). The microwave-absorbing properties' reflection loss (dB) and important parameters, such as complex relative permittivity ( ɛ r '- jɛ r ″) and complex relative permeability ( µ r '- jµ r ″) were measured in different microwave frequencies in the X-band (8.2-12.4 GHz) region. The composite material CFP3 showed a wider absorption frequency range and maximum reflection loss of - 28.4 dB (99.8% power absorption) at 8.1 GHz and - 9.6 dB (> 90% power absorption) at 11.2 GHz, and so the composite can be used as a microwave absorber; however, it can be more suitable for application in daily life for making cell phones above 9 GHz. Also the results showed that the thicker composites like CFP3 (4 mm) exhibit obviously better EMI SE as compared with the thinner ones (0.19, 0.19, 0.3 mm); this may be related to the low transmission of the EM wave from the composites.

Core-shell carbon nanosphere-TiO2 composite and hollow TiO2 nanospheres prepared by atomic layer deposition

NASA Astrophysics Data System (ADS)

Bakos, L. P.; Justh, N.; Hernádi, K.; Kiss, G.; Réti, B.; Erdélyi, Z.; Parditka, B.; Szilágyi, I. M.

2016-10-01

Core-shell carbon-TiO2 composite and hollow TiO2 nanospheres were prepared using carbon nanospheres as hard-templates, coating them with TiO2 using atomic layer deposition, and subsequent burning out of the carbon cores. The bare carbon, the composite carbon-TiO2 and the hollow TiO2 nanospheres were characterized with TG/DTA-MS, FTIR, XRD and SEM-EDX.

Environmentally friendly anti-icing

NASA Technical Reports Server (NTRS)

Zuk, John (Inventor); Haslim, Leonard A. (Inventor); Lockyer, Robert T. (Inventor)

1998-01-01

The present invention describes an aqueous, non-electrolytic, non-toxic, biodegradable, continuous single phase liquid anti-icing or deicing composition for use on the surfaces of, for example, aircraft, airport pavements, roadways, walkways, bridges, entrances, structures, canals, locks, components, vessels, nautical components, railroad switches, and motor vehicles. The anti-icing or deicing composition comprises: (a) water; (b) a non-toxic freezing point depressant selected from the group consisting of monohydric alcohols having from 2 to 6 carbon atoms, polyhydric alcohols having from 3 to 12 carbon atoms, monomethyl or ethyl ethers of polyhydric alcohols having from 3 to 12 atoms or mixtures thereof, wherein the freezing point depressant present is between about 14 to 60 percent by weight; (c) a thickener which is present in between about 0.01 and 10 percent by weight; and (d) optionally a corrosion inhibitor which is present in between about 0.01 and 0.1 percent by weight of the total composition. In one embodiment, the deicing composition further includes (e) a monohydric primary aliphatic unbranched alcohol as a means of forming a thin layer of the composition on the surface of the structure to be given ice protection, and/or as means of forming a homogenized foam with xanthan thickener; which alcohol is selected from the group consisting of alcohols having between 8 to 24 carbon atoms, preferably, 1-dodecanol. Compositions of water, propylene glycol, and/or propanol and xanthan are preferred.

Unusual large-pitch banding in poly(L-lactic acid): Effects of composition and geometry confinement

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

Woo, Eamor M.; Lugito, Graecia; Hsieh, Ya-Ting

2014-02-24

Lamellar patterns and orientations in blends of two crystalline polymers: poly(ethylene oxide) (PEO) and low-molecular-weight poly(L-lactic acid) (PLLA) were investigated using polarizing light optical microscopy (POM), and atomic and scanning electron microscopy (AFM, SEM). Specific etching off of PEO was used to reveal the complex earlier-grown PLLA lamellae patterns with various PEO content in blends. Banding of extremely long pitch (50 μm) in crystallized PLLA spherulites was induced by two kinetic factors: geometry confinement by top cover and introduction of diluent such as PEO. The mechanisms and correlation among the lamellar assembly, ring bands, and cracks are exemplified. Lamellar patternsmore » and ring-band types in blends were found to vary with respect to not only blend compositions, but also confinement of top-cover.« less

Development of Low Cost Gas Atomization of Precursor Powders for Simplified ODS Alloy Production

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

Anderson, Iver

2014-08-05

A novel gas atomization reaction synthesis (GARS) method was developed in this project to enable production (at our partner’s facility) a precursor Ni-Cr-Y-Ti powder with a surface oxide and an internal rare earth (RE) containing intermetallic compound (IMC) phase. Consolidation and heat-treatment experiments were performed at Ames Lab to promote the exchange of oxygen from the surface oxide to the RE intermetallic to form nano-metric oxide dispersoids. Alloy selection was aided by an internal oxidation and serial grinding experiments at Ames Lab and found that Hf-containing alloys may form more stable dispersoids than Ti-containing alloy, i.e., the Hf-containing system exhibitedmore » five different oxide phases and two different intermetallics compared to the two oxide phases and one intermetallic in the Ti-containing alloys. Since the simpler Ti-containing system was less complex to characterize, and make observations on the effects of processing parameters, the Ti-containing system was selected by Ames Lab for experimental atomization trials at our partner. An internal oxidation model was developed at Ames Lab and used to predict the heat treatment times necessary for dispersoid formation as a function of powder size and temperature. A new high-pressure gas atomization (HPGA) nozzle was developed at Ames Lab with the aim of promoting fine powder production at scales similar to that of the high gas-flow and melt-flow of industrial atomizers. The atomization nozzle was characterized using schlieren imaging and aspiration pressure testing at Ames Lab to determine the optimum melt delivery tip geometry and atomization pressure to promote enhanced secondary atomization mechanisms. Six atomization trials were performed at our partner to investigate the effects of: gas atomization pressure and reactive gas concentration on the particle size distribution (PSD) and the oxygen content of the resulting powder. Also, the effect on the rapidly solidified microstructure (as a function of powder size) was investigated at Ames Lab as a function of reactive gas composition and bulk alloy composition. The results indicated that the pulsatile gas atomization mechanism and a significantly enhanced yield of fine powders reported in the literature for this type of process were not observed. Also it was determined that reactive gas may marginally improve the fine powder yield but further experiments are required. The oxygen content in the gas also did not have any detrimental effect on the microstructure (i.e. did not significantly reduce undercooling). On the contrary, the oxygen addition to the atomization gas may have mitigated some potent catalytic nucleation sites, but not enough to significantly alter the microstructure vs. particle size relationship. Overall the downstream injection of oxygen was not found to significantly affect either the particle size distribution or undercooling (as inferred from microstructure and XRD observations) but injection further upstream, including in the gas atomization nozzle, remains to be investigated in later work.« less

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach

NASA Astrophysics Data System (ADS)

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material.Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. Electronic supplementary information (ESI) available: Fig. S1, AFM image (5 μm × 5 μm) of graphene nanoplate-MnO2 composite obtained at 3 h; Fig. S2, nitrogen adsorption/desorption isotherm of graphene nanoplate-MnO2 composite obtained at 3 h. See DOI: 10.1039/c1nr10229j

Characterizing Young Giant Planets with the Gemini Planet Imager: An Iterative Approach to Planet Characterization

NASA Technical Reports Server (NTRS)

Marley, Mark

2015-01-01

After discovery, the first task of exoplanet science is characterization. However experience has shown that the limited spectral range and resolution of most directly imaged exoplanet data requires an iterative approach to spectral modeling. Simple, brown dwarf-like models, must first be tested to ascertain if they are both adequate to reproduce the available data and consistent with additional constraints, including the age of the system and available limits on the planet's mass and luminosity, if any. When agreement is lacking, progressively more complex solutions must be considered, including non-solar composition, partial cloudiness, and disequilibrium chemistry. Such additional complexity must be balanced against an understanding of the limitations of the atmospheric models themselves. For example while great strides have been made in improving the opacities of important molecules, particularly NH3 and CH4, at high temperatures, much more work is needed to understand the opacity of atomic Na and K. The highly pressure broadened fundamental band of Na and K in the optical stretches into the near-infrared, strongly influencing the spectral shape of Y and J spectral bands. Discerning gravity and atmospheric composition is difficult, if not impossible, without both good atomic opacities as well as an excellent understanding of the relevant atmospheric chemistry. I will present examples of the iterative process of directly imaged exoplanet characterization as applied to both known and potentially newly discovered exoplanets with a focus on constraints provided by GPI spectra. If a new GPI planet is lacking, as a case study I will discuss HR 8799 c and d will explain why some solutions, such as spatially inhomogeneous cloudiness, introduce their own additional layers of complexity. If spectra of new planets from GPI are available I will explain the modeling process in the context of understanding these new worlds.

Production of fine calcium powders by centrifugal atomization with rotating quench bath

DOE PAGES

Tian, Liang; Ames Lab. and Iowa State Univ., Ames, IA; Anderson, Iver; ...

2016-02-08

Recently, a novel Al/Ca composite was produced by severe plastic deformation of Al powders and Ca granules for possible use as a high-voltage power transmission conductor. Since the strength of such composites is inversely proportional to the Ca filament size, fine Ca powders (less than ~250 μm) are needed to achieve the desired high strength for the powder metallurgy production of an Al-matrix composite reinforced by nano-scale Ca filaments. However, fine Ca powders are not commercially available. Therefore, we have developed a method to produce fine Ca powders via centrifugal atomization to supply Ca powder for prototype development of Al/Camore » composite conductor. A secondary goal of the project was to demonstrate that Ca powder can be safely prepared, stored, and handled and could potentially be scaled for commercial production. Our results showed that centrifugal atomization can yield as much as 83 vol. % Ca powder particles smaller than 250 μm. The mean particle size sometimes matches, sometimes deviates substantially from the predictions of the Champagne & Anger equation likely due to unexpected secondary atomization. The particle size distribution is typical for a ligament-disintegration atomization mode. Scanning electron micrographs showed that the morphology of these Ca powders varied with powder size. Spark testing and auto-ignition tests indicated that the atomized powders were difficult to ignite, providing confidence that this material can be handled safely in air.« less

Atom-Thin SnS2-xSex with Adjustable Compositions by Direct Liquid Exfoliation from Single Crystals.

PubMed

Yang, Zhanhai; Liang, Hui; Wang, Xusheng; Ma, Xinlei; Zhang, Tao; Yang, Yanlian; Xie, Liming; Chen, Dong; Long, Yujia; Chen, Jitao; Chang, Yunjie; Yan, Chunhua; Zhang, Xinxiang; Zhang, Xueji; Ge, Binghui; Ren, Zhian; Xue, Mianqi; Chen, Genfu

2016-01-26

Two-dimensional (2D) chalcogenide materials are fundamentally and technologically fascinating for their suitable band gap energy and carrier type relevant to their adjustable composition, structure, and dimensionality. Here, we demonstrate the exfoliation of single-crystal SnS2-xSex (SSS) with S/Se vacancies into an atom-thin layer by simple sonication in ethanol without additive. The introduction of vacancies at the S/Se site, the conflicting atomic radius of sulfur in selenium layers, and easy incorporation with an ethanol molecule lead to high ion accessibility; therefore, atom-thin SSS flakes can be effectively prepared by exfoliating the single crystal via sonication. The in situ pyrolysis of such materials can further adjust their compositions, representing tunable activation energy, band gap, and also tunable response to analytes of such materials. As the most basic and crucial step of the 2D material field, the successful synthesis of an uncontaminated and atom-thin sample will further push ahead the large-scale applications of 2D materials, including, but not limited to, electronics, sensing, catalysis, and energy storage fields.

A new technique for in situ measurement of the composition of neutral gas in interplanetary space

NASA Technical Reports Server (NTRS)

Gruntman, Michael A.

1993-01-01

Neutral atoms in interplanetary space play an important role in many processes relevant to the formation and evolution of the Solar System. An experimental approach is proposed for in situ atom detection based on the conversion of neutral atoms to negative ions at a specially prepared sensitive surface. Negative ions are subsequently analyzed and detected in an essentially noise-free mode. The use of the technique for in situ study of the composition of neutral interstellar atoms is considered. It is shown that interstellar H, D, and O atoms and possibly H2 molecules can be measured by the proposed technique. The experiment can be performed from a high-apogee Earth-orbiting satellite or from a deep space probe. Possible applications of the technique are discussed.

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic Resolution Electron Microscopy and Field Evaporation Simulation

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

Devaraj, Arun; Colby, Robert J.; Vurpillot, F.

2014-03-26

Metal-dielectric composite materials, specifically metal nanoparticles supported on or embedded in metal oxides, are widely used in catalysis. The accurate optimization of such nanostructures warrants the need for detailed three-dimensional characterization. Atom probe tomography is uniquely capable of generating sub-nanometer structural and compositional data with part-per-million mass sensitivity, but there are reconstruction artifacts for composites containing materials with strongly differing fields of evaporation, as for oxide-supported metal nanoparticles. By correlating atom probe tomography with scanning transmission electron microscopy for Au nanoparticles embedded in an MgO support, deviations from an ideal topography during evaporation are demonstrated directly, and correlated with compositionalmore » errors in the reconstructed data. Finite element simulations of the field evaporation process confirm that protruding Au nanoparticles will evolve on the tip surface, and that evaporation field variations lead to an inaccurate assessment of the local composition, effectively lowering the spatial resolution of the final reconstructed dataset. Cross-correlating the experimental data with simulations results in a more detailed understanding of local evaporation aberrations during APT analysis of metal-oxide composites, paving the way towards a more accurate three-dimensional characterization of this technologically important class of materials.« less

Three-dimensional nanometer scale analyses of precipitate structures and local compositions in titanium aluminide engineering alloys

NASA Astrophysics Data System (ADS)

Gerstl, Stephan S. A.

Titanium aluminide (TiAl) alloys are among the fastest developing class of materials for use in high temperature structural applications. Their low density and high strength make them excellent candidates for both engine and airframe applications. Creep properties of TiAl alloys, however, have been a limiting factor in applying the material to a larger commercial market. In this research, nanometer scale compositional and structural analyses of several TiAl alloys, ranging from model Ti-Al-C ternary alloys to putative commercial alloys with 10 components are investigated utilizing three dimensional atom probe (3DAP) and transmission electron microscopies. Nanometer sized borides, silicides, and carbide precipitates are involved in strengthening TiAl alloys, however, chemical partitioning measurements reveal oxygen concentrations up to 14 at. % within the precipitate phases, resulting in the realization of oxycarbide formation contributing to the precipitation strengthening of TiAl alloys. The local compositions of lamellar microstructures and a variety of precipitates in the TiAl system, including boride, silicide, binary carbides, and intermetallic carbides are investigated. Chemical partitioning of the microalloying elements between the alpha2/gamma lamellar phases, and the precipitate/gamma-matrix phases are determined. Both W and Hf have been shown to exhibit a near interfacial excess of 0.26 and 0.35 atoms nm-2 respectively within ca. 7 nm of lamellar interfaces in a complex TiAl alloy. In the case of needle-shaped perovskite Ti3AlC carbide precipitates, periodic domain boundaries are observed 5.3+/-0.8 nm apart along their growth axis parallel to the TiAl[001] crystallographic direction with concomitant composition variations after 24 hrs. at 800°C.

Nano-scale stoichiometry analysis of a high temperature superconductor by atom probe tomography

DOE PAGES

Pedrazzini, Stella; London, Andrew J.; Gault, Baptiste; ...

2017-01-31

The functional properties of the high-temperature superconductor Y 1Ba 2Cu 3O 7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y 7.7Ba 15.3Cu 23O 54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of themore » experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y 7.9Ba 10.4Cu 24.4O 57.2.« less

Isotope-abundance variations of selected elements (IUPAC technical report)

USGS Publications Warehouse

Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

Catalytic reforming methods

DOEpatents

Tadd, Andrew R; Schwank, Johannes

2013-05-14

A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

Laser-assisted atom probe tomography of four paired poly-Si/SiO2 multiple-stacks with each thickness of 10 nm

NASA Astrophysics Data System (ADS)

Kwak, C.-M.; Seol, J.-B.; Kim, Y.-T.; Park, C.-G.

2017-02-01

For the past 10 years, laser-assisted atom probe tomography (APT) analysis has been performed to quantify the near-atomic scale distribution of elements and their local chemical compositions within interfaces that determine the design, processing, and properties of virtually all materials. However, the nature of the occurring laser-induced emission at the surface of needle-shaped sample is highly complex and it has been an ongoing challenge to understand the surface-related interactions between laser-sources and tips containing non-conductive oxides for a robust and reliable analysis of multiple-stacked devices. Here, we find that the APT analysis of four paired poly-Si/SiO2 (conductive/non-conductive) multiple stacks with each thickness of 10 nm is governed by experimentally monitoring three experimental conditions, such as laser-beam energies ranged from 30 to 200 nJ, analysis temperatures varying with 30-100 K, and the inclination of aligned interfaces within a given tip toward analysis direction. Varying with laser-energy and analysis temperature, a drastic compositional ratio of doubly charged Si ions to single charged Si ions within conductive poly-Si layers is modified, as compared with ones detected in the non-conductive layers. Severe distorted APT images of multiple stacks are also inevitable, especially at the conductive layers, and leading to a lowering of the successful analysis yields. This lower throughput has been overcome though changing the inclination of interfaces within a given tip to analysis direction (planar interfaces parallel to the tip axis), but significant deviations in chemical compositions of a conductive layer counted from those of tips containing planar interfaces perpendicular to the tip axis are unavoidable owing to the Si2, SiH2O, and Si2O ions detected, for the first time, within poly-Si layers.

A new way to measure the composition of the interstellar gas surrounding the heliosphere

NASA Technical Reports Server (NTRS)

Gruntman, Michael A.

1993-01-01

The composition of neutral gas in the Local Interstellar Medium can be studied by direct, in situ measuring of interstellar neutral atoms penetrating into interplanetary space. A novel experimental approach for in situ atom detection, which has never been used earlier in space, is proposed. The technique is based on the conversion of neutral atoms to negative ions at a specially prepared sensitive surface. Negative ions are subsequently analyzed and detected in an essentially noise-free, multicoincidence mode. It is shown that interstellar hydrogen, deuterium, and oxygen atoms can be measured by the proposed technique. The experiment can be performed from a high-apogee Earth-orbiting satellite or from a deep space probe.

Carbon Displacement-Induced Single Carbon Atomic Chain Formation and its Effects on Sliding of SiC Fibers in SiC/graphene/SiC Composite

DOE PAGES

Wallace, Joseph B.; Chen, Di; Shao, Lin

2015-11-03

Understanding radiation effects on the mechanical properties of SiC composites is important to their application in advanced reactor designs. By means of molecular dynamics simulations, we found that due to strong interface bonding between the graphene layers and SiC, the sliding friction of SiC fibers is largely determined by the frictional behavior between graphene layers. Upon sliding, carbon displacements between graphene layers can act as seed atoms to induce the formation of single carbon atomic chains (SCACs) by pulling carbon atoms from the neighboring graphene planes. The formation, growth, and breaking of SCACs determine the frictional response to irradiation.

Separation of gases through gas enrichment membrane composites

DOEpatents

Swedo, R.J.; Kurek, P.R.

1988-07-19

Thin film composite membranes having as a permselective layer a film of a homopolymer of certain vinyl alkyl ethers are useful in the separation of various gases. Such homopolymers have a molecular weight of greater than 30,000 and the alkyl group of the vinyl alkyl monomer has from 4 to 20 carbon atoms with branching within the alkyl moiety at least at the carbon atom bonded to the ether oxygen or at the next adjacent carbon atom. These membranes show excellent hydrolytic stability, especially in the presence of acidic or basic gaseous components.

Separation of gases through gas enrichment membrane composites

DOEpatents

Swedo, Raymond J.; Kurek, Paul R.

1988-01-01

Thin film composite membranes having as a permselective layer a film of a homopolymer of certain vinyl alkyl ethers are useful in the separation of various gases. Such homopolymers have a molecular weight of greater than 30,000 and the alkyl group of the vinyl alkyl monomer has from 4 to 20 carbon atoms with branching within the alkyl moiety at least at the carbon atom bonded to the ether oxygen or at the next adjacent carbon atom. These membranes show excellent hydrolytic stability, especially in the presence of acidic or basic gaseous components.

Photon calorimeter

DOEpatents

Chow, Tze-Show

1988-04-22

A photon calorimeter is provided that comprises a laminar substrate that is uniform in density and homogeneous in atomic composition. A plasma-sprayed coating, that is generally uniform in density and homogeneous in atomic composition within the proximity of planes that are parallel to the surfaces of the substrate, is applied to either one or both sides of the laminar substrate. The plasma-sprayed coatings may be very efficiently spectrally tailored in atomic number. Thermocouple measuring junctions, are positioned within the plasma-sprayed coatings. The calorimeter is rugged, inexpensive, and equilibrates in temperature very rapidly. 4 figs.

Spontaneous resolution of binary copper(II) complexes with racemic dipeptides: crystal structures of glycyl-L-alpha-amino-n-butyrato copper(II) monohydrate, glycyl-D-valinato copper(II) hemihydrate, and glycyl-L-valinato copper(II) hemihydrate.

PubMed

Inomata, Yoshie; Yamaguchi, Takeshi; Tomita, Airi; Yamada, Dai; Howell, F Scott

2005-08-01

Copper(II) complexes with glycyl-DL-alpha-amino-n-butyric acid (H2gly-DL-but), glycyl-DL-valine (H2gly-DL-val), glycyl-DL-norleucine (H2gly-DL-norleu), glycyl-DL-threonine (H2gly-DL-thr), glycyl-DL-serine (H2gly-DL-ser), glycyl-DL-phenylalanine (H2gly-DL-phe), and glycyl-L-valine (H2gly-L-val), have been prepared and characterized by IR, powder diffuse reflection, CD and ORD spectra, and magnetic susceptibility measurements, and by single-crystal X-ray diffraction. The crystal structures of the copper complex with H2gly-DL-but, the copper complex with H2gly-DL-val, and [Cu(gly-L-val)]n.0.5nH2O have been determined by a single-crystal X-ray diffraction method. As for the structure of the copper complex with H2gly-DL-but, the configuration around the asymmetric carbon atom is similar to that of [Cu(gly-L-val)]n.0.5nH2O. Therefore it is concluded that the copper complex with H2gly-DL-but is [Cu(gly-L-but)]n.nH2O. On the contrary, as for the structure of the copper complex with H2gly-DL-val, the configuration around the asymmetric carbon atom is different from that of [Cu(gly-L-val)]n.0.5nH2O. Therefore it is concluded that the copper complex with H2gly-dl-val is [Cu(gly-D-val)]n.0.5nH2O. So during the crystallization of the copper(II) complexes with H2gly-DL-but and H2gly-DL-val, spontaneous resolution has been observed; the four complexes have separated as [Cu(gly-D-but)]n.nH2O, [Cu(gly-L-but)]n.nH2O, [Cu(gly-D-val)]n.0.5nH2O, and [Cu(gly-L-val)]n.0.5nH2O, respectively. [Cu(gly-L-but)]n.nH2O is orthorhombic with the space group P2(1)2(1)2(1). [Cu(gly-D-val)]n.0.5nH2O and [Cu(gly-L-val)]n.0.5nH2O are monoclinic with the space group C2. In these complexes, the copper atom is in a square-pyramidal geometry, ligated by a peptide nitrogen atom, an amino nitrogen atom, a carboxyl oxygen atom, and a carboxyl oxygen atom and a peptide oxygen atom from neighboring molecules. So these complexes consist of a two-dimensional polymer chain bridged by a carboxyl oxygen atom and a peptide oxygen atom from neighboring molecules. The axial oxygen atom is located above the basal plane and the side chain of an amino acid is located below it. These polymer chains consist of only one or the other type of optical isomers; no racemic dipeptides are found. Therefore, spontaneous resolution has been observed in the crystallization of copper(II) complexes with H2gly-DL-but and H2gly-DL-val. The crystal structure of [Cu(gly-D-val)]n.0.5nH2O agrees almost completely with that of [Cu(gly-L-val)]n.0.5nH2O, except for the configuration around the asymmetric carbon atom.

Red/near-infrared luminescence tuning of group-14 element complexes of dipyrrins based on a central atom.

PubMed

Yamamura, Masaki; Albrecht, Marcel; Albrecht, Markus; Nishimura, Yoshinobu; Arai, Tatsuo; Nabeshima, Tatsuya

2014-02-03

A dipyrrin complex has been one of the most utilized fluorescent dyes, and a variety of dipyrrin complexes show intriguing functions based on the various coordination structures of the central element. We now report the synthesis, structure, and photophysical properties of germanium and stannane complexes of the N2O2-type tetradentate dipyrrin, L·Ge and L·Sn, which are heavier analogues of the previously reported dipyrrin silicon complex, L·Si. The central group-14 atoms of the monomeric complexes have geometries close to trigonal bipyramidal (TBP), in which the contribution of the square-pyramidal (SP) character becomes higher as the central atom is heavier. Interestingly, L·Sn formed a dimeric structure in the crystal. All complexes L·Si, L·Ge, and L·Sn showed a fluorescence in the red/NIR region. Fluorescence quantum yields of L·Ge and L·Sn are higher than that of L·Si. These results indicated that the central atom on the dipyrrin complexes contributes not only to the geometry difference but also to tuning the fluorescence properties.

Fine tuning the ionic liquid-vacuum outer atomic surface using ion mixtures.

PubMed

Villar-Garcia, Ignacio J; Fearn, Sarah; Ismail, Nur L; McIntosh, Alastair J S; Lovelock, Kevin R J

2015-03-28

Ionic liquid-vacuum outer atomic surfaces can be created that are remarkably different from the bulk composition. In this communication we demonstrate, using low-energy ion scattering (LEIS), that for ionic liquid mixtures the outer atomic surface shows significantly more atoms from anions with weaker cation-anion interactions (and vice versa).

Atomic-level structural correlations across the morphotropic phase boundary of a ferroelectric solid solution: xBiMg 1/2Ti 1/2O 3-(1$-$x)PbTiO 3

DOE PAGES

Datta, Kaustuv; Neder, Reinhard B.; Chen, Jun; ...

2017-03-28

Revelation of unequivocal structural information at the atomic level for complex systems is uniquely important for deeper and generic understanding of the structure property connections and a key challenge in materials science. Here in this paper we report an experimental study of the local structure by applying total elastic scattering and Raman scattering analyses to an important non-relaxor ferroelectric solid solution exhibiting the so-called composition-induced morphotropic phase boundary (MPB), where concomitant enhancement of physical properties have been detected. The powerful combination of static and dynamic structural probes enabled us to derive direct correspondence between the atomic-level structural correlations and reportedmore » properties. The atomic pair distribution functions obtained from the neutron total scattering experiments were analysed through big-box atom-modelling implementing reverse Monte Carlo method, from which distributions of magnitudes and directions of off-centred cationic displacements were extracted. We found that an enhanced randomness of the displacement-directions for all ferroelectrically active cations combined with a strong dynamical coupling between the A- and B-site cations of the perovskite structure, can explain the abrupt amplification of piezoelectric response of the system near MPB. Finally, altogether this provides a more fundamental basis in inferring structure-property connections in similar systems including important implications in designing novel and bespoke materials.« less

Probing Single Pt Atoms in Complex Intermetallic Al13Fe4.

PubMed

Yamada, Tsunetomo; Kojima, Takayuki; Abe, Eiji; Kameoka, Satoshi; Murakami, Yumi; Gille, Peter; Tsai, An Pang

2018-03-21

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al 13 Fe 4 , was investigated using a single crystal prepared by the Czochralski method. High-angle annular dark-field scanning transmission electron microscopy showed that the Pt atoms were dispersed as single atoms and substituted at Fe sites in Al 13 Fe 4 . Single-crystal X-ray structural analysis revealed that the Pt atoms preferentially substitute at Fe(1). Unlike those that have been reported, Pt single atoms in the surface layers showed lower activity and selectivity than those of Al 2 Pt and bulk Pt for propyne hydrogenation, indicating that the active state of a given single-atom Pt site is strongly dominated by the bonding to surrounding Al atoms.

Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

DOE PAGES

Celik, Fuat E.; Mavrikakis, Manos

2015-01-12

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less

Stability of Surface and Subsurface Hydrogen on and in Au/Ni Near-Surface Alloys

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

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less

Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

NASA Astrophysics Data System (ADS)

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While the metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.

Predicting the Effect of Mutations on Protein-Protein Binding Interactions through Structure-Based Interface Profiles

PubMed Central

Brender, Jeffrey R.; Zhang, Yang

2015-01-01

The formation of protein-protein complexes is essential for proteins to perform their physiological functions in the cell. Mutations that prevent the proper formation of the correct complexes can have serious consequences for the associated cellular processes. Since experimental determination of protein-protein binding affinity remains difficult when performed on a large scale, computational methods for predicting the consequences of mutations on binding affinity are highly desirable. We show that a scoring function based on interface structure profiles collected from analogous protein-protein interactions in the PDB is a powerful predictor of protein binding affinity changes upon mutation. As a standalone feature, the differences between the interface profile score of the mutant and wild-type proteins has an accuracy equivalent to the best all-atom potentials, despite being two orders of magnitude faster once the profile has been constructed. Due to its unique sensitivity in collecting the evolutionary profiles of analogous binding interactions and the high speed of calculation, the interface profile score has additional advantages as a complementary feature to combine with physics-based potentials for improving the accuracy of composite scoring approaches. By incorporating the sequence-derived and residue-level coarse-grained potentials with the interface structure profile score, a composite model was constructed through the random forest training, which generates a Pearson correlation coefficient >0.8 between the predicted and observed binding free-energy changes upon mutation. This accuracy is comparable to, or outperforms in most cases, the current best methods, but does not require high-resolution full-atomic models of the mutant structures. The binding interface profiling approach should find useful application in human-disease mutation recognition and protein interface design studies. PMID:26506533

Icosahedral quasicrystals of intermetallic compounds are icosahedral twins of cubic crystals of three kinds, consisting of large (about 5000 atoms) icosahedral complexes in either a cubic body-centered or a cubic face-centered arrangement or smaller (about 1350 atoms) icosahedral complexes in the β-tungsten arrangement

PubMed Central

Pauling, Linus

1989-01-01

The twofold-axis electron-diffraction photographs of icosahedral quasicrystals are of three kinds, reflecting three different structures of the cubic crystals that by icosahedral twinning form the quasicrystals. The first kind, represented by Al13Cu4Fe3, contains two very large icosahedral complexes, each of about 4680 atoms, in the body-centered arrangement, with six smaller icosahedral complexes (104 atoms each) in the principal interstices. The second kind, represented by Al5Mn, contains four of the very large complexes in the face-centered arrangement (cubic close packing), with four of the smaller clusters in the interstices. The third kind, represented by Al6CuLi3, contains eight icosahedral complexes, each of about 1350 atoms, in the β-W arrangement. The supporting evidence for these cubic structures is discussed as well as other evidence showing that the simple quasicrystal theory, which states that quasicrystals do not involve any translational identity operations, has to be modified. Images PMID:16594078

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

Tian, Liang; Ames Lab. and Iowa State Univ., Ames, IA; Anderson, Iver

Recently, a novel Al/Ca composite was produced by severe plastic deformation of Al powders and Ca granules for possible use as a high-voltage power transmission conductor. Since the strength of such composites is inversely proportional to the Ca filament size, fine Ca powders (less than ~250 μm) are needed to achieve the desired high strength for the powder metallurgy production of an Al-matrix composite reinforced by nano-scale Ca filaments. However, fine Ca powders are not commercially available. Therefore, we have developed a method to produce fine Ca powders via centrifugal atomization to supply Ca powder for prototype development of Al/Camore » composite conductor. A secondary goal of the project was to demonstrate that Ca powder can be safely prepared, stored, and handled and could potentially be scaled for commercial production. Our results showed that centrifugal atomization can yield as much as 83 vol. % Ca powder particles smaller than 250 μm. The mean particle size sometimes matches, sometimes deviates substantially from the predictions of the Champagne & Anger equation likely due to unexpected secondary atomization. The particle size distribution is typical for a ligament-disintegration atomization mode. Scanning electron micrographs showed that the morphology of these Ca powders varied with powder size. Spark testing and auto-ignition tests indicated that the atomized powders were difficult to ignite, providing confidence that this material can be handled safely in air.« less

Synthesis and spectroscopic studies on the new Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transition metal complexes. Influence on biologically active peptides-regulating aminopeptidases.

PubMed

Hueso-Ureña, Francisco; Illán-Cabeza, Nuria A; Moreno-Carretero, Miguel N; Martínez-Martos, José M; Ramírez-Expósito, María J

2003-04-01

The synthesis, spectroscopic (IR, 1H and 13C NMR, UV-Vis-NIR, EPR), magnetic measurements and biological studies of a number of complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Au(III) and Hg(II) of the Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol and 5-aminouracil, ((5-[[(3-[[(2,4-dioxopyrimidin-5(1H,3H)-yl)imino]methyl]-2-hydroxy-5-methylphenyl)methylene]amino]pyrimidine-2,4(1H,3H)-dione, hereafter denoted as BDF5AU) are reported. In all cases, the complexes appear to be monomeric. The deprotonated ligand in the phenolic oxygen atom shows a tridentate coordination mode through the two azomethine nitrogen atoms and the phenolic oxygen atom. The coordination of the neutral ligand takes place through the phenolic oxygen atom and one azomethine nitrogen atom and the carbonylic oxygen atom in fourth position of one uracil ring. The biological properties of some perchlorate complexes on the activity of some neutral, acid, basic and omega aminopeptidases (AP) are assayed, demonstrating a general inhibitory effect. Neutral and basic AP are mainly inhibited by Cu(II), Ni(II) and Cd(II) complexes, although tyrosyl-AP is activated by Zn(II) complex. Glutamyl-AP but not aspartyl-AP is inhibited by all the complexes assayed excepting Zn(II) complex. Finally, omega AP is inhibited by Ni(II) and Cd(II) complexes. Copyright 2003 Elsevier Science Inc.

Hydridomethyl iridium complex

DOEpatents

Bergman, Robert G.; Buchanan, J. Michael; Stryker, Jeffrey M.; Wax, Michael J.

1989-01-01

A process for functionalizing methane comprising: (a) reacting methane with a hydridoalkyl metal complex of the formula: CpIr[P(R.sub.1).sub.3 ]H(R.sub.2) wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical having from 1 to 5 carbon atoms; Ir represents an iridium atom; P represents a phosphorus atom; R.sub.1 represents an alkyl group; R.sub.2 represents an alkyl group having at least two carbon atoms; and H represents a hydrogen atom, in the presence of a liquid alkane R.sub.3 H having at least three carbon atoms to form a hydridomethyl complex of the formula: CpIr[P(R.sub.1).sub.3 ]HMe where Me represents a methyl radical. (b) reacting said hydridomethyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X"X'"X"" or CHX'X"X'"; wherein X', X", X"', and X"" represent halogens selected from bromine, iodine and chlorine, to halomethyl complex of step (a) having the formula: CpIr[P(R.sub.1).sub.3 ]MeX: (c) reacting said halomethyl complex with a mercuric halide of the formula HgX.sub.2 to form a methyl mercuric halide of the formula HgMeX; and (d) reacting said methyl mercuric halide with a molecular halogen of the formula X.sub.2 to form methyl halide.

Quantitative analysis of doped/undoped ZnO nanomaterials using laser assisted atom probe tomography: Influence of the analysis parameters

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

Amirifar, Nooshin; Lardé, Rodrigue, E-mail: rodrigue.larde@univ-rouen.fr; Talbot, Etienne

2015-12-07

In the last decade, atom probe tomography has become a powerful tool to investigate semiconductor and insulator nanomaterials in microelectronics, spintronics, and optoelectronics. In this paper, we report an investigation of zinc oxide nanostructures using atom probe tomography. We observed that the chemical composition of zinc oxide is strongly dependent on the analysis parameters used for atom probe experiments. It was observed that at high laser pulse energies, the electric field at the specimen surface is strongly dependent on the crystallographic directions. This dependence leads to an inhomogeneous field evaporation of the surface atoms, resulting in unreliable measurements. We showmore » that the laser pulse energy has to be well tuned to obtain reliable quantitative chemical composition measurements of undoped and doped ZnO nanomaterials.« less

Understanding the detection of carbon in austenitic high-Mn steel using atom probe tomography.

PubMed

Marceau, R K W; Choi, P; Raabe, D

2013-09-01

A high-Mn TWIP steel having composition Fe-22Mn-0.6C (wt%) is considered in this study, where the need for accurate and quantitative analysis of clustering and short-range ordering by atom probe analysis requires a better understanding of the detection of carbon in this system. Experimental measurements reveal that a high percentage of carbon atoms are detected as molecular ion species and on multiple hit events, which is discussed with respect to issues such as optimal experimental parameters, correlated field evaporation and directional walk/migration of carbon atoms at the surface of the specimen tip during analysis. These phenomena impact the compositional and spatial accuracy of the atom probe measurement and thus require careful consideration for further cluster-finding analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Atomic-scale phase composition through multivariate statistical analysis of atom probe tomography data.

PubMed

Keenan, Michael R; Smentkowski, Vincent S; Ulfig, Robert M; Oltman, Edward; Larson, David J; Kelly, Thomas F

2011-06-01

We demonstrate for the first time that multivariate statistical analysis techniques can be applied to atom probe tomography data to estimate the chemical composition of a sample at the full spatial resolution of the atom probe in three dimensions. Whereas the raw atom probe data provide the specific identity of an atom at a precise location, the multivariate results can be interpreted in terms of the probabilities that an atom representing a particular chemical phase is situated there. When aggregated to the size scale of a single atom (∼0.2 nm), atom probe spectral-image datasets are huge and extremely sparse. In fact, the average spectrum will have somewhat less than one total count per spectrum due to imperfect detection efficiency. These conditions, under which the variance in the data is completely dominated by counting noise, test the limits of multivariate analysis, and an extensive discussion of how to extract the chemical information is presented. Efficient numerical approaches to performing principal component analysis (PCA) on these datasets, which may number hundreds of millions of individual spectra, are put forward, and it is shown that PCA can be computed in a few seconds on a typical laptop computer.

Surface composition of alloys

NASA Astrophysics Data System (ADS)

Sachtler, W. M. H.

1984-11-01

In equilibrium, the composition of the surface of an alloy will, in general, differ from that of the bulk. The broken-bond model is applicable to alloys with atoms of virtually equal size. If the heat of alloy formation is zero, the component of lower heat of atomization is found enriched in the surface. If both partners have equal heats of sublimination, the surface of a diluted alloy is enriched with the minority component. Size effects can enhance or weaken the electronic effects. In general, lattice strain can be relaxed by precipitating atoms of deviating size on the surface. Two-phase alloys are described by the "cherry model", i.e. one alloy phase, the "kernel" is surrounded by another alloy, the "flesh", and the surface of the outer phase, the "skin" displays a deviating surface composition as in monophasic alloys. In the presence of molecules capable of forming chemical bonds with individual metal atoms, "chemisorption induced surface segregation" can be observed at low temperatures, i.e. the surface becomes enriched with the metal forming the stronger chemisorption bonds.

Effect of additional elements on compositional modulated atomic layered structure of hexagonal Co{sub 80}Pt{sub 20} alloy films with superlattice diffraction

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

Hinata, Shintaro; Research Fellowship Division Japan Society for the Promotion of Science; Yamane, Akira

2016-05-15

The effect of additional element on compositionally modulated atomic layered structure of hexagonal Co{sub 80}Pt{sub 20} alloy films with superlattice diffraction was investigated. In this study it is found that the addition of Cr or W element to Co{sub 80}Pt{sub 20} alloy film shows less deterioration of hcp stacking structure and compositionally modulated atomic layer stacking structure as compared to Si or Zr or Ti with K{sub u} of around 1.4 or 1.0 × 10{sup 7} erg/cm{sup 3} at 5 at.% addition. Furthermore, for O{sub 2} addition of O{sub 2} ≥ 5.0 × 10{sup −3} Pa to CoPt alloy, compositionallymore » modulated atomic layer stacking structure will be deteriorated with enhancement of formation of hcp stacking structure which leads higher K{sub u} of 1.0 × 10{sup 7} erg/cm{sup 3}.« less

Site occupancy of interstitial deuterium atoms in face-centred cubic iron

PubMed Central

Machida, Akihiko; Saitoh, Hiroyuki; Sugimoto, Hidehiko; Hattori, Takanori; Sano-Furukawa, Asami; Endo, Naruki; Katayama, Yoshinori; Iizuka, Riko; Sato, Toyoto; Matsuo, Motoaki; Orimo, Shin-ichi; Aoki, Katsutoshi

2014-01-01

Hydrogen composition and occupation state provide basic information for understanding various properties of the metal–hydrogen system, ranging from microscopic properties such as hydrogen diffusion to macroscopic properties such as phase stability. Here the deuterization process of face-centred cubic Fe to form solid-solution face-centred cubic FeDx is investigated using in situ neutron diffraction at high temperature and pressure. In a completely deuterized specimen at 988 K and 6.3 GPa, deuterium atoms occupy octahedral and tetrahedral interstitial sites with an occupancy of 0.532(9) and 0.056(5), respectively, giving a deuterium composition x of 0.64(1). During deuterization, the metal lattice expands approximately linearly with deuterium composition at a rate of 2.21 Å3 per deuterium atom. The minor occupation of the tetrahedral site is thermally driven by the intersite movement of deuterium atoms along the ‹111› direction in the face-centred cubic metal lattice. PMID:25256789

Comparison of forcefields for molecular dynamics simulations of hydrocarbon phase diagrams

NASA Astrophysics Data System (ADS)

Pisarev, V. V.; Zakharov, S. A.

2018-01-01

Molecular dynamics calculations of vapor-liquid equilibrium of methane-n-butane mixture are performed. Three force-field models are tested: the TraPPE-UA united-atom forcefield, LOPLS-AA all-atom forcefield and a fully flexible version of the TraPPE-EH all-atom forcefield. All those forcefields reproduce well the composition of liquid phase in the mixture as a function of pressure at the 300 K isotherm, while significant discrepancies from experimental data are observed in the saturated vapor compositions with OPLS-AA and TraPPE-UA forcefields. The best agreement with the experimental phase diagram is found with TraPPE-EH forcefield which accurately reproduces compositions of both liquid and vapor phase. This forcefield can be recommended for simulation of two-phase hydrocarbon systems.

Oxygen-atom transfer chemistry and thermolytic properties of a di-tert-butylphosphate-ligated Mn4O4 cubane.

PubMed

Van Allsburg, Kurt M; Anzenberg, Eitan; Drisdell, Walter S; Yano, Junko; Tilley, T Don

2015-03-16

[Mn4O4{O2P(OtBu)2}6] (1), an Mn4O4 cubane complex combining the structural inspiration of the photosystem II oxygen-evolving complex with thermolytic precursor ligands, was synthesized and fully characterized. Core oxygen atoms within complex 1 are transferred upon reaction with an oxygen-atom acceptor (PEt3), to give the butterfly complex [Mn4O2{O2P(OtBu)2}6(OPEt3)2]. The cubane structure is restored by reaction of the latter complex with the O-atom donor PhIO. Complex 1 was investigated as a precursor to inorganic Mn metaphosphate/pyrophosphate materials, which were studied by X-ray absorption spectroscopy to determine the fate of the Mn4O4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn(II) species. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] (pin = pinacolate) is described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic Step Formation on Sapphire Surface in Ultra-precision Manufacturing

PubMed Central

Wang, Rongrong; Guo, Dan; Xie, Guoxin; Pan, Guoshun

2016-01-01

Surfaces with controlled atomic step structures as substrates are highly relevant to desirable performances of materials grown on them, such as light emitting diode (LED) epitaxial layers, nanotubes and nanoribbons. However, very limited attention has been paid to the step formation in manufacturing process. In the present work, investigations have been conducted into this step formation mechanism on the sapphire c (0001) surface by using both experiments and simulations. The step evolutions at different stages in the polishing process were investigated with atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM). The simulation of idealized steps was constructed theoretically on the basis of experimental results. It was found that (1) the subtle atomic structures (e.g., steps with different sawteeth, as well as steps with straight and zigzag edges), (2) the periodicity and (3) the degree of order of the steps were all dependent on surface composition and miscut direction (step edge direction). A comparison between experimental results and idealized step models of different surface compositions has been made. It has been found that the structure on the polished surface was in accordance with some surface compositions (the model of single-atom steps: Al steps or O steps). PMID:27444267

Atomic Step Formation on Sapphire Surface in Ultra-precision Manufacturing

NASA Astrophysics Data System (ADS)

Wang, Rongrong; Guo, Dan; Xie, Guoxin; Pan, Guoshun

2016-07-01

Surfaces with controlled atomic step structures as substrates are highly relevant to desirable performances of materials grown on them, such as light emitting diode (LED) epitaxial layers, nanotubes and nanoribbons. However, very limited attention has been paid to the step formation in manufacturing process. In the present work, investigations have been conducted into this step formation mechanism on the sapphire c (0001) surface by using both experiments and simulations. The step evolutions at different stages in the polishing process were investigated with atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM). The simulation of idealized steps was constructed theoretically on the basis of experimental results. It was found that (1) the subtle atomic structures (e.g., steps with different sawteeth, as well as steps with straight and zigzag edges), (2) the periodicity and (3) the degree of order of the steps were all dependent on surface composition and miscut direction (step edge direction). A comparison between experimental results and idealized step models of different surface compositions has been made. It has been found that the structure on the polished surface was in accordance with some surface compositions (the model of single-atom steps: Al steps or O steps).

Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin

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

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction,more » respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.« less

Photon Calorimeter

DOEpatents

Chow, Tze-Show

1989-01-01

A photon calorimeter (20, 40) is provided that comprises a laminar substrate (10, 22, 42) that is uniform in density and homogeneous in atomic composition. A plasma-sprayed coating (28, 48, 52), that is generally uniform in density and homogeneous in atomic composition within the proximity of planes that are parallel to the surfaces of the substrate, is applied to either one or both sides of the laminar substrate. The plasma-sprayed coatings may be very efficiently spectrally tailored in atomic number. Thermocouple measuring junctions (30, 50, 54) are positioned within the plasma-sprayed coatings. The calorimeter is rugged, inexpensive, and equilibrates in temperature very rapidly.

Collaborative Research: Nanopore Confinement of C-H-O Mixed Volatile Fluids Relevant to Subsurface Energy Systems

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

Grady, Brian P.

2015-03-11

The scientific objective of this proposal was to obtain a fundamental atomic- to macro-scale understanding of the sorptivity, structure and dynamics of simple and complex hydrocarbon (HC) fluids at mineral surfaces or within nanoporous matrices over temperatures, pressures and compositions encountered in near-surface and shallow crustal environments. The research supported by this award was complementary to that conducted by the group of Prof. David cole at Ohio State University. The scope of the present award was to utilize molecular-level modeling to provide critically important insights into the interfacial properties of mineral-volatile systems, assist in the interpretation of experimental data andmore » predict fluid behavior beyond the limits of current experimental capability. During the past three years the effort has focused primarily on the behavior of C-H volatiles including methane (CH 4) and propane (C 3H 8), mixed-volatile systems including hydrocarbon - CO 2 with and without H 2O present. The long-range goal is to quantitatively link structure, dynamics and reactivity in complex mineral-/C-H-O systems from the atomic to the molecular to the macroscopic levels. The results are relevant to areas of growing importance such as gas shale, HC-bearing hydrothermal systems, and CO 2 storage.« less

Formation of Glycerol through Hydrogenation of CO Ice under Prestellar Core Conditions

NASA Astrophysics Data System (ADS)

Fedoseev, G.; Chuang, K.-J.; Ioppolo, S.; Qasim, D.; van Dishoeck, E. F.; Linnartz, H.

2017-06-01

Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, I.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic-ray-induced UV photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via nonenergetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the “CO freeze-out stage” in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol—HOCH2CH(OH)CH2OH—a three-carbon-bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical-radical and radical-molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde—HOCH2CH(OH)CHO—is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars.

Aminotroponiminate calcium and strontium complexes.

PubMed

Datta, Simmi; Gamer, Michael T; Roesky, Peter W

2008-06-07

Heteroleptic aminotroponiminate complexes of calcium and strontium have been prepared. The monomeric calcium complex [((iPr)2ATI)CaI(THF)3] 1 ((iPr)2ATI = N-isopropyl-2-(isopropylamino)troponiminate) and the corresponding dimeric strontium compound [( (iPr)2ATI)SrI(THF)2]2 2 were obtained by reaction of [((iPr)2ATI)K] and MI2. Whereas the mixed ligand compound of composition [((iPr)2ATI)Ca(iPrAT)]2 3 (iPrAT = 2-(isopropylamino)troponate) was not obtained via a salt metathesis but by reaction of [Ca(N(SiMe3)2)2(THF)2] with ( (iPr)2ATI)H and (iPrAT)H, the diphosphanylamido complex [( (iPr)2ATI)Ca((Ph2P)2N)(THF)2] was obtained by reaction of CaI2 with the potassium compounds [( (iPr)2ATI)K] and [K(THF)n][N(PPh2)2]. The single crystal X-ray structures of all compounds were established and the latter compound shows a eta2-coordination mode of the ligand via the nitrogen and one phosphorus atom.

Composition Formulas of Inorganic Compounds in Terms of Cluster Plus Glue Atom Model.

PubMed

Ma, Yanping; Dong, Dandan; Wu, Aimin; Dong, Chuang

2018-01-16

The present paper attempts to identify the molecule-like structural units in inorganic compounds, by applying the so-called "cluster plus glue atom model". This model, originating from metallic glasses and quasi-crystals, describes any structure in terms of a nearest-neighbor cluster and a few outer-shell glue atoms, expressed in the cluster formula [cluster](glue atoms). Similar to the case for normal molecules where the charge transfer occurs within the molecule to meet the commonly known octet electron rule, the octet state is reached after matching the nearest-neighbor cluster with certain outer-shell glue atoms. These kinds of structural units contain information on local atomic configuration, chemical composition, and electron numbers, just as for normal molecules. It is shown that the formulas of typical inorganic compounds, such as fluorides, oxides, and nitrides, satisfy a similar octet electron rule, with the total number of valence electrons per unit formula being multiples of eight.

A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry.

PubMed

Thornton, Joel A; Kercher, James P; Riedel, Theran P; Wagner, Nicholas L; Cozic, Julie; Holloway, John S; Dubé, William P; Wolfe, Glenn M; Quinn, Patricia K; Middlebrook, Ann M; Alexander, Becky; Brown, Steven S

2010-03-11

Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury and hydrocarbons such as the greenhouse gas methane. Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone, a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon. Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions. We also suggest that a significant fraction of tropospheric chlorine atoms may arise directly from anthropogenic pollutants.

Surface effects on the mechanical elongation of AuCu nanowires: De-alloying and the formation of mixed suspended atomic chains

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

Lagos, M. J.; Laboratório Nacional de Nanotecnologia-LNNANO, 13083-970 Campinas-SP; Autreto, P. A. S.

2015-03-07

We report here an atomistic study of the mechanical deformation of Au{sub x}Cu{sub (1−x)} atomic-size wires (nanowires (NWs)) by means of high resolution transmission electron microscopy experiments. Molecular dynamics simulations were also carried out in order to obtain deeper insights on the dynamical properties of stretched NWs. The mechanical properties are significantly dependent on the chemical composition that evolves in time at the junction; some structures exhibit a remarkable de-alloying behavior. Also, our results represent the first experimental realization of mixed linear atomic chains (LACs) among transition and noble metals; in particular, surface energies induce chemical gradients on NW surfacesmore » that can be exploited to control the relative LAC compositions (different number of gold and copper atoms). The implications of these results for nanocatalysis and spin transport of one-atom-thick metal wires are addressed.« less

Formation of bimetallic clusters in superfluid helium nanodroplets analysed by atomic resolution electron tomography

PubMed Central

Haberfehlner, Georg; Thaler, Philipp; Knez, Daniel; Volk, Alexander; Hofer, Ferdinand; Ernst, Wolfgang E.; Kothleitner, Gerald

2015-01-01

Structure, shape and composition are the basic parameters responsible for properties of nanoscale materials, distinguishing them from their bulk counterparts. To reveal these in three dimensions at the nanoscale, electron tomography is a powerful tool. Advancing electron tomography to atomic resolution in an aberration-corrected transmission electron microscope remains challenging and has been demonstrated only a few times using strong constraints or extensive filtering. Here we demonstrate atomic resolution electron tomography on silver/gold core/shell nanoclusters grown in superfluid helium nanodroplets. We reveal morphology and composition of a cluster identifying gold- and silver-rich regions in three dimensions and we estimate atomic positions without using any prior information and with minimal filtering. The ability to get full three-dimensional information down to the atomic scale allows understanding the growth and deposition process of the nanoclusters and demonstrates an approach that may be generally applicable to all types of nanoscale materials. PMID:26508471

Multinuclear metal-binding ability of a carotene

PubMed Central

Horiuchi, Shinnosuke; Tachibana, Yuki; Yamashita, Mitsuki; Yamamoto, Koji; Masai, Kohei; Takase, Kohei; Matsutani, Teruo; Kawamata, Shiori; Kurashige, Yuki; Yanai, Takeshi; Murahashi, Tetsuro

2015-01-01

Carotenes are naturally abundant unsaturated hydrocarbon pigments, and their fascinating physical and chemical properties have been studied intensively not only for better understanding of the roles in biological processes but also for the use in artificial chemical systems. However, their metal-binding ability has been virtually unexplored. Here we report that β-carotene has the ability to assemble and align ten metal atoms to afford decanuclear homo- and heterometal chain complexes. The metallo–carotenoid framework shows reversible metalation–demetalation reactivity with multiple metals, which allows us to control the size of metal chains as well as the heterobimetallic composition and arrangement of the carotene-supported metal chains. PMID:25857402

Point-by-point compositional analysis for atom probe tomography.

PubMed

Stephenson, Leigh T; Ceguerra, Anna V; Li, Tong; Rojhirunsakool, Tanaporn; Nag, Soumya; Banerjee, Rajarshi; Cairney, Julie M; Ringer, Simon P

2014-01-01

This new alternate approach to data processing for analyses that traditionally employed grid-based counting methods is necessary because it removes a user-imposed coordinate system that not only limits an analysis but also may introduce errors. We have modified the widely used "binomial" analysis for APT data by replacing grid-based counting with coordinate-independent nearest neighbour identification, improving the measurements and the statistics obtained, allowing quantitative analysis of smaller datasets, and datasets from non-dilute solid solutions. It also allows better visualisation of compositional fluctuations in the data. Our modifications include:.•using spherical k-atom blocks identified by each detected atom's first k nearest neighbours.•3D data visualisation of block composition and nearest neighbour anisotropy.•using z-statistics to directly compare experimental and expected composition curves. Similar modifications may be made to other grid-based counting analyses (contingency table, Langer-Bar-on-Miller, sinusoidal model) and could be instrumental in developing novel data visualisation options.

Synthesis, crystal structure and DFT studies of a novel dinuclear copper(I) complex with triphenylphosphine and 2-mercaptonicotinic acid

NASA Astrophysics Data System (ADS)

Ahmad, Tayyaba; Mahmood, Rashid; Georgieva, Ivelina; Zahariev, Tsvetan; Tahir, Muhammad Nawaz; Shaheen, Muhammad Ashraf; Gilani, Mazhar Amjad; Ahmad, Saeed

2018-02-01

A novel dinuclear copper(I) complex, {[Cu2(Mnt)2(PPh3)2Cl2].2H2O.CH3CN}2 (1) (Mnt = Mercaptonicotinic acid, PPh3 = triphenylphosphine) was prepared and its structure was determined by X-ray crystallography. The complex 1 consists of two dinuclear molecules and in each molecule, the two copper atoms are bridged by S atoms of N-protonated mercaptonicotinic acid forming a four-membered ring. The planar Cu2S2 core is characterized by significant cuprophilic interactions (Cusbnd Cu distance = 2.7671(8), 2.8471(8) Å). Each copper atom in 1 is coordinated by two sulfur atoms of Mnt, one phosphorus atom of PPh3 and a chloride ion adopting a tetrahedral geometry. The calculated Gibbs energies for reaction in CH3CN supported the experimental structure and predicted more favorable formation of dinuclear Cu(I) complex as compared to the mononuclear Cu(I) complex. The dinuclear complex is stabilized by 65.98 kJ mol-1 by coupling of two mononuclear Cu(I) complexes. The IR spectra of 1 and Mnt ligand were reliably interpreted and the Mnt vibrations, which are sensitive to the ligand coordination to Cu(I) ion in 1 were selected with the help of DFT/ωB97XD calculations.

Imaging and three-dimensional reconstruction of chemical groups inside a protein complex using atomic force microscopy

NASA Astrophysics Data System (ADS)

Kim, Duckhoe; Sahin, Ozgur

2015-03-01

Scanning probe microscopes can be used to image and chemically characterize surfaces down to the atomic scale. However, the localized tip-sample interactions in scanning probe microscopes limit high-resolution images to the topmost atomic layer of surfaces, and characterizing the inner structures of materials and biomolecules is a challenge for such instruments. Here, we show that an atomic force microscope can be used to image and three-dimensionally reconstruct chemical groups inside a protein complex. We use short single-stranded DNAs as imaging labels that are linked to target regions inside a protein complex, and T-shaped atomic force microscope cantilevers functionalized with complementary probe DNAs allow the labels to be located with sequence specificity and subnanometre resolution. After measuring pairwise distances between labels, we reconstruct the three-dimensional structure formed by the target chemical groups within the protein complex using simple geometric calculations. Experiments with the biotin-streptavidin complex show that the predicted three-dimensional loci of the carboxylic acid groups of biotins are within 2 Å of their respective loci in the corresponding crystal structure, suggesting that scanning probe microscopes could complement existing structural biological techniques in solving structures that are difficult to study due to their size and complexity.

Methylocystis strain SB2 materials and methods

DOEpatents

Semrau, Jeremy D; Gallagher, Warren; Yoon, Sukhwan; Im, Jeongdae; DiSpririto, Alan A; Lee, Sung-Woo; Hartsel, Scott; McEllistrem, Marcus T

2014-01-14

The present disclosures provides isolated or purified compounds, each of which bind to a metal atom. Generally, the compounds are small in size (e.g., molecular weight of less than about 1 kDa) and peptidic in nature, inasmuch as the compounds comprise amino acids. In some embodiments, the compound comprises a structure of Formula I; M.sub.1-P.sub.1-M.sub.2-P.sub.2 wherein each of P.sub.1 and P.sub.2 is a peptide comprising at least two amino acids, M.sub.1 is a first metal binding moiety comprising a substituted imidazolone ring, M.sub.2 is a second metal binding moiety comprising a substituted oxazolone ring, and wherein M.sub.1 and M.sub.2 bind to a single metal atom. Also provided are related complexes, conjugates, cells which synthesize the compounds of the present disclosures, substantially homogenous cultures thereof, kits and compositions, and methods of making or using the materials of the present disclosures.

Metal nanoparticle-graphene oxide composites: Photophysical properties and sensing applications

NASA Astrophysics Data System (ADS)

Murphy, Sean J.

Composite nanomaterials allow for attractive properties of multiple functional components to be combined. Fundamental understanding of the interaction between different nanomaterials, their surroundings, and nearby molecular species is pertinent for implementation into devices. Metal nanoparticles have been used for their optical properties in many applications including stained glass, cancer therapy, solar steam generation, surface enhanced Raman spectroscopy (SERS), and catalysis. Carbon-based nanomaterials such as graphene and carbon nanotubes show potential for a wide variety of applications including solar energy harvesting, chemical sensors, and electronics. Combining useful and in some cases new properties of composite nanomaterials offers exciting opportunities in fundamental science and device development. In this dissertation, I aim to address understanding photoinduced interaction between porphyrin and silver nanoparticles, inter-sheet interaction between stacked graphene oxide (GO) sheets in thin films, complexation of reduced GO with Raman active target molecule in SERS applications, and efficacy of graphene-metal nanoparticle composites for sensing applications. Molecule-metal nanoparticle composite material made up of photoactive porphyrin and silver nanoparticles was studied using various spectroscopic tools. UV-visible absorption and surface enhanced Raman spectroscopic results suggest formation of a charge-transfer complex for porphyrin-silver nanoparticle composite. Ultrafast transient absorption and fluorescence upconversion spectroscopies further corroborate electronic interaction by providing evidence for excited state electron transfer between porphyrin and silver nanoparticles. Understanding electronic interaction between adsorbed photoactive molecules and metal nanoparticles may be of use for applications in photocatalysis or light-energy harvesting. Graphene oxide (GO) thin films have been prepared and studied using transient absorption microscopy (TAM). Transient absorption microscopy correlated with atomic force microscope allows for the morphological properties of GO thin film to be related to optical properties, namely dynamics of photoexcited carriers in GO. Results suggest short-timescale (ps -- ˜1 ns) dynamics of charge carriers in GO are affected very little by interaction with the glass substrate on which GO is placed. Also, the stack thickness or number of stacked GO sheets does not play a large role in the short-timescale dynamics of GO charge carriers. GO or reduced GO (RGO)-silver nanoparticles composites were produced using different methods: (1) chemical reduction of silver ion precursor and (2) photocatalytic reduction of GO and silver ion using TiO2 nanoparticles. Optical and morphological properties of composites were studied using spectroscopy and electron microscopy revealing a degree of control in metal nanoparticle growth and loading on the surface of RGO. Nanocomposites were shown to be capable of complexing with or adsorbing target molecular species. Complexation and adsorption are corroborated with demonstration that the composite nanomaterials act as effective SERRS sensors taking advantage of localized surface plasmon resonance of metal nanoparticles and the ability of RGO to interact with molecular and ionic species.

Role of string-like collective atomic motion on diffusion and structural relaxation in glass forming Cu-Zr alloys

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

Zhang, Hao; Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4; Zhong, Cheng

2015-04-28

We investigate Cu-Zr liquid alloys using molecular dynamics simulation and well-accepted embedded atom method potentials over a wide range of chemical composition and temperature as model metallic glass-forming (GF) liquids. As with other types of GF materials, the dynamics of these complex liquids are characterized by “dynamic heterogeneity” in the form of transient polymeric clusters of highly mobile atoms that are composed in turn of atomic clusters exhibiting string-like cooperative motion. In accordance with the string model of relaxation, an extension of the Adam-Gibbs (AG) model, changes in the activation free energy ΔG{sub a} with temperature of both the Cumore » and Zr diffusion coefficients D, and the alpha structural relaxation time τ{sub α} can be described to a good approximation by changes in the average string length, L. In particular, we confirm that the strings are a concrete realization of the abstract “cooperatively rearranging regions” of AG. We also find coexisting clusters of relatively “immobile” atoms that exhibit predominantly icosahedral local packing rather than the low symmetry packing of “mobile” atoms. These two distinct types of dynamic heterogeneity are then associated with different fluid structural states. Glass-forming liquids are thus analogous to polycrystalline materials where the icosahedrally packed regions correspond to crystal grains, and the strings reside in the relatively disordered grain boundary-like regions exterior to these locally well-ordered regions. A dynamic equilibrium between localized (“immobile”) and wandering (“mobile”) particles exists in the liquid so that the dynamic heterogeneity can be considered to be type of self-assembly process. We also characterize changes in the local atomic free volume in the course of string-like atomic motion to better understand the initiation and propagation of these fluid excitations.« less

Platinum clusters with precise numbers of atoms for preparative-scale catalysis.

PubMed

Imaoka, Takane; Akanuma, Yuki; Haruta, Naoki; Tsuchiya, Shogo; Ishihara, Kentaro; Okayasu, Takeshi; Chun, Wang-Jae; Takahashi, Masaki; Yamamoto, Kimihisa

2017-09-25

Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt 10 ) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.

Activity descriptor identification for oxygen reduction on platinum-based bimetallic nanoparticles: in situ observation of the linear composition-strain-activity relationship.

PubMed

Jia, Qingying; Liang, Wentao; Bates, Michael K; Mani, Prasanna; Lee, Wendy; Mukerjee, Sanjeev

2015-01-27

Despite recent progress in developing active and durable oxygen reduction catalysts with reduced Pt content, lack of elegant bottom-up synthesis procedures with knowledge over the control of atomic arrangement and morphology of the Pt-alloy catalysts still hinders fuel cell commercialization. To follow a less empirical synthesis path for improved Pt-based catalysts, it is essential to correlate catalytic performance to properties that can be easily controlled and measured experimentally. Herein, using Pt-Co alloy nanoparticles (NPs) with varying atomic composition as an example, we show that the atomic distribution of Pt-based bimetallic NPs under operating conditions is strongly dependent on the initial atomic ratio by employing microscopic and in situ spectroscopic techniques. The PtxCo/C NPs with high Co content possess a Co concentration gradient such that Co is concentrated in the core and gradually depletes in the near-surface region, whereas the PtxCo/C NPs with low Co content possess a relatively uniform distribution of Co with low Co population in the near-surface region. Despite their different atomic structure, the oxygen reduction reaction (ORR) activity of PtxCo/C and Pt/C NPs is linearly related to the bulk average Pt-Pt bond length (RPt-Pt). The RPt-Pt is further shown to contract linearly with the increase in Co/Pt composition. These linear correlations together demonstrate that (i) the improved ORR activity of PtxCo/C NPs over pure Pt NPs originates predominantly from the compressive strain and (ii) the RPt-Pt is a valid strain descriptor that bridges the activity and atomic composition of Pt-based bimetallic NPs.

Process for functionalizing alkanes

DOEpatents

Bergman, Robert G.; Janowicz, Andrew H.; Periana-Pillai, Roy A.

1985-01-01

Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising: (a) reacting said saturated hydrocarbons of the formula: RH where: H represents a hydrogen atom, and R represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRhPMe.sub.3 H.sub.2 where: Cp represents a pentamethylated cyclopentadienyl radical, Rh represents a rhodium atom, P represents a phosphorous atom, Me represents a methyl group, H represents a hydrogen atom, in the presence of ultraviolet radiation at a temperature maintained at about -60.degree. to -17.degree. C. to form a hydridoalkyl complex of the formula: CpRhPMe.sub.3 RH (b) reacting said hydridoalkyl complex with a haloform of the formula: CHX.sub.3 where: X represents a bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e. ambient) to form a functional haloalkyl compound.

A molecular view of the role of chirality in charge-driven polypeptide complexation

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

Hoffmann, K. Q.; Perry, S. L.; Leon, L.

Polyelectrolyte molecules of opposite charge are known to form stable complexes in solution. Depending on the system conditions, such complexes can be solid or liquid. The latter are known as complex coacervates, and they appear as a second liquid phase in equilibrium with a polymer-dilute aqueous phase. This work considers the complexation between poly(glutamic acid) and poly(lysine), which is of particular interest because it enables examination of the role of chirality in ionic complexation, without changes to the overall chemical composition. Systematic atomic-level simulations are carried out for chains of poly(glutamic acid) and poly(lysine) with varying combinations of chirality alongmore » the backbone. Achiral chains form unstructured complexes. In contrast, homochiral chains lead to formation of stable beta-sheets between molecules of opposite charge, and experiments indicate that beta-sheet formation is correlated with the formation of solid precipitates. Changes in chirality along the peptide backbone are found to cause "kinks" in the beta-sheets. These are energetically unfavorable and result in irregular structures that are more difficult to pack together. Taken together, these results provide new insights that may be of use for the development of simple yet strong bioinspired materials consisting of beta-rich domains and amorphous regions.« less

Syntheses and structures of ruthenium(II) N,S-heterocyclic carbene diphosphine complexes and their catalytic activity towards transfer hydrogenation.

PubMed

Ding, Nini; Hor, T S Andy

2011-06-06

Phosphine exchange of [Ru(II) Br(MeCOO)(PPh(3))(2)(3-RBzTh)] (3-RBzTh=3-benzylbenzothiazol-2-ylidene) with a series of diphosphines (bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethylene (dppv), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1,4-bis(diphenylphosphino)butane (dppb), and 1,3-(diphenylphosphino)propane (dppp)) gave mononuclear and neutral octahedral complexes [RuBr(MeCOO)(η(2)-P(2))(3-RBzTh)] (P(2)=dppm (2), dppv (3), dppf (4), dppb (5), or dppp (6)), the coordination spheres of which contained four different ligands, namely, a chelating diphosphine, carboxylate, N,S-heterocyclic carbene (NSHC), and a bromide. Two geometric isomers of 6 (6a and 6b) have been isolated. The structures of these products, which have been elucidated by single-crystal X-ray crystallography, show two structural types, I and II, depending on the relative dispositions of the ligands. Type I structures contain a carbenic carbon atom trans to the oxygen atom, whereas two phosphorus atoms are trans to bromine and oxygen atoms. The type II system comprises a carbene carbon atom trans to one of the phosphorus atoms, whereas the other phosphorus is trans to the oxygen atom, with the bromine trans to the remaining oxygen atom. Complexes 2, 3, 4, and 6a belong to type I, whereas 5 and 6b are of type II. The kinetic product 6b eventually converts into 6a upon standing. These complexes are active towards catalytic reduction of para-methyl acetophenone by 2-propanol at 82 °C under 1% catalyst load giving the corresponding alcohols. The dppm complex 2 shows the good yields (91-97%) towards selected ketones. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of macromolecules, ligands and macromolecule-ligand complexes

DOEpatents

Von Dreele, Robert B [Los Alamos, NM

2008-12-23

A method for determining atomic level structures of macromolecule-ligand complexes through high-resolution powder diffraction analysis and a method for providing suitable microcrystalline powder for diffraction analysis are provided. In one embodiment, powder diffraction data is collected from samples of polycrystalline macromolecule and macromolecule-ligand complex and the refined structure of the macromolecule is used as an approximate model for a combined Rietveld and stereochemical restraint refinement of the macromolecule-ligand complex. A difference Fourier map is calculated and the ligand position and points of interaction between the atoms of the macromolecule and the atoms of the ligand can be deduced and visualized. A suitable polycrystalline sample of macromolecule-ligand complex can be produced by physically agitating a mixture of lyophilized macromolecule, ligand and a solvent.

Building a pseudo-atomic model of the anaphase-promoting complex.

PubMed

Kulkarni, Kiran; Zhang, Ziguo; Chang, Leifu; Yang, Jing; da Fonseca, Paula C A; Barford, David

2013-11-01

The anaphase-promoting complex (APC/C) is a large E3 ubiquitin ligase that regulates progression through specific stages of the cell cycle by coordinating the ubiquitin-dependent degradation of cell-cycle regulatory proteins. Depending on the species, the active form of the APC/C consists of 14-15 different proteins that assemble into a 20-subunit complex with a mass of approximately 1.3 MDa. A hybrid approach of single-particle electron microscopy and protein crystallography of individual APC/C subunits has been applied to generate pseudo-atomic models of various functional states of the complex. Three approaches for assigning regions of the EM-derived APC/C density map to specific APC/C subunits are described. This information was used to dock atomic models of APC/C subunits, determined either by protein crystallography or homology modelling, to specific regions of the APC/C EM map, allowing the generation of a pseudo-atomic model corresponding to 80% of the entire complex.

Synthesis and investigation of Pd(I) carbonyl complexes with heteroorganic ligands

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

Lamberov, A.A.; Polovnyak, V.K.; Akhmetov, N.S.

1987-09-10

Pd(I) carbonyl complexes are attracting attention because they have been shown to have catalytic properties in a series of organic syntheses. The stability and catalytic properties of these compounds are determined by the nature of the phosphine ligand and the bridge coordination of the carbonylgroup. Through the partial replacement of carbonyl and acido ligands by heteroorganic ligands in carbonyl halogenide and carbonyl acetate Pd(I) complexes, new stable Pd(I) complexes were obtained: (PdLX)/sub 2/CO, where L = PPh/sub 3/, X = OAc; L = AsPh/sub 3/, X = Cl, Br, OAc; L = SbPh/sub 3/, X = Cl Br, OAc; Lmore » = Ph/sub 2/PCH/sub 2/PPh/sub 2/, Ph/sub 2/AsCH/sub 2/AsPh/sub 2/, X = OAc. Atoms of the heteroorganic and acido ligands are equivalently coordinated to the palladium atoms. The carbonyl group in the complexes has bridge coordination to palladium atoms in the Pd(CO)Pd fragment; in complexes with bidentate heteroorganic ligands the covalent bond between palladium atoms is absent.« less

Synthesizing (ZrAl3 + AlN)/Mg-Al composites by a 'matrix exchange' method

NASA Astrophysics Data System (ADS)

Gao, Tong; Li, Zengqiang; Hu, Kaiqi; Han, Mengxia; Liu, Xiangfa

2018-06-01

A method named 'matrix exchange' to synthesize ZrAl3 and AlN reinforced Mg-Al composite was developed in this paper. By inserting Al-10ZrN master alloy into Mg matrix and reheating the cooled ingot to 550 °C, Al and Mg atoms diffuse to the opposite side. As a result, liquid melt occurs once the interface areas reach to proper compositions. Then dissolved Al atoms react with ZrN, leading to the in-situ formation of ZrAl3 and AlN particles, while the Al matrix is finally replaced by Mg. This study provides a new insight for preparing Mg composites.

Experimental and numerical measurements of adhesion energies between PHEMA and PGLYMA with hydroxyapatite crystal.

PubMed

Youssefian, Sina; Liu, Pingsheng; Askarinejad, Sina; Shalchy, Faezeh; Song, Jie; Rahbar, Nima

2015-07-16

Synthetic orthopaedic materials consisting of a single bioinert polymeric material do not meet the complex biological and physical requirements of scaffold-guided bone tissue repair and regeneration. Of particular interest is the design of biocompatible hydrogel-hydroxyapatite composite bone substitutes with outstanding interfacial adhesion that would warranty the ability for the composite to withstand functional loadings without exhibiting brittle fractures during the dynamic guided tissue regeneration. For this purpose, the hydroxylated side chain of chemically cross-linked poly (2-hydroxyethyl methacrylate) (pHEMA) is substitute with a carboxylated side chain to make poly (glycerol methacrylate) (pGLYMA). Here, we carry out atomistic simulations and atomic force microscopy to predict and experimentally determine the interfacial adhesion energies of pHEMA and pGLYMA with the surface of single-crystalline hydroxyapatite (HA) whiskers. Both experimental and numerical results showed that pGLYMA has stronger adhesion forces with HA and may be used for preparing a high-affinity polymer-HA composite. The high adhesive interactions between pGLYMA and HA were found to be due to strong electrostatic energies.

Atomic and molecular layer deposition for surface modification

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

Vähä-Nissi, Mika, E-mail: mika.vaha-nissi@vtt.fi; Sievänen, Jenni; Salo, Erkki

2014-06-01

Atomic and molecular layer deposition (ALD and MLD, respectively) techniques are based on repeated cycles of gas–solid surface reactions. A partial monolayer of atoms or molecules is deposited to the surface during a single deposition cycle, enabling tailored film composition in principle down to molecular resolution on ideal surfaces. Typically ALD/MLD has been used for applications where uniform and pinhole free thin film is a necessity even on 3D surfaces. However, thin – even non-uniform – atomic and molecular deposited layers can also be used to tailor the surface characteristics of different non-ideal substrates. For example, print quality of inkjetmore » printing on polymer films and penetration of water into porous nonwovens can be adjusted with low-temperature deposited metal oxide. In addition, adhesion of extrusion coated biopolymer to inorganic oxides can be improved with a hybrid layer based on lactic acid. - Graphical abstract: Print quality of a polylactide film surface modified with atomic layer deposition prior to inkjet printing (360 dpi) with an aqueous ink. Number of printed dots illustrated as a function of 0, 5, 15 and 25 deposition cycles of trimethylaluminum and water. - Highlights: • ALD/MLD can be used to adjust surface characteristics of films and fiber materials. • Hydrophobicity after few deposition cycles of Al{sub 2}O{sub 3} due to e.g. complex formation. • Same effect on cellulosic fabrics observed with low temperature deposited TiO{sub 2}. • Different film growth and oxidation potential with different precursors. • Hybrid layer on inorganic layer can be used to improve adhesion of polymer melt.« less

Atomic contributions from spin-orbit coupling to 29Si NMR chemical shifts in metallasilatrane complexes.

PubMed

Autschbach, Jochen; Sutter, Kiplangat; Truflandier, Lionel A; Brendler, Erica; Wagler, Jörg

2012-10-01

New members of a novel class of metallasilatrane complexes [X-Si-(μ-mt)(4)-M-Y], with M=Ni, Pd, Pt, X=F, Cl, Y=Cl, Br, I, and mt=2-mercapto-1-methylimidazolide, have been synthesized and characterized structurally by X-ray diffraction and by (29)Si solid-state NMR. Spin-orbit (SO) effects on the (29)Si chemical shifts induced by the metal, by the sulfur atoms in the ligand, and by heavy halide ligands Y=Cl, Br, I were investigated with the help of relativistic density functional calculations. Operators used in the calculations were constructed such that SO coupling can selectively be switched off for certain atoms. The unexpectedly large SO effects on the (29)Si shielding in the Ni complex with X=Y=Cl reported recently originate directly from the Ni atom, not from other moderately heavy atoms in the complex. With respect to Pd, SO effects are amplified for Ni owing to its smaller ligand-field splitting, despite the smaller nuclear charge. In the X=Cl, Y=Cl, Br, I series of complexes the Y ligand strongly modulates the (29)Si shift by amplifying or suppressing the metal SO effects. The pronounced delocalization of the partially covalent M←Y bond plays an important role in modulating the (29)Si shielding. We also demonstrate an influence from the X ligand on the (29)Si SO shielding contributions originating at Y. The NMR spectra for [X-Si-(μ-mt)(4)-M-Y] must be interpreted mainly based on electronic and relativistic effects, rather than structural differences between the complexes. The results highlight the sometimes unintuitive role of SO coupling in NMR spectra of complexes containing heavy atoms. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic spectral-product representations of molecular electronic structure: metric matrices and atomic-product composition of molecular eigenfunctions.

PubMed

Ben-Nun, M; Mills, J D; Hinde, R J; Winstead, C L; Boatz, J A; Gallup, G A; Langhoff, P W

2009-07-02

Recent progress is reported in development of ab initio computational methods for the electronic structures of molecules employing the many-electron eigenstates of constituent atoms in spectral-product forms. The approach provides a universal atomic-product description of the electronic structure of matter as an alternative to more commonly employed valence-bond- or molecular-orbital-based representations. The Hamiltonian matrix in this representation is seen to comprise a sum over atomic energies and a pairwise sum over Coulombic interaction terms that depend only on the separations of the individual atomic pairs. Overall electron antisymmetry can be enforced by unitary transformation when appropriate, rather than as a possibly encumbering or unnecessary global constraint. The matrix representative of the antisymmetrizer in the spectral-product basis, which is equivalent to the metric matrix of the corresponding explicitly antisymmetric basis, provides the required transformation to antisymmetric or linearly independent states after Hamiltonian evaluation. Particular attention is focused in the present report on properties of the metric matrix and on the atomic-product compositions of molecular eigenstates as described in the spectral-product representations. Illustrative calculations are reported for simple but prototypically important diatomic (H(2), CH) and triatomic (H(3), CH(2)) molecules employing algorithms and computer codes devised recently for this purpose. This particular implementation of the approach combines Slater-orbital-based one- and two-electron integral evaluations, valence-bond constructions of standard tableau functions and matrices, and transformations to atomic eigenstate-product representations. The calculated metric matrices and corresponding potential energy surfaces obtained in this way elucidate a number of aspects of the spectral-product development, including the nature of closure in the representation, the general redundancy or linear dependence of its explicitly antisymmetrized form, the convergence of the apparently disparate atomic-product and explicitly antisymmetrized atomic-product forms to a common invariant subspace, and the nature of a chemical bonding descriptor provided by the atomic-product compositions of molecular eigenstates. Concluding remarks indicate additional studies in progress and the prognosis for performing atomic spectral-product calculations more generally and efficiently.

Synthesis of Nanocrystalline SnOx (x = 1–2) Thin Film Using a Chemical Bath Deposition Method with Improved Deposition Time, Temperature and pH

PubMed Central

Ebrahimiasl, Saeideh; Yunus, Wan Md. Zin Wan; Kassim, Anuar; Zainal, Zulkarnain

2011-01-01

Nanocrystalline SnOx (x = 1–2) thin films were prepared on glass substrates by a simple chemical bath deposition method. Triethanolamine was used as complexing agent to decrease time and temperature of deposition and shift the pH of the solution to the noncorrosive region. The films were characterized for composition, surface morphology, structure and optical properties. X-ray diffraction analysis confirms that SnOx thin films consist of a polycrystalline structure with an average grain size of 36 nm. Atomic force microscopy studies show a uniform grain distribution without pinholes. The elemental composition was evaluated by energy dispersive X-ray spectroscopy. The average O/Sn atomic percentage ratio is 1.72. Band gap energy and optical transition were determined from optical absorbance data. The film was found to exhibit direct and indirect transitions in the visible spectrum with band gap values of about 3.9 and 3.7 eV, respectively. The optical transmittance in the visible region is 82%. The SnOx nanocrystals exhibit an ultraviolet emission band centered at 392 nm in the vicinity of the band edge, which is attributed to the well-known exciton transition in SnOx. Photosensitivity was detected in the positive region under illumination with white light. PMID:22163690

Characterization of Cell Surface and EPS Remodeling of Azospirillum brasilense Chemotaxis-like 1 Signal Transduction Pathway mutants by Atomic Force Microscopy

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

Billings, Amanda N; Siuti, Piro; Bible, Amber

2011-01-01

To compete in complex microbial communities, bacteria must quickly sense environmental changes and adjust cellular functions for optimal growth. Chemotaxis-like signal transduction pathways are implicated in the modulation of multiple cellular responses, including motility, EPS production, and cell-to-cell interactions. Recently, the Che1 chemotaxis-like pathway from Azospirillum brasilense was shown to modulate flocculation. In A. brasilense, cell surface properties, including EPS production, are thought to play a direct role in promoting flocculation. Using atomic force microscopy (AFM), we have detected distinct changes in the surface morphology of flocculating A. brasilense Che1 mutant strains that are absent in the wild type strain.more » Whereas the wild type strain produces a smooth mucosal extracellular matrix, the flocculating Che1 mutant strains produce distinctive extracellular fibril structures. Further analyses using flocculation inhibition and lectin-binding assays suggest that the composition of EPS components in the extracellular matrix differs between the cheA1 and cheY1 mutants, despite an apparent similarity in the macroscopic floc structures. Collectively, these data indicate that mutations in the Che1 pathway that result in increased flocculation are correlated with distinctive changes in the extracellular matrix structure produced by the mutants, including likely changes in the EPS structure and/or composition.« less

Influence of hydrocarbon fuel structural constitution and flame temperature on soot formation in laminar diffusion flames

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

Gulder, O.L.

1989-11-01

A systematic study of soot formation along the centerlines of axisymmetric laminar diffusion flames of a large number of liquid hydrocarbons, hydrocarbon blends, and transportation fuels were made. Measurements of the attenuation of a laser beam across the flame diameter were used to obtain the soot volume fraction, assuming Rayleigh extinction. Two sets of hydrocarbon blends were designed such that the molecular fuel composition varied considerably but the temperature fields in the flames were kept practically constant. Thus it was possible to separate the effects of molecular structure and the flame temperature on soot formation. It was quantitatively shown thatmore » the smoke height is a lumped measure of fuel molecular constitution and hydrogen-to-carbon ratio. Hydrocarbon fuel molecular composition was characterized by six carbon atom types that can be obtained, for complex hydrocarbon mixtures like transportation fuels, from proton nuclear magnetic resonance (/sup 1/H NMR) measurements. Strong attenuation of the laser beam was observed at heights very close to the burner rim. Visible flame profiles along the flame length were shown to have good self-similarity. Kent's model for diffusion flames was modified to include the effects of differences in flame temperatures and molecular diffusivities between fuels. An analysis based on the present data provides an assessment of the degree of contribution of different carbon atom types to the maximum soot volume fractions.« less

Independent evolution of functionally exchangeable mitochondrial outer membrane import complexes

PubMed Central

Dimmer, Kai S

2018-01-01

Assembly and/or insertion of a subset of mitochondrial outer membrane (MOM) proteins, including subunits of the main MOM translocase, require the fungi-specific Mim1/Mim2 complex. So far it was unclear which proteins accomplish this task in other eukaryotes. Here, we show by reciprocal complementation that the MOM protein pATOM36 of trypanosomes is a functional analogue of yeast Mim1/Mim2 complex, even though these proteins show neither sequence nor topological similarity. Expression of pATOM36 rescues almost all growth, mitochondrial biogenesis, and morphology defects in yeast cells lacking Mim1 and/or Mim2. Conversely, co-expression of Mim1 and Mim2 restores the assembly and/or insertion defects of MOM proteins in trypanosomes ablated for pATOM36. Mim1/Mim2 and pATOM36 form native-like complexes when heterologously expressed, indicating that additional proteins are not part of these structures. Our findings indicate that Mim1/Mim2 and pATOM36 are the products of convergent evolution and arose only after the ancestors of fungi and trypanosomatids diverged. PMID:29923829

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2‧-bipyridine

NASA Astrophysics Data System (ADS)

Koch, Angira; Kumar, Arvind; Singh, Suryabhan; Borthakur, Rosmita; Basumatary, Debajani; Lal, Ram A.; Shangpung, Sankey

2015-03-01

The synthesis of the heterobinuclear copper-zinc complex [CuZn(bz)3(bpy)2]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 Å. The complex is normal paramagnetic having μeff value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants Aav = 63 × 10-4 cm-1, characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g|| = 2.254 and g⊥ = 2.071 and A|| = 160 × 10-4 cm-1. The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution.

Composition Analysis of III-Nitrides at the Nanometer Scale: Comparison of Energy Dispersive X-ray Spectroscopy and Atom Probe Tomography.

PubMed

Bonef, Bastien; Lopez-Haro, Miguel; Amichi, Lynda; Beeler, Mark; Grenier, Adeline; Robin, Eric; Jouneau, Pierre-Henri; Mollard, Nicolas; Mouton, Isabelle; Monroy, Eva; Bougerol, Catherine

2016-12-01

The enhancement of the performance of advanced nitride-based optoelectronic devices requires the fine tuning of their composition, which has to be determined with a high accuracy and at the nanometer scale. For that purpose, we have evaluated and compared energy dispersive X-ray spectroscopy (EDX) in a scanning transmission electron microscope (STEM) and atom probe tomography (APT) in terms of composition analysis of AlGaN/GaN multilayers. Both techniques give comparable results with a composition accuracy better than 0.6 % even for layers as thin as 3 nm. In case of EDX, we show the relevance of correcting the X-ray absorption by simultaneous determination of the mass thickness and chemical composition at each point of the analysis. Limitations of both techniques are discussed when applied to specimens with different geometries or compositions.

Process for making solid-state radiation-emitting composition

DOEpatents

Ashley, Carol S.; Brinker, C. Jeffrey; Reed, Scott; Walko, Robert J.

1993-01-01

The invention provides a process for loading an aerogel substrate with tritium and the resultant compositions. According to the process, an aerogel substrate is hydrolyzed so that surface OH groups are formed. The hydrolyzed aerogel is then subjected to tritium exchange employing, for example, a tritium-containing gas, whereby tritium atoms replace H atoms of surface OH groups. OH and/or CH groups of residual alcohol present in the aerogel may also undergo tritium exchange.

Composition containing aerogel substrate loaded with tritium

DOEpatents

Ashley, Carol S.; Brinker, C. Jeffrey; Ellefson, Robert E.; Gill, John T.; Reed, Scott; Walko, Robert J.

1992-01-01

The invention provides a process for loading an aerogel substrate with tritium and the resultant compositions. According to the process, an aerogel substrate is hydrolyzed so that surface OH groups are formed. The hydrolyzed aerogel is then subjected to tritium exchange employing, for example, a tritium-containing gas, whereby tritium atoms replace H atoms of surface OH groups. OH and/or CH groups of residual alcohol present in the aerogel may also undergo tritium exchange.

Process for making solid-state radiation-emitting composition

DOEpatents

Ashley, C.S.; Brinker, C.J.; Reed, S.; Walko, R.J.

1993-08-31

The invention provides a process for loading an aerogel substrate with tritium and the resultant compositions. According to the process, an aerogel substrate is hydrolyzed so that surface OH groups are formed. The hydrolyzed aerogel is then subjected to tritium exchange employing, for example, a tritium-containing gas, whereby tritium atoms replace H atoms of surface OH groups. OH and/or CH groups of residual alcohol present in the aerogel may also undergo tritium exchange.

Band shift of 2D transition-metal dichalcogenide alloys: size and composition effects

NASA Astrophysics Data System (ADS)

Zhao, Yipeng; Zhang, Zhe; Ouyang, Gang

2018-04-01

Band engineering of 2D transition-metal dichalcogenides (2D-TMDs) is a vital task for their applications in electronic and optoelectronic nanodevices. In this study, we investigate the joint effect from size and composition contributions on the band shift of 2D-TMD alloys in terms of atomic bond relaxation consideration. A theoretical model is proposed to pursue the underlying mechanism, which can connect the band offset with the atomic bonding identities in the 2D-TMD alloys. We reveal that the bandgap of 2D-TMD alloys presents a bowing shape owing to the size-dependent interaction among atoms and shows blue shift or red shift due to different intermixing of components. It is demonstrated that both size and composition can be performed as the useful methods to modulate the band shift, which suggests an effective way to realize the desirable properties of 2D-TMD alloys.

Theoretical predictions of a bucky-diamond SiC cluster.

PubMed

Yu, Ming; Jayanthi, C S; Wu, S Y

2012-06-15

A study of structural relaxations of Si(n)C(m) clusters corresponding to different compositions, different relative arrangements of Si/C atoms, and different types of initial structure, reveals that the Si(n)C(m) bucky-diamond structure can be obtained for an initial network structure constructed from a truncated bulk 3C-SiC for a magic composition corresponding to n = 68 and m = 79. This study was performed using a semi-empirical Hamiltonian (SCED-LCAO) since it allowed an extensive search of different types of initial structures. However, the bucky-diamond structure predicted by this method was also confirmed by a more accurate density functional theory (DFT) based method. The bucky-diamond structure exhibited by a SiC-based system represents an interesting paradigm where a Si atom can form three-coordinated as well as four-coordinated networks with carbon atoms and vice versa and with both types of network co-existing in the same structure. Specifically, the bucky-diamond structure of the Si(68)C(79) cluster consists of a 35-atom diamond-like inner core (four-atom coordinations) suspended inside a 112-atom fullerene-like shell (three-atom coordinations).

Elemental and lattice-parameter mapping of binary oxide superlattices of (LaNiO 3 ) 4 /(LaMnO 3 ) 2 at atomic resolution

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

Kwon, Ji-Hwan; Lu, Ping; Hoffman, Jason

2016-12-19

We construct the elemental distribution and lattice strain maps from the measured atomic column positions in a (LaNiO3)(4)/(LaMnO3)(2) superlattice over a large field of view. The correlation between the distribution of B-cations and the lattice parameter in the form of Vegard's law is validated using atomic resolution energy dispersive x-ray spectroscopy (EDS). The maps show negligible Mn intermixing in the LaNiO3 layer, while Ni intermixing in the LaMnO3 layer improves away from the substrate interface to 9.5 atomic% from the 8th period onwards, indicating that the superlattice interfacial sharpness is established as the distance from the substrate increases. The mapsmore » allow an observation of the compositional defects of the B-sites, which is not possible by Z-contrast alone. Thus, this study demonstrates a promising approach for atomic scale correlative study of lattice strain and composition, and a method for the calibration of atomic resolution EDS maps.« less

Specific Adaptation of Gas Atomization Processing for Al-Based Alloy Powder for Additive Manufacturing

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

Anderson, Iver; Siemon, John

The initial three atomization attempts resulted in “freeze-outs” within the pour tubes in the pilot-scale system and yielded no powder. Re-evaluation of the alloy liquidus temperatures and melting characteristics, in collaboration with Alcoa, showed further superheat to be necessary to allow the liquid metal to flow through the pour tube to the atomization nozzle. A subsequent smaller run on the experimental atomization system verified these parameters and was successful, as were all successive runs on the larger pilot scale system. One alloy composition froze-out part way through the atomization on both pilot scale runs. SEM images showed needle formation andmore » phase segregations within the microstructure. Analysis of the pour tube freeze-out microstructures showed that large needles formed within the pour tube during the atomization experiment, which eventually blocked the melt stream. Alcoa verified the needle formation in this alloy using theoretical modeling of phase solidification. Sufficient powder of this composition was still generated to allow powder characterization and additive manufacturing trials at Alcoa.« less

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

Allen, C.A.W.; Watts, K.C.

Engine results using biofuels have varied considerably in the reported literature. This article addresses two potential sources of this variation, atomization differences and impurities due to lack of quality control during production. Atomization is the first process encountered during the combustion of fuels in a compression ignition engine and is largely determined by the fuel's viscosity and surface tension. Previous work using five experimentally produced methyl ester biodiesel fuels showed that the viscosity and surface tension could be predicted from their fatty acid ester composition, and the atomization characteristics in turn could be predicted from their viscosity and surface tension.more » This article utilizes the results of that work to give a quantitative comparison of the atomization characteristics of fifteen biodiesel fuel types using the fuel's viscosity and surface tension, predicted directly from the fatty acid composition of the fuels. Except for coconut and rapeseed biodiesel fuels, all of the rest of the 15 biodiesel fuels had similar atomization characteristics. Since the most likely contaminant in the fuel from the processing was residual glycerides, their effect on viscosity and surface tension was studied experimentally and their effect on the atomization characteristics was computed.« less

Local and average structures of BaTiO 3-Bi(Zn 1/2Ti 1/2)O 3

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

Usher, Tedi-Marie; Iamsasri, Thanakorn; Forrester, Jennifer S.

The complex crystallographic structures of (1-x)BaTiO 3-xBi(Zn 1/2Ti 1/2)O 3 (BT-xBZT) are examined using high resolution synchrotron X-ray diffraction, neutron diffraction, and neutron pair distribution function (PDF) analyses. The short-range structures are characterized from the PDFs, and a combined analysis of the X-ray and neutron diffraction patterns is used to determine the long-range structures. Our results demonstrate that the structure appears different when averaged over different length scales. In all compositions, the local structures determined from the PDFs show local tetragonal distortions (i.e., c/a > 1). But, a box-car fitting analysis of the PDFs reveals variations at different length scales.more » For 0.80BT-0.20BZT and 0.90BT-0.10BZT, the tetragonal distortions decrease at longer atom-atom distances (e.g., 30 vs. 5 ). When the longest distances are evaluated (r > 40 ), the lattice parameters approach cubic. Neutron and X-ray diffraction yield further information about the long-range structure. Compositions 0.80BT-0.20BZT and 0.90BT-0.10BZT appear cubic by Bragg diffraction (no peak splitting), consistent with the PDFs at long distances. However, these patterns cannot be adequately fit using a cubic lattice model; modeling their structures with the P4mm space group allows for a better fit to the patterns because the space group allows for c-axis atomic displacements that occur at the local scale. Furthermore, for the compositions 0.92BT-0.08BZT and 0.94BT-0.06BZT, strong tetragonal distortions are observed at the local scale and a less-distorted tetragonal structure is observed at longer length scales. In Rietveld refinements, the latter is modeled using a tetragonal phase. Since the peak overlap in these two-phase compositions limits the ability to model the local-scale structures as tetragonal, it is approximated in the refinements as a cubic phase. These results demonstrate that alloying BT with BZT results in increased disorder and disrupts the long-range ferroelectric symmetry present in BT, while the large tetragonal distortion present in BZT persists at the local scale.« less

Local and average structures of BaTiO 3-Bi(Zn 1/2Ti 1/2)O 3

DOE PAGES

Usher, Tedi-Marie; Iamsasri, Thanakorn; Forrester, Jennifer S.; ...

2016-11-11

The complex crystallographic structures of (1-x)BaTiO 3-xBi(Zn 1/2Ti 1/2)O 3 (BT-xBZT) are examined using high resolution synchrotron X-ray diffraction, neutron diffraction, and neutron pair distribution function (PDF) analyses. The short-range structures are characterized from the PDFs, and a combined analysis of the X-ray and neutron diffraction patterns is used to determine the long-range structures. Our results demonstrate that the structure appears different when averaged over different length scales. In all compositions, the local structures determined from the PDFs show local tetragonal distortions (i.e., c/a > 1). But, a box-car fitting analysis of the PDFs reveals variations at different length scales.more » For 0.80BT-0.20BZT and 0.90BT-0.10BZT, the tetragonal distortions decrease at longer atom-atom distances (e.g., 30 vs. 5 ). When the longest distances are evaluated (r > 40 ), the lattice parameters approach cubic. Neutron and X-ray diffraction yield further information about the long-range structure. Compositions 0.80BT-0.20BZT and 0.90BT-0.10BZT appear cubic by Bragg diffraction (no peak splitting), consistent with the PDFs at long distances. However, these patterns cannot be adequately fit using a cubic lattice model; modeling their structures with the P4mm space group allows for a better fit to the patterns because the space group allows for c-axis atomic displacements that occur at the local scale. Furthermore, for the compositions 0.92BT-0.08BZT and 0.94BT-0.06BZT, strong tetragonal distortions are observed at the local scale and a less-distorted tetragonal structure is observed at longer length scales. In Rietveld refinements, the latter is modeled using a tetragonal phase. Since the peak overlap in these two-phase compositions limits the ability to model the local-scale structures as tetragonal, it is approximated in the refinements as a cubic phase. These results demonstrate that alloying BT with BZT results in increased disorder and disrupts the long-range ferroelectric symmetry present in BT, while the large tetragonal distortion present in BZT persists at the local scale.« less

Chemical composition of individual aerosol particles in workplace air during production of manganese alloys.

PubMed

Gunst, S; Weinbruch, S; Wentzel, M; Ortner, H M; Skogstad, A; Hetland, S; Thomassen, Y

2000-02-01

Aerosol particle samples were collected at ELKEM ASA ferromanganese (FeMn) and silicomanganese (SiMn) smelters at Porsgrunn, Norway, during different production steps: raw material mixing, welding of protective steel casings, tapping of FeMn and slag, crane operation moving the ladles with molten metal, operation of the Metal Oxygen Refinement (MOR) reactor and casting of SiMn. Aerosol fractions were assessed for the analysis of the bulk elemental composition as well as for individual particle analysis. The bulk elemental composition was determined by inductively coupled plasma atomic emission spectrometry. For individual particle analysis, an electron microprobe was used in combination with wavelength-dispersive techniques. Most particles show a complex composition and cannot be attributed to a single phase. Therefore, the particles were divided into six groups according to their chemical composition: Group I, particles containing mainly metallic Fe and/or Mn; Group II, slag particles containing mainly Fe and/or Mn oxides; Group III, slag particles consisting predominantly of oxidized flux components such as Si, Al, Mg, Ca, Na and K; Group IV, particles consisting mainly of carbon; Group V, mixtures of particles from Groups II, III and IV; Group VI, mixtures of particles from Groups II and III. In raw material mixing, particles originating from the Mn ores were mostly found. In the welding of steel casings, most particles were assigned to Group II, Mn and Fe oxides. During the tapping of slag and metal, mostly slag particles from Group III were found (oxides of the flux components). During movement of the ladles, most particles came from Group II. At the MOR reactor, most of the particles belonged to the slag phase consisting of the flux components (Group III). The particles collected during the casting of SiMn were mainly attributed to the slag phase (Groups III and V). Due to the compositional complexity of the particles, toxicological investigations on the kinetics of pure compounds may not be easily associated with the results of this study.

Spectroscopic characterization and biological studies in vitro of a new silver complex with furosemide: Prospective of application as an antimicrobial agent

NASA Astrophysics Data System (ADS)

Lustri, Wilton R.; Lazarini, Silmara C.; Lustri, Bruna Cardinali; Corbi, Pedro P.; Silva, Maria Aline C.; Resende Nogueira, Flávia Aparecida; Aquino, Renata; Amaral, André C.; Treu Filho, Oswaldo; Massabni, Antonio Carlos; da Silva Barud, Hernane

2017-04-01

The present article describes the synthesis and biological studies in vitro of a novel silver complex with furosemide (Ag-FSE). Elemental, thermal and mass spectrometric analysis indicated a 1:1 metal/ligand composition, with the molecular formula AgC12H10ClN2O5S. Infrared and nuclear magnetic resonance studies suggest coordination of the ligand to the silver ion by the oxygen atoms of the carboxylate group. Additional Density Functional Theory (DFT) studies led to the proposition of the structure of the Ag-FSE complex. The antibacterial activities of the complex were primarily evaluated by antibiogram assays using the disc diffusion method and minimum inhibitory concentrations (MIC). Moreover, the mutagenicity of the complex was also evaluated to ensure that it is safe for subsequent application. The Ag-FSE complex has shown a significant in vitro antibacterial activity against Gram-positive Staphylococcus aureus (ATCC 25923), Gram negative Escherichia coli (ATCC 25922) and Pseudomonas aeruginosa (ATCC 27853), and yeast Candida albicans (ATCC 90028). The absence of a mutagenic activity of Ag-FSE against Salmonella Typhimurium bacterial strains in the Ames assay is an extremely important finding for its future use as a drug in medicine.

Probes for dark matter physics

NASA Astrophysics Data System (ADS)

Khlopov, Maxim Yu.

The existence of cosmological dark matter is in the bedrock of the modern cosmology. The dark matter is assumed to be nonbaryonic and consists of new stable particles. Weakly Interacting Massive Particle (WIMP) miracle appeals to search for neutral stable weakly interacting particles in underground experiments by their nuclear recoil and at colliders by missing energy and momentum, which they carry out. However, the lack of WIMP effects in their direct underground searches and at colliders can appeal to other forms of dark matter candidates. These candidates may be weakly interacting slim particles, superweakly interacting particles, or composite dark matter, in which new particles are bound. Their existence should lead to cosmological effects that can find probes in the astrophysical data. However, if composite dark matter contains stable electrically charged leptons and quarks bound by ordinary Coulomb interaction in elusive dark atoms, these charged constituents of dark atoms can be the subject of direct experimental test at the colliders. The models, predicting stable particles with charge ‑ 2 without stable particles with charges + 1 and ‑ 1 can avoid severe constraints on anomalous isotopes of light elements and provide solution for the puzzles of dark matter searches. In such models, the excessive ‑ 2 charged particles are bound with primordial helium in O-helium atoms, maintaining specific nuclear-interacting form of the dark matter. The successful development of composite dark matter scenarios appeals for experimental search for doubly charged constituents of dark atoms, making experimental search for exotic stable double charged particles experimentum crucis for dark atoms of composite dark matter.

Understanding Chemistry: Current and Possible

ERIC Educational Resources Information Center

Sanderson, R. T.

1976-01-01

Describes an instructional approach for teaching the cause-and-effect relationship between the qualities of atoms and the properties of their chemical compositions. Discusses atomic structure, ionization energies, homonuclear and heteronuclear bonding, and bond dissociation. (MLH)

System Concept for Remote Measurement of Asteroid Molecular Composition

NASA Astrophysics Data System (ADS)

Hughes, G. B.; Lubin, P. M.; Zhang, Q.; Brashears, T.; Cohen, A. N.; Madajian, J.

2016-12-01

We propose a method for probing the molecular composition of cold solar system targets (asteroids, comets, planets, moons) from a distant vantage, such as from a spacecraft orbiting the object. A directed energy beam is focused on the target. With sufficient flux, the spot temperature rises rapidly, and evaporation of surface materials occurs. The melted spot creates a high-temperature blackbody source, and ejected material creates a plume of surface materials in front of the spot. Molecular and atomic absorption of the blackbody radiation occurs within the ejected plume. Bulk composition of the surface material is investigated by using a spectrometer to view the heated spot through the ejected material. Our proposed method differs from technologies such as Laser-Induced Breakdown Spectroscopy (LIBS), which atomizes and ionizes materials in the target; scattered ions emit characteristic radiation, and the LIBS detector performs atomic composition analysis by observing emission spectra. Standoff distance for LIBS is limited by the strength of characteristic emission, and distances greater than 10 m are problematic. Our proposed method detects atomic and molecular absorption spectra in the plume; standoff distance is limited by the size of heated spot, and the plume opacity; distances on the order of tens of kilometers are immediately feasible. Simulations have been developed for laser heating of a rocky target, with concomitant evaporation. Evaporation rates lead to determination of plume density and opacity. Absorption profiles for selected materials are estimated from plume properties. Initial simulations of absorption profiles with laser heating show great promise for molecular composition analysis from tens of kilometers distance. This paper explores the feasibility a hypothetical mission that seeks to perform surface molecular composition analysis of a near-earth asteroid while the craft orbits the asteroid. Such a system has compelling potential benefit for solar system exploration.

Atomically thin layers of B-N-C-O with tunable composition.

PubMed

Ozturk, Birol; de-Luna-Bugallo, Andres; Panaitescu, Eugen; Chiaramonti, Ann N; Liu, Fangze; Vargas, Anthony; Jiang, Xueping; Kharche, Neerav; Yavuzcetin, Ozgur; Alnaji, Majed; Ford, Matthew J; Lok, Jay; Zhao, Yongyi; King, Nicholas; Dhar, Nibir K; Dubey, Madan; Nayak, Saroj K; Sridhar, Srinivas; Kar, Swastik

2015-07-01

In recent times, atomically thin alloys of boron, nitrogen, and carbon have generated significant excitement as a composition-tunable two-dimensional (2D) material that demonstrates rich physics as well as application potentials. The possibility of tunably incorporating oxygen, a group VI element, into the honeycomb sp(2)-type 2D-BNC lattice is an intriguing idea from both fundamental and applied perspectives. We present the first report on an atomically thin quaternary alloy of boron, nitrogen, carbon, and oxygen (2D-BNCO). Our experiments suggest, and density functional theory (DFT) calculations corroborate, stable configurations of a honeycomb 2D-BNCO lattice. We observe micrometer-scale 2D-BNCO domains within a graphene-rich 2D-BNC matrix, and are able to control the area coverage and relative composition of these domains by varying the oxygen content in the growth setup. Macroscopic samples comprising 2D-BNCO domains in a graphene-rich 2D-BNC matrix show graphene-like gate-modulated electronic transport with mobility exceeding 500 cm(2) V(-1) s(-1), and Arrhenius-like activated temperature dependence. Spin-polarized DFT calculations for nanoscale 2D-BNCO patches predict magnetic ground states originating from the B atoms closest to the O atoms and sizable (0.6 eV < E g < 0.8 eV) band gaps in their density of states. These results suggest that 2D-BNCO with novel electronic and magnetic properties have great potential for nanoelectronics and spintronic applications in an atomically thin platform.

Synthesis and the crystal and molecular structure of the germanium(IV) complex with propylene-1,3-diaminetetraacetic acid [Ge(Pdta)

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

Sergienko, V. S., E-mail: sergienko@igic.ras.ru; Martsinko, E. E.; Seifullina, I. I.

2015-09-15

The germanium(IV) complex with propylene-1,3-diaminetetraacetic acid (H{sub 4}Pdta) is studied by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction study reveals two crystallographically independent [Ge(Pdta)] molecules of similar structure. Both Ge atoms are octahedrally coordinated by four O atoms and two N atoms (at the cis positions) of the hexadentate pentachelate Pdta{sup 4–} ligand. An extended system of weak C—H···O hydrogen bonds connects complex molecules into a supramolecular 3D framework.

Synthesis and the crystal and molecular structure of the germanium(IV) complex with propylene-1,3-diaminetetraacetic acid [Ge( Pdta)

NASA Astrophysics Data System (ADS)

Sergienko, V. S.; Martsinko, E. E.; Seifullina, I. I.; Churakov, A. V.; Chebanenko, E. A.

2015-09-01

The germanium(IV) complex with propylene-1,3-diaminetetraacetic acid (H4 Pdta) is studied by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction study reveals two crystallographically independent [Ge( Pdta)] molecules of similar structure. Both Ge atoms are octahedrally coordinated by four O atoms and two N atoms (at the cis positions) of the hexadentate pentachelate Pdta 4- ligand. An extended system of weak С—Н···О hydrogen bonds connects complex molecules into a supramolecular 3D framework.

Process for functionalizing alkanes

DOEpatents

Bergman, Robert G.; Janowicz, Andrew H.; Periana, Roy A.

1988-01-01

Process for functionalizing saturated hydrocarbons comprising: (a) reacting said saturated hydrocarbons of the formula: R.sub.1 H wherein H represents a hydrogen atom; and R.sub.1 represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R.sub.2).sub.3 ]H.sub.2 wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical; Rh represents a rhodium atom; P represents a phosphorus atom; R.sub.2 represents a hydrocarbon radical; H represents a hydrogen atom, in the presence of ultraviolet radiation to form a hydridoalkyl complex of the formula: CpRh[P(R.sub.2).sub.3 ](R.sub.1)H (b) reacting said hydridoalkyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X''X'''X'''' or CHX'X''X''' wherein X', X'', X'", X"" represent halogens selected from bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e., ambient) to form a functional haloalkyl compound.

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach.

PubMed

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO(2) composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO(2) nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. This journal is © The Royal Society of Chemistry 2011

Composite materials flown on the Long Duration Exposure Facility

NASA Technical Reports Server (NTRS)

George, Pete E.; Dursch, Harry W.; Pippin, H. Gary

1995-01-01

Organic composite test specimens were flown on several LDEF experiments. Both bare and coated composites were flown. Atomic oxygen eroded bare composite material, with the resins being recessed at a greater rate than the fibers. Selected coating techniques protected the composite substrate in each case. Tensile and optical properties are reported for numerous specimens. Fiberglass and metal matrix composites were also flown.

Theoretical study of the structures and chemical ordering of CoPd nanoalloys supported on MgO(001)

NASA Astrophysics Data System (ADS)

Taran, Songul; Garip, Ali Kemal; Arslan, Haydar

2016-06-01

Metal nanoalloys on oxide surface are a widely studied topic in surface science and technology. In this study, the structures of CoPd nanoalloys adsorbed on MgO(001) have been searched by basin-hopping global optimization method within an atomistic model. Two different sizes (34 and 38 atom) have been considered for all compositions of CoPd/MgO(001) nanoalloys. Co and Pd atoms, for all the compositions, have cube-on-cube (001) epitaxy with substrate at interface. For both sizes, we have found that Pd rich composition nanoalloys have three layers, Co rich composition nanoalloys have four layers in morphology. Excess energy and second difference in energy analyzes have been performed to investigate the relative stability of nanoalloys with respect to their size and composition.

Differential dpa calculations with SPECTRA-PKA

NASA Astrophysics Data System (ADS)

Gilbert, M. R.; Sublet, J.-Ch.

2018-06-01

The processing code SPECTRA-PKA produces energy spectra of primary atomic recoil events (or primary knock-on atoms, PKAs) for any material composition exposed to an irradiation spectrum. Such evaluations are vital inputs for simulations aimed at understanding the evolution of damage in irradiated material, which is generated in cascade displacement events initiated by PKAs. These PKA spectra present the full complexity of the input (to SPECTRA-PKA) nuclear data-library evaluations of recoil events. However, the commonly used displacements per atom (dpa) measure, which is an integral measure over all possible recoil events of the displacement damage dose, is still widely used and has many useful applications - as both a comparative and correlative quantity. This paper describes the methodology employed that allows the SPECTRA-PKA code to evaluate dpa rates using the energy-dependent recoil (PKA) cross section data used for the PKA distributions. This avoids the need for integral displacement kerma cross sections and also provides new insight into the relative importance of different reaction channels (and associated different daughter residual and emitted particles) to the total integrated dpa damage dose. Results are presented for Fe, Ni, W, and SS316. Fusion dpa rates are compared to those in fission, highlighting the increased contribution to damage creation in the former from high-energy threshold reactions.

Resolving mass spectral overlaps in atom probe tomography by isotopic substitutions - case of TiSi15N.

PubMed

Engberg, David L J; Johnson, Lars J S; Jensen, Jens; Thuvander, Mattias; Hultman, Lars

2018-01-01

Mass spectral overlaps in atom probe tomography (APT) analyses of complex compounds typically limit the identification of elements and microstructural analysis of a material. This study concerns the TiSiN system, chosen because of severe mass-to-charge-state ratio overlaps of the 14 N + and 28 Si 2+ peaks as well as the 14 N 2 + and 28 Si + peaks. By substituting 14 N with 15 N, mass spectrum peaks generated by ions composed of one or more N atoms will be shifted toward higher mass-to-charge-state ratios, thereby enabling the separation of N from the predominant Si isotope. We thus resolve thermodynamically driven Si segregation on the nanometer scale in cubic phase Ti 1- x Si x 15 N thin films for Si contents 0.08 ≤ x ≤ 0.19 by APT, as corroborated by transmission electron microscopy. The APT analysis yields a composition determination that is in good agreement with energy dispersive X-ray spectroscopy and elastic recoil detection analyses. Additionally, a method for determining good voxel sizes for visualizing small-scale fluctuations is presented and demonstrated for the TiSiN system. Copyright © 2017 Elsevier B.V. All rights reserved.

Uranium and organic matters: use of pyrolysis-gas chromatography, carbon, hydrogen, and uranium contents to characterize the organic matter from sandstone-type deposits

USGS Publications Warehouse

Leventhal, Joel S.

1979-01-01

Organic matter seems to play an important role in the genesis of uranium deposits in sandstones in the western United States. Organic materials associated with ore from the Texas coastal plain, Tertiary basins of Wyoming, Grants mineral belt of New Mexico, and the Uravan mineral belt of Utah and Colorado vary widely in physical appearance and chemical composition. Partial characterization of organic materials is achieved by chemical analyses to determine atomic hydrogen-to-carbon (H/C) ratios and by gas chromatographic analyses to determine the molecular fragments evolved during stepwise pyrolysis. From the pyrolysis experiments the organic materials can be classified and grouped: (a) lignites from Texas and Wyoming and (b) hydrogen poor materials, from Grants and Uravan mineral belts and Wyoming; (c) naphthalene-containing materials from Grants mineral belt and Wyoming; and (d) complex and aromatic materials from Uravan, Grants and Wyoming. The organic materials analyzed have atomic H/C ratios that range from approximately 0.3 to at least 1.5. The samples with higher H/C ratios yield pyrolysis products that contain as many as 30 carbon atoms per molecule. Samples with low H/C ratios are commonly more uraniferous and yield mostly methane and low-molecular-weight gases during pyrolysis.

Electrochemical hydrogen storage alloys and batteries fabricated from Mg containing base alloys

DOEpatents

Ovshinsky, Stanford R.; Fetcenko, Michael A.

1996-01-01

An electrochemical hydrogen storage material comprising: (Base Alloy).sub.a M.sub.b where, Base Alloy is an alloy of Mg and Ni in a ratio of from about 1:2 to about 2:1, preferably 1:1; M represents at least one modifier element chosen from the group consisting of Co, Mn, Al, Fe, Cu, Mo, W, Cr, V, Ti, Zr, Sn, Th, Si, Zn, Li, Cd, Na, Pb, La, Mm, and Ca; b is greater than 0.5, preferably 2.5, atomic percent and less than 30 atomic percent; and a+b=100 atomic percent. Preferably, the at least one modifier is chosen from the group consisting of Co, Mn, Al, Fe, and Cu and the total mass of the at least one modifier element is less than 25 atomic percent of the final composition. Most preferably, the total mass of said at least one modifier element is less than 20 atomic percent of the final composition.

Interstellar Ice Chemistry: From Water to Complex Organics

NASA Astrophysics Data System (ADS)

Oberg, Karin I.; Fayolle, E.; Linnartz, H.; van Dishoeck, E.; Fillion, J.; Bertin, M.

2013-06-01

Molecular cloud cores, protostellar envelopes and protoplanetary disk midplanes are all characterized by freeze-out of atoms and molecules (other than H and H2) onto interstellar dust grains. On the grain surface, atom addition reactions, especially hydrogenation, are efficient and H2O forms readily from O, CH3OH from CO etc. The result is an icy mantle typically dominated by H2O, but also rich in CO2, CO, NH3, CH3OH and CH4. These ices are further processed through interactions with radiation, electrons and energetic particles. Because of the efficiency of the freeze-out process, and the complex chemistry that succeeds it, these icy grain mantles constitute a major reservoir of volatiles during star formation and are also the source of much of the chemical evolution observed in star forming regions. Laboratory experiments allow us to explore how molecules and radicals desorb, dissociate, diffuse and react in ices when exposed to different sources of energy. Changes in ice composition and structure is constrained using infrared spectroscopy and mass spectrometry. By comparing ice desorption, segregation, and chemistry efficiencies under different experimental conditions, we can characterize the basic ice processes, e.g. diffusion of different species, that underpin the observable changes in ice composition and structure. This information can then be used to predict the interstellar ice chemical evolution. I will review some of the key laboratory discoveries on ice chemistry during the past few years and how they have been used to predict and interpret astronomical observations of ice bands and gas-phase molecules associated with ice evaporation. These include measurements of thermal diffusion in and evaporation from ice mixtures, non-thermal diffusion efficiencies (including the recent results on frequency resolved UV photodesorption), and the expected temperature dependencies of the complex ice chemistry regulated by radical formation and diffusion. Based on these examples I will argue that the combination of laboratory experiments and observations is crucial to formulate and to test hypotheses on key processes that regulate the interstellar ice chemistry.

Defect engineering of complex semiconductor alloys: Cu2-2xMxO1-yXy

NASA Astrophysics Data System (ADS)

Lany, Stephan; Stevanovic, Vladan

2013-03-01

The electrical properties of semiconductors are generally controlled via doping, i.e., the incorporation of dilute concentrations of aliovalent impurity atoms, whereas the band structure properties (gap, effective masses, optical properties) are manipulated by alloying, i.e., the incorporation of much larger amounts of isovalent elements. Theoretical approaches usually address either doping or alloying, but rarely both problems at the same time. By combining defect supercell calculations, GW quasi-particle energy calculation, and thermodynamic modeling, we study the range of electrical and band structure properties accessible by alloying aliovalent cations (M = Mg, Zn, Cd) and isovalent anions (X = S, Se) in Cu2O. In order to extend dilute defect models to higher concentrations, we take into account the association/dissociation of defect pairs and complexes, as well as the composition dependence of the band gap and the band edge energies. Considering a composition window for the Cu2-2xMxO1-yXy alloys of 0 <= (x,y) <= 0.2, we predict a wide range of possible band gaps from 1.7 to 2.6 eV, and net doping concentrations between p = 1019 cm-3 and n = 1017cm-3, notably achieving type conversion from p- to n-type at Zn or Cd compositions around x = 0.1. This work is supported as part of the SunShot initiative by the U. S. Department of Energy, Office of Energy Efficiency and Renewable Energy under Contract No. DE-AC36-08GO28308 to NREL.

Production of complex organic molecules: H-atom addition versus UV irradiation

NASA Astrophysics Data System (ADS)

Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

2017-05-01

Complex organic molecules (COMs) have been identified in different environments in star-forming regions. Laboratory studies show that COMs form in the solid state, on icy grains, typically following a 'non-energetic' (atom-addition) or 'energetic' (UV-photon absorption) trigger. So far, such studies have been largely performed for single processes. Here, we present the first work that quantitatively investigates both the relative importance and the cumulative effect of '(non-)energetic' processing. We focus on astronomically relevant CO:CH3OH = 4:1 ice analogues exposed to doses relevant for the collapse stage of dense clouds. Hydrogenation experiments result in the formation of methyl formate (MF; HC(O)OCH3), glycolaldehyde (GA; HC(O)CH2OH) and ethylene glycol (EG; H2C(OH)CH2OH) at 14 K. The absolute abundances and the abundance fractions are found to be dependent on the H-atom/CO:CH3OH-molecule ratios and on the overall deposition rate. In the case that ices are exposed to UV photons only, several different COMs are found. Typically, the abundance fractions are 0.2 for MF, 0.3 for GA and 0.5 for EG as opposed to the values found in pure hydrogenation experiments without UV in which MF is largely absent: 0.0, 0.2-0.6 and 0.8-0.4, respectively. In experiments where both are applied, overall COM abundances drop to about half of those found in the pure UV irradiation experiments, but the composition fractions are very similar. This implies COM ratios can be used as a diagnostic tool to derive the processing history of an ice. Solid-state branching ratios derived here for GA and EG compare well with observations, while the MF case cannot be explained by solid-state conditions investigated here.

Exsolution as an Example of Complex-System Behavior

NASA Astrophysics Data System (ADS)

Mogk, D. W.; Dutrow, B. L.

2010-12-01

Exsolution in minerals is an important process that occurs in a wide range of mineral groups (e.g. alkali feldspars, pyroxenes, amphiboles, carbonates, oxides, sulfides) in response to changing physical conditions. Exsolution describes a physical process in which a mineral with an initially homogeneous solid solution separates into at least two distinct derivative minerals of disparate composition and is typically interpreted as the product of unmixing in response to lattice strain during slow cooling. Such a process is typically taught in introductory mineralogy and petrology courses, in part because exsolution textures can be readily observed in hand sample or thin section. Exsolution is typically represented on equilibrium binary phase diagrams (T-X), and compositions of the unmixed products can be used in geothermobarometry to calculate temperatures and pressures of initial equilibration or compositions of the unmixed products. Although central to course content, traditional approaches to teaching exsolution are largely descriptive, and do not address the underlying principles that drive this phenomenon: that is, dissipation of energy results in segregating and self-organizing behavior of the system. This process exemplifies complex-system behavior. We use perthite formation (i.e. exsolution in the alkali feldspar system) in a series of scaffolded exercises to teach and more completely demonstrate complex-system behavior. These exercises include the use of: 1) hand samples and a series of optical and TEM photomicrographs to display the scale invariance of perthite textures; 2) a puzzle activity in which a chessboard is used as an analog model of atomic positions and nickels and pennies are used to represent individual atoms (Na and K respectively); sequential moves to optimize contacts with similar coins approximates minimization of lattice energies and reveals a power-law relationship as the system becomes increasingly segregated as a function of time to create exsolution textures; 3) the NetLogo computer modeling program to demonstrate segregating behavior; 4) visualizations based on the binary alkali feldspar phase diagram to demonstrate changes to the state of the system over a range of temperatures, and 5) a series of follow-on thought questions. An interesting apparent paradox that our students should consider concerns the flow of mass and energy in natural systems. Commonly, we simply note that mass and energy typically flow down natural gradients (thermal, chemical potential) to attain a homogeneous equilibrium state; however, exsolution produces a segregated state of the system in the lowest energy configuration. Why? Complex-system behavior can be discovered in a wide range of geological phenomena such as exsolution, and could be explicitly identified throughout the geoscience curriculum as a mechanism to teach about interacting systems.

Microsolvation effect and hydrogen-bonding pattern of taurine-water TA-(H2O)n (n = 1-3) complexes.

PubMed

Dai, Yumei; Wang, Yuhua; Huang, Zhengguo; Wang, Hongke; Yu, Lei

2012-01-01

The microsolvation of taurine (TA) with one, two or three water molecules was investigated by a density functional theory (DFT) approach. Quantum theory of atoms in molecules (QTAIM) analyses were employed to elucidate the hydrogen bond (H-bond) interaction characteristics in TA-(H(2)O)(n) (n = 1-3) complexes. The results showed that the intramolecular H-bond formed between the hydroxyl and the N atom of TA are retained in most TA-(H(2)O)(n) (n = 1-3) complexes, and are strengthened via cooperative effects among multiple H-bonds from n = 1-3. A trend of proton transformation exists from the hydroxyl to the N atom, which finally results in the cleavage of the origin intramolecular H-bond and the formation of a new intramolecular H-bond between the amino and the O atom of TA. Therefore, the most stable TA-(H(2)O)(3) complex becomes a zwitterionic complex rather than a neutral type. A many-body interaction analysis showed that the major contributors to the binding energies for complexes are the two-body energies, while three-body energies and relaxation energies make significant contributions to the binding energies for some complexes, whereas the four-body energies are too small to be significant.

2-tert-Butyl-5-(2-pyridyl)-2H-tetrazole as a chelating ligand in the direct synthesis of novel Cu(II) and heterobimetallic Cu(II)/Mn(II) complexes.

PubMed

Mosalkova, Anastasiya P; Voitekhovich, Sergei V; Lyakhov, Alexander S; Ivashkevich, Ludmila S; Lach, Jochen; Kersting, Berthold; Gaponik, Pavel N; Ivashkevich, Oleg A

2013-02-28

For the first time, a representative of the 2,5-disubstituted tetrazoles, namely, 2-tert-butyl-5-(2-pyridyl)-2H-tetrazole (L), has been found to participate in oxidative dissolution of copper powder in homometalic systems Cu0–L–NH4X–DMSO (X = Cl, SCN, ClO4) and heterobimetallic ones Cu0–Mn(OAc)2–L–NH4OAc–Solv (Solv = DMSO, DMF), providing the formation of molecular homometallic complexes [CuL2Cl2] (1), [CuL2(SCN)2] (2), and [CuL2(H2O)](ClO4)2 (3), heterobimetallic complex [Cu2MnL2(OAc)6] (4) from DMF solution and its mixture with complex [Cu2MnL2(OAc)6]·2DMSO (5) from DMSO solution. Free ligand L and complexes 1–4 were characterized by elemental analysis, IR spectroscopy, thermal and X-ray single crystal analyses, whereas complex 5 was characterized by X-ray analysis only. Compounds 1–3 are mononuclear complexes, with chelating coordination mode of L via the tetrazole ring N4 and pyridine ring N7 atoms. Heterobimetallic complexes 4 and 5 possess trinuclear structures, with a linear Cu–Mn–Cu arrangement of the metal atoms, linked by the acetate anions; each copper(II) atom is decorated by a chelating unit of L via the tetrazole ring N1 and pyridine ring N7 atoms in complex 4, and via the N4, N7 atoms in complex 5. Temperature-dependent magnetic susceptibility measurements of complex 4 revealed a weak antiferromagnetic coupling between the paramagnetic copper(II) and manganese(II) ions (J = −2.5 cm(−1), g(Cu) = 2.25 and g(Mn) = 2.01), with magnetic exchange through the acetato bridges.

Effects of NOx on the molecular composition of secondary organic aerosol formed by the ozonolysis and photooxidation of α-pinene

NASA Astrophysics Data System (ADS)

Park, Jun-Hyun; Babar, Zaeem Bin; Baek, Sun Jong; Kim, Hyun Sik; Lim, Ho-Jin

2017-10-01

The molecular composition of secondary organic aerosol (SOA), obtained from the ozonolysis and photooxidation of α-pinene, was investigated using ultrahigh-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) in negative ion mode electrospray ionization (ESI). SOA formation was performed in an indoor smog chamber. The molecular formulae of individual species were identified on the basis of the measured ionic mass using guidelines, such as number of atoms, elemental ratios, and the nitrogen rule. In each of the SOAs obtained, 815-3501 monomeric and oligomeric (mainly dimeric) species were identified below m/z 800. From ozonolysis, mainly 95% of the typical oxygenated species (CHO) were detected, whereas from photooxidation under high NOx conditions, 32% of nitrogen-containing species (CHON) were detected. Several common intense species (e.g., C9H14O6, C10H14O6, C10H16O5, C17H26O7, C19H28O9, C10H15NO8, and C10H15NO9) could be listed as candidate tracers for the conventional tracers for α-pinene SOA. The increased percentage of CHON as a primary effect of NOx on the SOA composition evidently affected other physicochemical parameters, such as elemental ratios (i.e., O/C, H/C, and N/C), the double-bond equivalent (DBE), the carbon oxidation state (OSC), and the organic-mass-to-carbon ratio (OM/OC). The O/C and OM/OC for CHON were greater than those observed for CHO, indicating that nitrogen preferentially exists in the oxidized form (e.g., -ONO2). The complexity of oligomerization was observed in DBE and OM/OC according to the number of carbon atoms.

Product ion isotopologue pattern: A tool to improve the reliability of elemental composition elucidations of unknown compounds in complex matrices.

PubMed

Kaufmann, A; Walker, S; Mol, G

2016-04-15

Elucidation of the elemental compositions of unknown compounds (e.g., in metabolomics) generally relies on the availability of accurate masses and isotopic ratios. This study focuses on the information provided by the abundance ratio within a product ion pair (monoisotopic versus the first isotopic peak) when isolating and fragmenting the first isotopic ion (first isotopic mass spectrum) of the precursor. This process relies on the capability of the quadrupole within the Q Orbitrap instrument to isolate a very narrow mass window. Selecting only the first isotopic peak (first isotopic mass spectrum) leads to the observation of a unique product ion pair. The lighter ion within such an isotopologue pair is monoisotopic, while the heavier ion contains a single carbon isotope. The observed abundance ratio is governed by the percentage of carbon atoms lost during the fragmentation and can be described by a hypergeometric distribution. The observed carbon isotopologue abundance ratio (product ion isotopologue pattern) gives reliable information regarding the percentage of carbon atoms lost in the fragmentation process. It therefore facilitates the elucidation of the involved precursor and product ions. Unlike conventional isotopic abundances, the product ion isotopologue pattern is hardly affected by isobaric interferences. Furthermore, the appearance of these pairs greatly aids in cleaning up a 'matrix-contaminated' product ion spectrum. The product ion isotopologue pattern is a valuable tool for structural elucidation. It increases confidence in results and permits structural elucidations for heavier ions. This tool is also very useful in elucidating the elemental composition of product ions. Such information is highly valued in the field of multi-residue analysis, where the accurate mass of product ions is required for the confirmation process. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Development of new portable miniaturize solid phase microextraction of silver-APDC complex using micropipette tip in-syringe system couple with electrothermal atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Naeemullah; Kazi, Tasneem Gul; Afridi, Hassan Imran; Shah, Faheem; Arain, Sadaf Sadia; Arain, Salma Aslam; Panhwar, Abdul Haleem; Arain, Mariam Shahzadi; Samoon, Muhammad Kashif

2016-02-01

An innovative and simple miniaturized solid phase microextraction (M-SPME) method, was developed for preconcentration and determination of silver(I) in the fresh and waste water samples. For M-SPME, a micropipette tip packed with activated carbon cloth (ACC) as sorbent, in a syringe system. The size, morphology and elemental composition of ACC before and after adsorption of analyte have been characterized by scanning electron microscopy and energy dispersive spectroscopy. The sample solution treated with a complexing reagent, ammonium pyrrolidine dithiocarbamate (APDC), was drawn into the syringe filled with ACC and dispensed manually for 2 to 10 aspirating/dispensing cycle. Then the Ag- complex sorbed on the ACC in micropipette was quantitatively eluted by drawing and dispensing of different concentrations of acids for 2 to 5 aspirating/dispensing cycles. The extracted Ag ions with modifier were injected directly into the electrothermal atomic absorption spectrometry for analysis. The influence of different variables on the extraction efficiency, including the concentration of ligand, pH, sample volume, eluent type, concentration and volume was investigated. Validity and accuracy of the developed method was checked by the standard addition method. Reliability of the proposed methodology was checked by the relative standard deviation (%RSD), which was found to be < 5%. Under the optimized experimental variables, the limits of detection (LOD) and enhancement factors (EF), were obtained to be 0.86 ng L- 1 and 120, respectively. The proposed method was successfully applied for the determination of trace levels of silver ions in fresh and waste water samples.

Formation of Glycerol through Hydrogenation of CO Ice under Prestellar Core Conditions

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

Fedoseev, G.; Chuang, K.-J.; Qasim, D.

Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, i.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic-ray-induced UV photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via nonenergetic atom addition reactions between accreting H atoms and CO molecules,more » a process that dominates surface chemistry during the “CO freeze-out stage” in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol—HOCH{sub 2}CH(OH)CH{sub 2}OH—a three-carbon-bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical–radical and radical–molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde—HOCH{sub 2}CH(OH)CHO—is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars.« less

Building Complex Kondo Impurities by Manipulating Entangled Spin Chains.

PubMed

Choi, Deung-Jang; Robles, Roberto; Yan, Shichao; Burgess, Jacob A J; Rolf-Pissarczyk, Steffen; Gauyacq, Jean-Pierre; Lorente, Nicolás; Ternes, Markus; Loth, Sebastian

2017-10-11

The creation of molecule-like structures in which magnetic atoms interact controllably is full of potential for the study of complex or strongly correlated systems. Here, we create spin chains in which a strongly correlated Kondo state emerges from magnetic coupling of transition-metal atoms. We build chains up to ten atoms in length by placing Fe and Mn atoms on a Cu 2 N surface with a scanning tunneling microscope. The atoms couple antiferromagnetically via superexchange interaction through the nitrogen atom network of the surface. The emergent Kondo resonance is spatially distributed along the chain. Its strength can be controlled by mixing atoms of different transition metal elements and manipulating their spatial distribution. We show that the Kondo screening of the full chain by the electrons of the nonmagnetic substrate depends on the interatomic entanglement of the spins in the chain, demonstrating the prerequisites to build and probe spatially extended strongly correlated nanostructures.

Detection of percolating paths in polyhedral segregated network composites using electrostatic force microscopy and conductive atomic force microscopy

NASA Astrophysics Data System (ADS)

Waddell, J.; Ou, R.; Capozzi, C. J.; Gupta, S.; Parker, C. A.; Gerhardt, R. A.; Seal, K.; Kalinin, S. V.; Baddorf, A. P.

2009-12-01

Composite specimens possessing polyhedral segregated network microstructures require a very small amount of nanosize filler, <1 vol %, to reach percolation because percolation occurs by accumulation of the fillers along the edges of the deformed polymer matrix particles. In this paper, electrostatic force microscopy (EFM) and conductive atomic force microscopy (C-AFM) were used to confirm the location of the nanosize fillers and the corresponding percolating paths in polymethyl methacrylate/carbon black composites. The EFM and C-AFM images revealed that the polyhedral polymer particles were coated with filler, primarily on the edges as predicted by the geometric models provided.

Effects of Atomic-Scale Structure on the Fracture Properties of Amorphous Carbon - Carbon Nanotube Composites

NASA Technical Reports Server (NTRS)

Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.

2015-01-01

The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT composites.

The Atom and the Ocean, Understanding the Atom Series.

ERIC Educational Resources Information Center

Hull, E. W. Seabrook

Included is a brief description of the characteristics of the ocean, its role as a resource for food and minerals, its composition and its interactions with land and air. The role of atomic physics in oceanographic exploration is illustrated by the use of nuclear reactors to power surface and submarine research vessels and the design and use of…

Regulation of the protein-conducting channel by a bound ribosome

PubMed Central

Gumbart, James; Trabuco, Leonardo G.; Schreiner, Eduard; Villa, Elizabeth; Schulten, Klaus

2009-01-01

Summary During protein synthesis, it is often necessary for the ribosome to form a complex with a membrane-bound channel, the SecY/Sec61 complex, in order to translocate nascent proteins across a cellular membrane. Structural data on the ribosome-channel complex are currently limited to low-resolution cryo-electron microscopy maps, including one showing a bacterial ribosome bound to a monomeric SecY complex. Using that map along with available atomic-level models of the ribosome and SecY, we have determined, through molecular dynamics flexible fitting (MDFF), an atomic-resolution model of the ribosome-channel complex. We characterized computationally the sites of ribosome-SecY interaction within the complex and determined the effect of ribosome binding on the SecY channel. We also constructed a model of a ribosome in complex with a SecY dimer by adding a second copy of SecY to the MDFF-derived model. The study involved 2.7-million-atom simulations over altogether nearly 50 ns. PMID:19913480

Synthesis and Fluorescence Properties of Structurally Characterized Heterobimetalic Cu(II)⁻Na(I) Bis(salamo)-Based Complex Bearing Square Planar, Square Pyramid and Triangular Prism Geometries of Metal Centers.

PubMed

Dong, Xiu-Yan; Zhao, Qing; Wei, Zhi-Li; Mu, Hao-Ran; Zhang, Han; Dong, Wen-Kui

2018-04-25

A novel heterotrinuclear complex [Cu₂(L)Na( µ -NO₃)]∙CH₃OH∙CHCl₃ derived from a symmetric bis(salamo)-type tetraoxime H₄L having a naphthalenediol unit, was prepared and structurally characterized via means of elemental analyses, UV-Vis, FT-IR, fluorescent spectra and single-crystal X-ray diffraction. The heterobimetallic Cu(II)⁻Na(I) complex was acquired via the reaction of H₄L with 2 equivalents of Cu(NO₃)₂·2H₂O and 1 equivalent of NaOAc. Clearly, the heterotrinuclear Cu(II)⁻Na(I) complex has a 1:2:1 ligand-to-metal (Cu(II) and Na(I)) ratio. X-ray diffraction results exhibited the different geometric behaviors of the Na(I) and Cu(II) atoms in the heterotrinuclear complex; the both Cu(II) atoms are sited in the N₂O₂ coordination environments of fully deprotonated (L) 4− unit. One Cu(II) atom (Cu1) is five-coordinated and possesses a geometry of slightly distorted square pyramid, while another Cu(II) atom (Cu2) is four-coordination possessing a square planar coordination geometry. Moreover, the Na(I) atom is in the O₆ cavity and adopts seven-coordination with a geometry of slightly distorted single triangular prism. In addition, there are abundant supramolecular interactions in the Cu(II)⁻Na(I) complex. The fluorescence spectra showed the Cu(II)⁻Na(I) complex possesses a significant fluorescent quenching and exhibited a hypsochromic-shift compared with the ligand H₄L.

Structural evolution and atomic dynamics in Ni-Nb metallic glasses: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Xu, T. D.; Wang, X. D.; Zhang, H.; Cao, Q. P.; Zhang, D. X.; Jiang, J. Z.

2017-10-01

The composition and temperature dependence of static and dynamic structures in NixNb1-x (x = 50-70 at. %) were systematically studied using molecular dynamics with a new-released semi-empirical embedded atom method potential by Mendelev. The calculated pair correlation functions and the structure factor match well with the experimental data, demonstrating the reliability of the potential within relatively wide composition and temperature ranges. The local atomic structures were then characterized by bond angle distributions and Voronoi tessellation methods, demonstrating that the icosahedral ⟨0,0,12,0⟩ is only a small fraction in the liquid state but increases significantly during cooling and becomes dominant at 300 K. The most abundant clusters are identified as ⟨0,0,12,0⟩ and distorted icosahedron ⟨0,2,8,2⟩. The large fraction of these two clusters hints that the relatively good glass forming ability is near the eutectic point. Unlike Cu-Zr alloys, both the self-diffusion coefficient and shear viscosity are insensitive to compositions upon cooling in Ni-Nb alloys. The breakdown of the Stokes-Einstein relation happens at around 1.6Tg (Tg: glass transition temperature). In the amorphous state, the solid and liquid-like atoms can be distinguished based on the Debye-Waller factor ⟨u2⟩. The insensitivity of the dynamic properties of Ni-Nb alloys to compositions may result from the relatively simple solidification process in the phase diagram, in which only one eutectic point exists in the studied composition range.

New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

NASA Astrophysics Data System (ADS)

Mudsainiyan, R. K.; Jassal, A. K.; Chawla, S. K.

2015-10-01

A mesoporous 3D polymeric complex (I) having formula {[Zr(IV)O-μ3-(EDTA)Fe(III)OH]·H2O}n has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of -OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (336·454·530)·(36). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and -OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n-π* transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N2 (SBET=8.7693 m2/g) and a maximum amount of H2 (high surface area=1044.86 m2/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. -7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex.

Highly atom-economic synthesis of graphene/Mn3O4 hybrid composites for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Jiangying, Qu; Feng, Gao; Quan, Zhou; Zhiyu, Wang; Han, Hu; Beibei, Li; Wubo, Wan; Xuzhen, Wang; Jieshan, Qiu

2013-03-01

A highly atom-economic procedure for the preparation of reduced graphene oxide/Mn3O4 (rGO/Mn3O4) composites is reported. Pristine graphene oxide/manganese sulfate (GO/MnSO4) suspension produced by modified Hummers method is utilized with high efficiency, which has been in situ converted into GO/Mn3O4 hybrid composite by air oxidation, then into rGO/Mn3O4 composite by means of dielectric barrier discharge (DBD) plasma-assisted deoxygenation. The Mn3O4 content of the rGO/Mn3O4 composites can be readily tailored. It is observed that Mn3O4 nanoparticles of 15-24 nm are well-dispersed on graphene sheets with Mn3O4 loading as high as 90%. The specific capacitance of the as-prepared rGO/Mn3O4 hybrids with 90% Mn3O4 reaches 193 F g-1 when employed as the electrode material in neutral Na2SO4 electrolyte solutions (76 F g-1 for pristine graphene and 95 F g-1 for pure Mn3O4), which indicates the positive synergetic effects from both graphene and attached Mn3O4. The method developed in this study should offer a new technique for the large scale and highly atom-economic production of graphene/MnOx composites for many applications.

Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

DOEpatents

Anderson, Iver E.; Lograsso, Barbara K.; Ellis, Timothy W.

1994-01-01

A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material.

Nickel(II) and copper(II) complexes of N,N-dialkyl-N‧-3-chlorobenzoylthiourea: Synthesis, characterization, crystal structures, Hirshfeld surfaces and antimicrobial activity

NASA Astrophysics Data System (ADS)

Binzet, Gun; Gumus, Ilkay; Dogen, Aylin; Flörke, Ulrich; Kulcu, Nevzat; Arslan, Hakan

2018-06-01

We synthesized four new N,N-dialkyl-N‧-3-chlorobenzoylthiourea ligands (Alkyl: Dimethyl, diethyl, di-n-propyl and di-n-butyl) and their metal complexes with copper and nickel atoms. The structure of all synthesized compounds was fully characterized by physicochemical, spectroscopic and single crystal X-ray diffraction analysis techniques. The physical, spectral and analytical data of the newly synthesized metal complexes have shown the formation of 1:2 (metal:ligand) ratio. The benzoylthiourea ligands coordinate with metal atoms through oxygen and sulphur atoms. The metal atoms are in slightly distorted square-planar coordination geometry in Ni(II) or Cu(II) complex. Two oxygen and two sulphur atoms are mutually cis to each other in Ni(II) or Cu(II) complex. The intermolecular contacts in the compounds, which are HL1 and HL3, were examined by Hirshfeld surfaces and fingerprint plots using the data obtained from X-ray single crystal diffraction measurement. Besides these, their antimicrobial activities against Gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus, Streptococcus pyogenes and Enterococcus faecalis) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and anti-yeast activity (Candida glabrata, Candida parapsilosis and Candida albicans) were investigated. This exhibited some promising results towards testing organism. Among all the compounds, Ni(L1)2 complex showed high activity against Bacillus subtilis with MIC values at 7.81 μg/mL.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

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

Yan, Ling -Hao; Wu, Rong -Ting; Bao, De -Liang

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H 2Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H 2Nc molecules and formed Fe-H 2Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H 2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform sizemore » and adsorbed dispersively at the interstitial positions of Fe-H 2Nc complex monolayer. Furthermore, the H 2Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.« less

Compositionally Dependent Nonlinear Optical Bandgap Behavior of Mixed Anodic Oxides in Niobium-Titanium System.

PubMed

Bleckenwegner, Petra; Mardare, Cezarina Cela; Cobet, Christoph; Kollender, Jan Philipp; Hassel, Achim Walter; Mardare, Andrei Ionut

2017-02-13

Optical bandgap mapping of Nb-Ti mixed oxides anodically grown on a thin film parent metallic combinatorial library was performed via variable angle spectroscopic ellipsometry (VASE). A wide Nb-Ti compositional spread ranging from Nb-90 at.% Ti to Nb-15 at.% Ti deposited by cosputtering was used for this purpose. The Nb-Ti library was stepwise anodized at potentials up to 10 V SHE, and the anodic oxides optical properties were mapped along the Nb-Ti library with 2 at.% resolution. The surface dissimilarities along the Nb-Ti compositional gradient were minimized by tuning the deposition parameters, thus allowing a description of the mixed Nb-Ti oxides based on a single Tauc-Lorentz oscillator for data fitting. Mapping of the Nb-Ti oxides optical bandgap along the entire compositional spread showed a clear deviation from the linear model based on mixing individual Nb and Ti electronegativities proportional to their atomic fractions. This is attributed to the strong amorphization and an in-depth compositional gradient of the mixed oxides. A systematic optical bandgap decrease toward values as low as 2.0 eV was identified at approximately 50 at.% Nb. Mixing of Nb 2 O 5 and TiO 2 with both amorphous and crystalline phases is concluded, whereas the possibility of complex Nb a Ti b O y oxide formation during anodization is unlikely.

Faceting, composition and crystal phase evolution in III-V antimonide nanowire heterostructures revealed by combining microscopy techniques.

PubMed

Xu, Tao; Dick, Kimberly A; Plissard, Sébastien; Nguyen, Thanh Hai; Makoudi, Younes; Berthe, Maxime; Nys, Jean-Philippe; Wallart, Xavier; Grandidier, Bruno; Caroff, Philippe

2012-03-09

III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100-x Al x Metallic Glasses

NASA Astrophysics Data System (ADS)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-03-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated <0, 0, 12, 0> and 13-coordinated <0, 1, 10, 2>) and by playing a main role in the structure stability of the Ti-Al MGs.

Composition formulas of binary eutectics

PubMed Central

Ma, Y. P.; Dong, D. D.; Dong, C.; Luo, L. J.; Wang, Q.; Qiang, J. B.; Wang, Y. M.

2015-01-01

The present paper addresses the long-standing composition puzzle of eutectic points by introducing a new structural tool for the description of short-range-order structural unit, the cluster-plus-glue-atom model. In this model, any structure is dissociated into a 1st-neighbor cluster and a few glue atoms between the clusters, expressed by a cluster formula [cluster]gluex. This model is applied here to establish the structural model for eutectic liquids, assuming that a eutectic liquid consist of two subunits issued from the relevant eutectic phases, each being expressed by the cluster formula for ideal metallic glasses, i.e., [cluster](glue atom)1 or 3. A structural unit is then composed of two clusters from the relevant eutectic phases plus 2, 4, or 6 glue atoms. Such a dual cluster formulism is well validated in all boron-containing (except those located by the extreme phase diagram ends) and in some commonly-encountered binary eutectics, within accuracies below 1 at.%. The dual cluster formulas vary extensively and are rarely identical even for eutectics of close compositions. They are generally formed with two distinctly different cluster types, with special cluster matching rules such as cuboctahedron plus capped trigonal prism and rhombidodecahedron plus octahedral antiprism. PMID:26658618

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100- x Al x Metallic Glasses

NASA Astrophysics Data System (ADS)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-06-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated <0, 0, 12, 0> and 13-coordinated <0, 1, 10, 2>) and by playing a main role in the structure stability of the Ti-Al MGs.

Advances in Understanding of Swift Heavy-Ion Tracks in Complex Ceramics

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

Lang, Maik; Devanathan, Ram; Toulemonde, Marcel

2015-02-01

Tracks produced by swift heavy ions in ceramics are of interest for fundamental science as well as for applications covering different fields such as nanotechnology or fission-track dating of minerals. In the case of pyrochlores with general formula A2B2O7, the track structure and radiation sensitivity shows a clear dependence on the composition. Ion irradiated Gd2Zr2O7, e.g., retains its crystallinity while amorphous tracks are produced in Gd2Ti2O7. Tracks in Ti-containing compositions have a complex morphology consisting of an amorphous core surrounded by a shell of a disordered, defect-fluorite phase. The size of the amorphous core decreases with decreasing energy loss andmore » with increasing Zr content, while the shell thickness seems to be similar over a wide range of energy loss values. The large data set and the complex track structure has made pyrochlore an interesting model system for a general theoretical description of track formation including thermal spike calculations (providing the spatial and temporal evolution of temperature around the ion trajectory) and molecular dynamics (MD) simulations (describing the response of the atomic system).Recent MD advances consider the sudden temperature increase by inserting data from the thermal spike. The combination allows the reproduction of the core-shell track characteristic and sheds light on the early stages of track formation including recrystallization of the molten material produced by the thermal spike.« less

Simulation of field-induced molecular dissociation in atom-probe tomography: Identification of a neutral emission channel

NASA Astrophysics Data System (ADS)

Zanuttini, David; Blum, Ivan; Rigutti, Lorenzo; Vurpillot, François; Douady, Julie; Jacquet, Emmanuelle; Anglade, Pierre-Matthieu; Gervais, Benoit

2017-06-01

We investigate the dynamics of dicationic metal-oxide molecules under large electric-field conditions, on the basis of ab initio calculations coupled to molecular dynamics. Applied to the case of ZnO2 + in the field of atom probe tomography (APT), our simulation reveals the dissociation into three distinct exit channels. The proportions of these channels depend critically on the field strength and on the initial molecular orientation with respect to the field. For typical field strength used in APT experiments, an efficient dissociation channel leads to emission of neutral oxygen atoms, which escape detection. The calculated composition biases and their dependence on the field strength show remarkable consistency with recent APT experiments on ZnO crystals. Our work shows that bond breaking in strong static fields may lead to significant neutral atom production, and therefore to severe elemental composition biases in measurements.

Correlating structural dynamics and catalytic activity of AgAu nanoparticles with ultrafast spectroscopy and all-atom molecular dynamics simulations.

PubMed

Ferbonink, G F; Rodrigues, T S; Dos Santos, D P; Camargo, P H C; Albuquerque, R Q; Nome, R A

2018-05-29

In this study, we investigated hollow AgAu nanoparticles with the goal of improving our understanding of the composition-dependent catalytic activity of these nanoparticles. AgAu nanoparticles were synthesized via the galvanic replacement method with controlled size and nanoparticle compositions. We studied extinction spectra with UV-Vis spectroscopy and simulations based on Mie theory and the boundary element method, and ultrafast spectroscopy measurements to characterize decay constants and the overall energy transfer dynamics as a function of AgAu composition. Electron-phonon coupling times for each composition were obtained from pump-power dependent pump-probe transients. These spectroscopic studies showed how nanoscale surface segregation, hollow interiors and porosity affect the surface plasmon resonance wavelength and fundamental electron-phonon coupling times. Analysis of the spectroscopic data was used to correlate electron-phonon coupling times to AgAu composition, and thus to surface segregation and catalytic activity. We have performed all-atom molecular dynamics simulations of model hollow AgAu core-shell nanoparticles to characterize nanoparticle stability and equilibrium structures, besides providing atomic level views of nanoparticle surface segregation. Overall, the basic atomistic and electron-lattice dynamics of core-shell AgAu nanoparticles characterized here thus aid the mechanistic understanding and performance optimization of AgAu nanoparticle catalysts.

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

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

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 –4. Heteroatomic molecules, especially those containing multiple S and N atoms, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

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

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg-DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 -4. Heteroatomic molecules, especially those containing multiple S and N atoms, were found to bemore » among the most important in forming strong complexes with Hg. Major Hg-DOM complexes of C10H21N2S4Hg+ and C8H17N2S4Hg+ were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. These findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg-DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE PAGES

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.; ...

2016-12-22

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 –4. Heteroatomic molecules, especially those containing multiple S and N atoms, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Making More-Complex Molecules Using Superthermal Atom/Molecule Collisions

NASA Technical Reports Server (NTRS)

Shortt, Brian; Chutjian, Ara; Orient, Otto

2008-01-01

A method of making more-complex molecules from simpler ones has emerged as a by-product of an experimental study in outer-space atom/surface collision physics. The subject of the study was the formation of CO2 molecules as a result of impingement of O atoms at controlled kinetic energies upon cold surfaces onto which CO molecules had been adsorbed. In this study, the O/CO system served as a laboratory model, not only for the formation of CO2 but also for the formation of other compounds through impingement of rapidly moving atoms upon molecules adsorbed on such cold interstellar surfaces as those of dust grains or comets. By contributing to the formation of increasingly complex molecules, including organic ones, this study and related other studies may eventually contribute to understanding of the origins of life.

Silver clusters encapsulated in C{sub 60}: A density functional study

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

Dhiman, Shobhna; Kumar, Ranjan; Dharamvir, Keya

2015-08-28

We explore the possibility of formation of endohedral complexes of Ag{sub n} atoms (n=1-9) inside C{sub 60} molecule using density functional theory and molecular dynamics. The obtained results reveal that Ag{sub n} (n=8) atoms can form stable complexes with the C{sub 60} molecule. Encapsulation of large number of Ag{sub n} atoms (n>8) make C{sub 60} cage instable, showing distortion of cage. Binding energy/atom increases with the number of Ag atoms up to n=4, after that it increases. Ionization potential decreases till n=4 and then increases, electron affinity increases till n=4 and then shows oscillatory nature as a function of Agmore » atoms inside the cage. Homo –Lumo gap shows no systematic pattern. Our results agreed well with the data available.« less

[Relationship between the culture medium and the fatty acid composition of diphtheria and non-pathogenic corynebacteria].

PubMed

Vasiurenko, Z P; Siniak, K M

1977-04-01

The gasochromatic method was applied to the study of the cellular fatty acids composition in diphtheria and nonpathogenic corynebacteria (diphtheroids and psendo diptheria bacillus). Marked differences in the content of unsaturated fatty acids were revealed in them. Thus, palmito leic acid served the preponderant unsaturated fatty acid in Corynebacteria diphtheriae, and unsaturated fatty acids with 18 carbon atoms (octadeconoic and linoleic)--in nonpathogenic corynebacteria. The mentioned changes permit use this sign as differential. When grown on Loeffler's medium all the corynebacteria under study had a similar fatty acid composition characterized by the prevalence of unsaturated fatty acids with 18 carbon atoms. On the basis of studying the fatty acid spectrum of the nutrient media used it is supposed that one of the factors determining the revealed dependence of the corynebacterial fatty acid composition on the culture medium was the fatty acid composition of the latter.

Irradiation-enhanced α' precipitation in model FeCrAl alloys

DOE PAGES

Edmondson, Philip D.; Briggs, Samuel A.; Yamamoto, Yukinori; ...

2016-02-17

We have irradiated the model FeCrAl alloys with varying compositions (Fe(10–18)Cr(10–6)Al at.%) with a neutron at ~ 320 to damage levels of ~ 7 displacements per atom (dpa) to investigate the compositional influence on the formation of irradiation-induced Cr-rich α' precipitates using atom probe tomography. In all alloys, significant number densities of these precipitates were observed. Cluster compositions were investigated and it was found that the average cluster Cr content ranged between 51.1 and 62.5 at.% dependent on initial compositions. Furthermore, this is significantly lower than the Cr-content of α' in binary FeCr alloys. As a result, significant partitioning ofmore » the Al from the α' precipitates was also observed.« less

Novel Organotin(IV) Schiff Base Complexes with Histidine Derivatives: Synthesis, Characterization, and Biological Activity

PubMed Central

Garza-Ortiz, Ariadna; Camacho-Camacho, Carlos; Sainz-Espuñes, Teresita; Rojas-Oviedo, Irma; Gutiérrez-Lucas, Luis Raúl; Gutierrez Carrillo, Atilano; Vera Ramirez, Marco A.

2013-01-01

Five novel tin Schiff base complexes with histidine analogues (derived from the condensation reaction between L-histidine and 3,5-di-tert-butyl-2-hydroxybenzaldehyde) have been synthesized and characterized. Characterization has been completed by IR and high-resolution mass spectroscopy, 1D and 2D solution NMR (1H, 13C  and 119Sn), as well as solid state 119Sn NMR. The spectroscopic evidence shows two types of structures: a trigonal bipyramidal stereochemistry with the tin atom coordinated to five donating atoms (two oxygen atoms, one nitrogen atom, and two carbon atoms belonging to the alkyl moieties), where one molecule of ligand is coordinated in a three dentate fashion. The second structure is spectroscopically described as a tetrahedral tin complex with four donating atoms (one oxygen atom coordinated to the metal and three carbon atoms belonging to the alkyl or aryl substituents), with one molecule of ligand attached. The antimicrobial activity of the tin compounds has been tested against the growth of bacteria in vitro to assess their bactericidal properties. While pentacoordinated compounds 1, 2, and 3 are described as moderate effective to noneffective drugs against both Gram-positive and Gram-negative bacteria, tetracoordinated tin(IV) compounds 4 and 5 are considered as moderate effective and most effective compounds, respectively, against the methicillin-resistant Staphylococcus aureus strains (Gram-positive). PMID:23864839

Two novel mixed-ligand complexes containing organosulfonate ligands.

PubMed

Li, Mingtian; Huang, Jun; Zhou, Xuan; Fang, Hua; Ding, Liyun

2008-07-01

The structures reported herein, viz. bis(4-aminonaphthalene-1-sulfonato-kappaO)bis(4,5-diazafluoren-9-one-kappa(2)N,N')copper(II), [Cu(C(10)H(8)NO(3)S)(2)(C(11)H(6)N(2)O)(2)], (I), and poly[[[diaquacadmium(II)]-bis(mu-4-aminonaphthalene-1-sulfonato)-kappa(2)O:N;kappa(2)N:O] dihydrate], {[Cd(C(10)H(8)NO(3)S)(2)(H(2)O)(2)].2H(2)O}(n), (II), are rare examples of sulfonate-containing complexes where the anion does not fulfill a passive charge-balancing role, but takes an active part in coordination as a monodentate and/or bridging ligand. Monomeric complex (I) possesses a crystallographic inversion center at the Cu(II) atom, and the asymmetric unit contains one-half of a Cu atom, one complete 4-aminonaphthalene-1-sulfonate (ans) ligand and one 4,5-diazafluoren-9-one (DAFO) ligand. The Cu(II) atom has an elongated distorted octahedral coordination geometry formed by two O atoms from two monodentate ans ligands and by four N atoms from two DAFO molecules. Complex (II) is polymeric and its crystal structure is built up by one-dimensional chains and solvent water molecules. Here also the cation (a Cd(II) atom) lies on a crystallographic inversion center and adopts a slightly distorted octahedral geometry. Each ans anion serves as a bridging ligand linking two Cd(II) atoms into one-dimensional infinite chains along the [010] direction, with each Cd(II) center coordinated by four ans ligands via O and N atoms and by two aqua ligands. In both structures, there are significant pi-pi stacking interactions between adjacent ligands and hydrogen bonds contribute to the formation of two- and three-dimensional networks.

Influence of beta instabilities on the early stages of nucleation and growth of alpha in beta titanium alloys

NASA Astrophysics Data System (ADS)

Nag, Soumya

Microstructural evolution in beta Titanium alloys is an important factor that governs the properties exhibited by them. Intricate understanding of complex phase transformations in these alloys is vital to tailor their microstructures and in turn their properties to our advantage. One such important subject of study is the nucleation and growth of alpha precipitates triggered by the compositional instabilities in the beta matrix, instilled in them during non equilibrium heat treatments. The present work is an effort to investigate such a phenomenon. Here studies have been conducted primarily on two different beta-Titanium alloys of commercial relevance- Ti5553 (Ti-5Al-5Mo-5V-3Cr-0.5Fe), an alloy used in the aerospace industry for landing gear applications and, TNZT (Ti-35Nb-7Zr-5Ta), a potential load bearing orthopedic implant alloy. Apart from the effect of thermal treatment on these alloys, the focus of this work is to study the interplay between different alpha and beta stabilizers present in them. For this, advanced nano-scale characterization tools such as High Resolution STEM, High Resolution TEM, EFTEM and 3D Atom Probe have been used to determine the structure, distribution and composition of the non equilibrium instabilities such as beta' and o, and also to investigate the subsequent nucleation of stable alpha. Thus in this work, very early stages of phase separation via spinodal decomposition and second phase nucleation in titanium alloys are successfully probed at an atomic resolution. For the first time, atomically resolved HRSTEM 'Z'-contrast image is recorded showing modulated structures within the as-quenched beta matrix. Also in the same condition HRTEM results showed the presence of nanoscale alpha regions. These studies are revalidated by conventional selected area diffraction and 3D atom probe reconstruction results. Also TEM dark field and selected are diffraction studies are conducted to understand the effect of quenching and subsequent aging of o precipitates. Using 3D atom probe tomography, the elemental partitioning involved in coarsening of o is investigated in detail. Finally by performing a series of well planned heat treatments, an effort is made to reason out the influence of these instabilities on the morphology, volume fraction and nucleation site of alpha.

System and process for dissolution of solids

DOEpatents

Liezers, Martin; Farmer, III, Orville T.

2017-10-10

A system and process are disclosed for dissolution of solids and "difficult-to-dissolve" solids. A solid sample may be ablated in an ablation device to generate nanoscale particles. Nanoparticles may then swept into a coupled plasma device operating at atmospheric pressure where the solid nanoparticles are atomized. The plasma exhaust may be delivered directly into an aqueous fluid to form a solution containing the atomized and dissolved solids. The composition of the resulting solution reflects the composition of the original solid sample.

Development and characterisation of semi-crystalline composite granules: The effect of particle chemistry and the electrostatic charging

NASA Astrophysics Data System (ADS)

Haque, Syed N.; Hussain, Tariq; Chowdhry, Babur Z.; Douroumis, Dennis; Scoutaris, Nikolaos; Nokhodchi, Ali; Maniruzzaman, Mohammed

2017-12-01

This study investigated the surface of semi-crystalline composite granules produced via a novel mechano-chemical process and assessed the effect of electrostatic charging. Ibuprofen (IBU), a model drug with low solubility and known associated processing challenges was loaded in composite granules to improve its processibility and dissolution rates. Synthetic amorphous mesoporous magnesium alumina metasilicate (MAS) was co-processed with hydrophilic HPMC polymer in the presence of polyethylene glycol 2000 (PEG) and deionised water. The solid state analyses conducted by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) revealed the existence of semi-crystalline IBU in the complex composite structures. Dynamic vapour sorption (DVS) study showed the water sorption and desorption profiles of the manufactured composite granules as well as the effect of water on the solid-state stability of IBU in various formulations. Advanced surface analysis conducted via energy dispersive X-ray (EDS) revealed homogenous distribution of the drug/excipients on the surface of the granules while atomic force microscopy (AFM) complemented the findings. The electrostatic charge analysis showed variable charge property which is affected by the size of the particles/granules. As expected, the in vitro dissolution study showed about 5 fold increase in the release rates of IBU compared to that of the bulk drug. The mechanochemical processing has been demonstrated as an efficient technique to develop semi-crystalline composite granules with enhanced dissolution rates of water insoluble drugs.

HM{sup +}–RG complexes (M = group 2 metal; RG = rare gas): Physical vs. chemical interactions

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

Harris, Joe P.; Dodson, Hannah; Wright, Timothy G., E-mail: Tim.Wright@nottingham.ac.uk

2015-04-21

Previous work on the HM{sup +}–He complexes (M = Be–Ra) has been extended to the cases of the heavier rare gas atoms, HM{sup +}–RG (RG = Ne–Rn). Optimized geometries and harmonic vibrational frequencies have been calculated using MP2 theory and quadruple-ζ quality basis sets. Dissociation energies for the loss of the rare gas atom have been calculated at these optimized geometries using coupled cluster with single and double excitations and perturbative triples, CCSD(T)theory, extrapolating interaction energies to the basis set limit. Comparisons are made between the present data and the previously obtained helium results, as well as to those ofmore » the bare HM{sup +} molecules; furthermore, comparisons are made to the related M{sup +}–RG and M{sup 2+}–RG complexes. Partial atomic charge analyses have also been undertaken, and these used to test a simple charge-induced dipole model. Molecular orbital diagrams are presented together with contour plots of the natural orbitals from the quadratic configuration with single and double excitations (QCISD) density. The conclusion is that the majority of these complexes are physically bound, with very little sharing of electron density; however, for M = Be, and to a lesser extent M = Mg, some evidence for chemical effects is seen in HM{sup +}–RG complexes involving RG atoms with the higher atomic numbers.« less

Mathematical modeling of chemical composition modification and etching of polymers under the atomic oxygen influence

NASA Astrophysics Data System (ADS)

Chirskaia, Natalia; Novikov, Lev; Voronina, Ekaterina

2016-07-01

Atomic oxygen (AO) of the upper atmosphere is one of the most important space factors that can cause degradation of spacecraft surface. In our previous mathematical model the Monte Carlo method and the "large particles" approximation were used for simulating processes of polymer etching under the influence of AO [1]. The interaction of enlarged AO particles with the polymer was described in terms of probabilities of reactions such as etching of polymer and specular and diffuse scattering of the AO particles on polymer. The effects of atomic oxygen on protected polymers and microfiller containing composites were simulated. The simulation results were in quite good agreement with the results of laboratory experiments on magnetoplasmadynamic accelerator of the oxygen plasma of SINP MSU [2]. In this paper we present a new model that describes the reactions of AO interactions with polymeric materials in more detail. Reactions of formation and further emission of chemical compounds such as CO, CO _{2}, H _{2}O, etc. cause the modification of the chemical composition of the polymer and change the probabilities of its consequent interaction with the AO. The simulation results are compared with the results of previous simulation and with the results of laboratory experiments. The reasons for the differences between the results of natural experiments on spacecraft, laboratory experiments and simulations are discussed. N. Chirskaya, M. Samokhina, Computer modeling of polymer structures degradation under the atomic oxygen exposure, WDS'12 Proceedings of Contributed Papers: Part III - Physics, Matfyzpress Prague, 2012, pp. 30-35. E. Voronina, L. Novikov, V. Chernik, N. Chirskaya, K. Vernigorov, G. Bondarenko, and A. Gaidar, Mathematical and experimental simulation of impact of atomic oxygen of the earth's upper atmosphere on nanostructures and polymer composites, Inorganic Materials: Applied Research, 2012, vol. 3, no. 2, pp. 95-101.

Low Earth Orbital Atomic Oxygen Interactions With Spacecraft Materials

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; deGroh, Kim K.; Miller, Sharon K.

2004-01-01

Atomic oxygen, formed in Earth s thermosphere, interacts readily with many materials on spacecraft flying in low Earth orbit (LEO). All hydrocarbon based polymers and graphite are easily oxidized upon the impact of approx.4.5 eV atomic oxygen as the spacecraft ram into the residual atmosphere. The resulting interactions can change the morphology and reduce the thickness of these materials. Directed atomic oxygen erosion will result in the development of textured surfaces on all materials with volatile oxidation products. Examples from space flight samples are provided. As a result of the erosive properties of atomic oxygen on polymers and composites, protective coatings have been developed and are used to increase the functional life of polymer films and composites that are exposed to the LEO environment. The atomic oxygen erosion yields for actual and predicted LEO exposure of numerous materials are presented. Results of in-space exposure of vacuum deposited aluminum protective coatings on polyimide Kapton indicate high rates of degradation are associated with aluminum coatings on both surfaces of the Kapton. Computational modeling predictions indicate that less trapping of the atomic oxygen occurs, with less resulting damage, if only the space-exposed surface is coated with vapor deposited aluminum rather than having both surfaces coated.

Stability, surface features, and atom leaching of palladium nanoparticles: toward prediction of catalytic functionality.

PubMed

Ramezani-Dakhel, Hadi; Mirau, Peter A; Naik, Rajesh R; Knecht, Marc R; Heinz, Hendrik

2013-04-21

Surfactant-stabilized metal nanoparticles have shown promise as catalysts although specific surface features and their influence on catalytic performance have not been well understood. We quantify the thermodynamic stability, the facet composition of the surface, and distinct atom types that affect rates of atom leaching for a series of twenty near-spherical Pd nanoparticles of 1.8 to 3.1 nm size using computational models. Cohesive energies indicate higher stability of certain particles that feature an approximate 60/20/20 ratio of {111}, {100}, and {110} facets while less stable particles exhibit widely variable facet composition. Unique patterns of atom types on the surface cause apparent differences in binding energies and changes in reactivity. Estimates of the relative rate of atom leaching as a function of particle size were obtained by the summation of Boltzmann-weighted binding energies over all surface atoms. Computed leaching rates are in good qualitative correlation with the measured catalytic activity of peptide-stabilized Pd nanoparticles of the same shape and size in Stille coupling reactions. The agreement supports rate-controlling contributions by atom leaching in the presence of reactive substrates. The computational approach provides a pathway to estimate the catalytic activity of metal nanostructures of engineered shape and size, and possible further refinements are described.

Crystal structure of the ternary silicide Gd2Re3Si5.

PubMed

Fedyna, Vitaliia; Kozak, Roksolana; Gladyshevskii, Roman

2014-12-01

A single crystal of the title compound, the ternary silicide digadolinium trirhenium penta-silicide, Gd2Re3Si5, was isolated from an alloy of nominal composition Gd20Re30Si50 synthesized by arc melting and investigated by X-ray single-crystal diffraction. Its crystal structure belongs to the U2Mn3Si5 structure type. All atoms in the asymmetric lie on special positions. The Gd site has site symmetry m..; the two Mn atoms have site symmetries m.. and 2.22; the three Si atoms have site symmetries m.., ..2 and 4.. . The coordination polyhedra of the Gd atoms have 21 vertices, while those of the Re atoms are cubo-octa-hedra and 13-vertex polyhedra. The Si atoms are arranged as tricapped trigonal prisms, bicapped square anti-prisms, or 11-vertex polyhedra. The crystal structure of the title compound is also related to the structure types CaBe2Ge2 and W5Si3. It can be represented as a stacking of Gd-centred polyhedra of composition [GdSi9]. The Re atoms form infinite chains with an Re-Re distance of 2.78163 (5) Å and isolated squares with an Re-Re distance of 2.9683 (6) Å.

Crystal structure of the ternary silicide Gd2Re3Si5

PubMed Central

Fedyna, Vitaliia; Kozak, Roksolana; Gladyshevskii, Roman

2014-01-01

A single crystal of the title compound, the ternary silicide digadolinium trirhenium penta­silicide, Gd2Re3Si5, was isolated from an alloy of nominal composition Gd20Re30Si50 synthesized by arc melting and investigated by X-ray single-crystal diffraction. Its crystal structure belongs to the U2Mn3Si5 structure type. All atoms in the asymmetric lie on special positions. The Gd site has site symmetry m..; the two Mn atoms have site symmetries m.. and 2.22; the three Si atoms have site symmetries m.., ..2 and 4.. . The coordination polyhedra of the Gd atoms have 21 vertices, while those of the Re atoms are cubo­octa­hedra and 13-vertex polyhedra. The Si atoms are arranged as tricapped trigonal prisms, bicapped square anti­prisms, or 11-vertex polyhedra. The crystal structure of the title compound is also related to the structure types CaBe2Ge2 and W5Si3. It can be represented as a stacking of Gd-centred polyhedra of composition [GdSi9]. The Re atoms form infinite chains with an Re—Re distance of 2.78163 (5) Å and isolated squares with an Re—Re distance of 2.9683 (6) Å. PMID:25552967

‘Pd20Sn13’ revisited: crystal structure of Pd6.69Sn4.31

PubMed Central

Klein, Wilhelm; Jin, Hanpeng; Hlukhyy, Viktor; Fässler, Thomas F.

2015-01-01

The crystal structure of the title compound was previously reported with composition ‘Pd20Sn13’ [Sarah et al. (1981 ▸). Z. Metallkd, 72, 517–520]. For the original structure model, as determined from powder X-ray data, atomic coordinates from the isostructural compound Ni13Ga3Ge6 were transferred. The present structure determination, resulting in a composition Pd6.69Sn4.31, is based on single crystal X-ray data and includes anisotropic displacement parameters for all atoms as well as standard uncertainties for the atomic coordinates, leading to higher precision and accuracy for the structure model. Single crystals of the title compound were obtained via a solid-state reaction route, starting from the elements. The crystal structure can be derived from the AlB2 type of structure after removing one eighth of the atoms at the boron positions and shifting adjacent atoms in the same layer in the direction of the voids. One atomic site is partially occupied by both elements with a Pd:Sn ratio of 0.38 (3):0.62 (3). One Sn and three Pd atoms are located on special positions with site symmetry 2. (Wyckoff letter 3a and 3b). PMID:26279872

Complex structure of the carbon arc discharge for synthesis of nanotubes

DOE PAGES

Vekselman, V.; Feurer, M.; Huang, T.; ...

2017-06-06

Comprehensive non-invasive spectroscopic techniques and electrical measurements of the carbon arc revealed two distinguishable plasma synthesis regions in the radial direction normal to the arc axis. These regions, which are defined as the arc core and the arc periphery, are shown to have very different compositions of carbon species with different densities and temperatures. The colder arc periphery is dominated by carbon diatomic molecules (C 2), which are in the minority in the composition of the hot arc core. These differences are due to a highly non-uniform distribution of the arc current, which is mainly conducted through the arc coremore » populated with carbon atoms and ions. Therefore, the ablation of the graphite anode is governed by the arc core, while the formation of carbon molecules occurs in the colder arc periphery. Furthermore, this result is consistent with previous predictions that the plasma environment in the arc periphery is suitable for synthesis of carbon nanotubes.« less

Biomass-directed synthesis of 20 g high-quality boron nitride nanosheets for thermoconductive polymeric composites.

PubMed

Wang, Xue-Bin; Weng, Qunhong; Wang, Xi; Li, Xia; Zhang, Jun; Liu, Fei; Jiang, Xiang-Fen; Guo, Hongxuan; Xu, Ningsheng; Golberg, Dmitri; Bando, Yoshio

2014-09-23

Electrically insulating boron nitride (BN) nanosheets possess thermal conductivity similar to and thermal and chemical stabilities superior to those of electrically conductive graphenes. Currently the production and application of BN nanosheets are rather limited due to the complexity of the BN binary compound growth, as opposed to massive graphene production. Here we have developed the original strategy "biomass-directed on-site synthesis" toward mass production of high-crystal-quality BN nanosheets. The strikingly effective, reliable, and high-throughput (dozens of grams) synthesis is directed by diverse biomass sources through the carbothermal reduction of gaseous boron oxide species. The produced BN nanosheets are single crystalline, laterally large, and atomically thin. Additionally, they assemble themselves into the same macroscopic shapes peculiar to original biomasses. The nanosheets are further utilized for making thermoconductive and electrically insulating epoxy/BN composites with a 14-fold increase in thermal conductivity, which are envisaged to be particularly valuable for future high-performance electronic packaging materials.

Effect Of Chromium Underlayer On The Properties Of Nano-Crystalline Diamond Films

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

Garratt, Elias; AlFaify, Salem; Yoshitake, T.

2013-01-11

This paper investigated the effect of chromium underlayer on the structure, microstructure and composition of the nano-crystalline diamond films. Nano-crystalline diamond thin films were deposited at high temperature in microwave-induced plasma diluted with nitrogen, on silicon substrate with a thin film of chromium as an underlayer. The composition, structure and microstructure of the deposited layers were analyzed using non-Rutherford Backscattering Spectrometry, Raman Spectroscopy, Near-Edge X-Ray Absorption Fine Structure, X-ray Diffraction and Atomic Force Microscopy. Nanoindentation studies showed that the films deposited on chromium underlayer have higher hardness values compared to those deposited on silicon without an underlayer. Diamond and graphiticmore » phases of the films evaluated by x-ray and optical spectroscopic analysis determined consistency between sp2 and sp3 phases of carbon in chromium sample to that of diamond grown on silicon. Diffusion of chromium was observed using ion beam analysis which was correlated with the formation of chromium complexes by x-ray diffraction.« less

Complex structure of the carbon arc discharge for synthesis of nanotubes

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

Vekselman, V.; Feurer, M.; Huang, T.

Comprehensive non-invasive spectroscopic techniques and electrical measurements of the carbon arc revealed two distinguishable plasma synthesis regions in the radial direction normal to the arc axis. These regions, which are defined as the arc core and the arc periphery, are shown to have very different compositions of carbon species with different densities and temperatures. The colder arc periphery is dominated by carbon diatomic molecules (C 2), which are in the minority in the composition of the hot arc core. These differences are due to a highly non-uniform distribution of the arc current, which is mainly conducted through the arc coremore » populated with carbon atoms and ions. Therefore, the ablation of the graphite anode is governed by the arc core, while the formation of carbon molecules occurs in the colder arc periphery. Furthermore, this result is consistent with previous predictions that the plasma environment in the arc periphery is suitable for synthesis of carbon nanotubes.« less

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

Grimme, Stefan, E-mail: grimme@thch.uni-bonn.de; Brandenburg, Jan Gerit; Bannwarth, Christoph

A density functional theory (DFT) based composite electronic structure approach is proposed to efficiently compute structures and interaction energies in large chemical systems. It is based on the well-known and numerically robust Perdew-Burke-Ernzerhoff (PBE) generalized-gradient-approximation in a modified global hybrid functional with a relatively large amount of non-local Fock-exchange. The orbitals are expanded in Ahlrichs-type valence-double zeta atomic orbital (AO) Gaussian basis sets, which are available for many elements. In order to correct for the basis set superposition error (BSSE) and to account for the important long-range London dispersion effects, our well-established atom-pairwise potentials are used. In the design ofmore » the new method, particular attention has been paid to an accurate description of structural parameters in various covalent and non-covalent bonding situations as well as in periodic systems. Together with the recently proposed three-fold corrected (3c) Hartree-Fock method, the new composite scheme (termed PBEh-3c) represents the next member in a hierarchy of “low-cost” electronic structure approaches. They are mainly free of BSSE and account for most interactions in a physically sound and asymptotically correct manner. PBEh-3c yields good results for thermochemical properties in the huge GMTKN30 energy database. Furthermore, the method shows excellent performance for non-covalent interaction energies in small and large complexes. For evaluating its performance on equilibrium structures, a new compilation of standard test sets is suggested. These consist of small (light) molecules, partially flexible, medium-sized organic molecules, molecules comprising heavy main group elements, larger systems with long bonds, 3d-transition metal systems, non-covalently bound complexes (S22 and S66×8 sets), and peptide conformations. For these sets, overall deviations from accurate reference data are smaller than for various other tested DFT methods and reach that of triple-zeta AO basis set second-order perturbation theory (MP2/TZ) level at a tiny fraction of computational effort. Periodic calculations conducted for molecular crystals to test structures (including cell volumes) and sublimation enthalpies indicate very good accuracy competitive to computationally more involved plane-wave based calculations. PBEh-3c can be applied routinely to several hundreds of atoms on a single processor and it is suggested as a robust “high-speed” computational tool in theoretical chemistry and physics.« less

Variation in the terrestrial isotopic composition and atomic weight of argon

USGS Publications Warehouse

Böhlke, John Karl

2014-01-01

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios (40Ar/36Ar, 38Ar/36Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40Ar, as some samples contain almost pure radiogenic 40Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36Ar and 38Ar. Within this interval, measurements of different isotope ratios (40Ar/36Ar or 38Ar/36Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

The effects of atomic oxygen on the thermal emittance of high temperature radiator surfaces

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Hotes, Deborah L.; Paulsen, Phillip E.

1989-01-01

Radiator surfaces on high temperature space power systems such as SP-100 space nuclear power system must maintain a high emittance level in order to reject waste heat effectively. One of the primary materials under consideration for the radiators is carbon-carbon composite. Since carbon is susceptible to attack by atomic oxygen in the low earth orbital environment, it is important to determine the durability of carbon composites in this environment as well as the effect atomic oxygen has on the thermal emittance of the surface if it is to be considered for use as a radiator. Results indicate that the thermal emittance of carbon-carbon composite (as low as 0.42) can be enhanced by exposure to a directed beam of atomic oxygen to levels above 0.85 at 800 K. This emittance enhancement is due to a change in the surface morphology as a result of oxidation. High aspect ratio cones are formed on the surface which allow more efficient trapping of incident radiation. Erosion of the surface due to oxidation is similar to that for carbon, so that at altitudes less than approximately 600 km, thickness loss of the radiator could be significant (as much as 0.1 cm/year). A protective coating or oxidation barrier forming additive may be needed to prevent atomic oxygen attack after the initial high emittance surface is formed. Textured surfaces can be formed in ground based facilities or possibly in space if emittance is not sensitive to the orientation of the atomic oxygen arrival that forms the texture.

A basin-hopping Monte Carlo investigation of the structural and energetic properties of 55- and 561-atom bimetallic nanoclusters: the examples of the ZrCu, ZrAl, and CuAl systems.

PubMed

De Souza, Douglas G; Cezar, Henrique M; Rondina, Gustavo G; de Oliveira, Marcelo F; Da Silva, Juarez L F

2016-05-05

We report a basin-hopping Monte Carlo investigation within the embedded-atom method of the structural and energetic properties of bimetallic ZrCu, ZrAl, and CuAl nanoclusters with 55 and 561 atoms. We found that unary Zr55, Zr561, Cu55, Cu561, Al55, and Al561 systems adopt the well known compact icosahedron (ICO) structure. The excess energy is negative for all systems and compositions, which indicates an energetic preference for the mixing of both chemical species. The ICO structure is preserved if a few atoms of the host system are replaced by different species, however, the composition limit in which the ICO structure is preserved depends on both the host and new chemical species. Using several structural analyses, three classes of structures, namely ideal ICO, nearly ICO, and distorted ICO structures, were identified. As the amounts of both chemical species change towards a more balanced composition, configurations far from the ICO structure arise and the dominant structures are nearly spherical, which indicates a strong minimization of the surface energy by decreasing the number of atoms with lower coordination on the surface. The average bond lengths follow Vegard's law almost exactly for ZrCu and ZrAl, however, this is not the case for CuAl. Furthermore, the radial distribution allowed us to identify the presence of an onion-like behavior in the surface of the 561-atom CuAl nanocluster with the Al atoms located in the outermost surface shell, which can be explained by the lower surface energies of the Al surfaces compared with the Cu surfaces. In ZrCu and ZrAl the radial distribution indicates a nearly homogeneous distribution for the chemical species, however, with a slightly higher concentration of Al atoms on the ZrAl surface, which can also be explained by the lower surface energy.

Atomic scale structure and chemistry of interfaces by Z-contrast imaging and electron energy loss spectroscopy in the stem

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

McGibbon, M.M.; Browning, N.D.; Chisholm, M.F.

The macroscopic properties of many materials are controlled by the structure and chemistry at grain boundaries. A basic understanding of the structure-property relationship requires a technique which probes both composition and chemical bonding on an atomic scale. High-resolution Z-contrast imaging in the scanning transmission electron microscope (STEM) forms an incoherent image in which changes in atomic structure and composition across an interface can be interpreted directly without the need for preconceived atomic structure models. Since the Z-contrast image is formed by electrons scattered through high angles, parallel detection electron energy loss spectroscopy (PEELS) can be used simultaneously to provide complementarymore » chemical information on an atomic scale. The fine structure in the PEEL spectra can be used to investigate the local electronic structure and the nature of the bonding across the interface. In this paper we use the complimentary techniques of high resolution Z-contrast imaging and PEELS to investigate the atomic structure and chemistry of a 25{degree} symmetric tilt boundary in a bicrystal of the electroceramic SrTiO{sub 3}.« less

Tailoring characteristic thermal stability of Ni-Au binary nanocrystals via structure and composition engineering: theoretical insights into structural evolution and atomic inter-diffusion

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

Li, Bangquan; Wang, Hailong; Xing, Guozhong

We report on the structural evolution and atomic inter-diffusion characteristics of the bimetallic Ni-Au nanocrystals (NCs) by molecular dynamics simulations studies. Our results reveal that the thermal stability dynamics of Ni-Au NCs strongly depends on the atomic configurations. By engineering the structural construction with Ni:Au = 1:1 atomic composition, compared with core-shell Au@Ni and alloy NCs, the melting point of core-shell Ni@Au NCs is significantly enhanced up to 1215 K. Unexpectedly, with atomic ratio of Au:Ni= 1:9, the melting process initiates from the atoms in the shell of Ni@Au and alloy NCs, while starts from the core of Au@Ni NCs.more » The corresponding features and evolution process of structural motifs, mixing and segregation are illustrated via a series of dynamic simulations videos. Moreover, our results revealed that the face centered cubic phase Au{sub 0.75}Ni{sub 0.25} favorably stabilizes in NCs form but does not exist in the bulk counterpart, which elucidates the anomalies of previously reported experimental results on such bimetallic NCs.« less

Atomic-Resolution Spectrum Imaging of Semiconductor Nanowires.

PubMed

Zamani, Reza R; Hage, Fredrik S; Lehmann, Sebastian; Ramasse, Quentin M; Dick, Kimberly A

2018-03-14

Over the past decade, III-V heterostructure nanowires have attracted a surge of attention for their application in novel semiconductor devices such as tunneling field-effect transistors (TFETs). The functionality of such devices critically depends on the specific atomic arrangement at the semiconductor heterointerfaces. However, most of the currently available characterization techniques lack sufficient spatial resolution to provide local information on the atomic structure and composition of these interfaces. Atomic-resolution spectrum imaging by means of electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) is a powerful technique with the potential to resolve structure and chemical composition with sub-angstrom spatial resolution and to provide localized information about the physical properties of the material at the atomic scale. Here, we demonstrate the use of atomic-resolution EELS to understand the interface atomic arrangement in three-dimensional heterostructures in semiconductor nanowires. We observed that the radial interfaces of GaSb-InAs heterostructure nanowires are atomically abrupt, while the axial interface in contrast consists of an interfacial region where intermixing of the two compounds occurs over an extended spatial region. The local atomic configuration affects the band alignment at the interface and, hence, the charge transport properties of devices such as GaSb-InAs nanowire TFETs. STEM-EELS thus represents a very promising technique for understanding nanowire physical properties, such as differing electrical behavior across the radial and axial heterointerfaces of GaSb-InAs nanowires for TFET applications.

Practical Applications of Cosmic Ray Science: Spacecraft, Aircraft, Ground-Based Computation and Control Systems, Exploration, and Human Health and Safety

NASA Technical Reports Server (NTRS)

Koontz, Steve

2015-01-01

In this presentation a review of galactic cosmic ray (GCR) effects on microelectronic systems and human health and safety is given. The methods used to evaluate and mitigate unwanted cosmic ray effects in ground-based, atmospheric flight, and space flight environments are also reviewed. However not all GCR effects are undesirable. We will also briefly review how observation and analysis of GCR interactions with planetary atmospheres and surfaces and reveal important compositional and geophysical data on earth and elsewhere. About 1000 GCR particles enter every square meter of Earth’s upper atmosphere every second, roughly the same number striking every square meter of the International Space Station (ISS) and every other low- Earth orbit spacecraft. GCR particles are high energy ionized atomic nuclei (90% protons, 9% alpha particles, 1% heavier nuclei) traveling very close to the speed of light. The GCR particle flux is even higher in interplanetary space because the geomagnetic field provides some limited magnetic shielding. Collisions of GCR particles with atomic nuclei in planetary atmospheres and/or regolith as well as spacecraft materials produce nuclear reactions and energetic/highly penetrating secondary particle showers. Three twentieth century technology developments have driven an ongoing evolution of basic cosmic ray science into a set of practical engineering tools needed to design, test, and verify the safety and reliability of modern complex technological systems and assess effects on human health and safety effects. The key technology developments are: 1) high altitude commercial and military aircraft; 2) manned and unmanned spacecraft; and 3) increasingly complex and sensitive solid state micro-electronics systems. Space and geophysical exploration needs drove the development of the instruments and analytical tools needed to recover compositional and structural data from GCR induced nuclear reactions and secondary particle showers. Finally, the possible role of GCR secondary particle showers in addressing an important homeland security problem, finding nuclear contraband and weapons, will be briefly reviewed.

Nanoscopic diffusion studies on III-V compound semiconductor structures: Experiment and theory

NASA Astrophysics Data System (ADS)

Gonzalez Debs, Mariam

The electronic structure of multilayer semiconductor heterostructures is affected by the detailed compositional profiles throughout the structure and at critical interfaces. The extent of interdiffusion across these interfaces places limits on both the processing time and temperatures for many applications based on the resultant compositional profile and associated electronic structure. Atomic and phenomenological methods were used in this work through the combination of experiment and theory to understand the nanoscopic mechanisms in complex heterostructures. Two principal studies were conducted. Tin diffusion in GaAs was studied by fitting complex experimental diffusion profiles to a phenomenological model which involved the diffusion of substitutional and interstitial dopant atoms. A methodology was developed combining both the atomistic model and the use of key features within these experimentally-obtained diffusion profiles to determine meaningful values of the transport and defect reaction rate parameters. Interdiffusion across AlSb/GaSb multi-quantum well interfaces was also studied. The chemical diffusion coefficient characterizing the AlSb/GaSb diffusion couple was quantitatively determined by fitting the observed photoluminescence (PL) peak shifts to the solution of the Schrodinger equation using a potential derived from the solution of the diffusion equation to quantify the interband transition energy shifts. First-principles calculations implementing Density Functional Theory were performed to study the thermochemistry of point defects as a function of local environment, allowing a direct comparison of interfacial and bulk diffusion phenomena within these nanoscopic structures. Significant differences were observed in the Ga and Al vacancy formation energies at the AlSb/GaSb interface when compared to bulk AlSb and GaSb with the largest change found for Al vacancies. The AlSb/GaSb structures were further studied using positron annihilation spectroscopy (PAS) to investigate the role of vacancies in the interdiffusion of Al and Ga in the superlattices. The PL and PAS experimental techniques together with the phenomenological and atomistic modeling allowed for the determination of the underlying mass transport mechanisms at the nanoscale.

Synthesis, spectroscopic, thermal, voltammetric studies and biological activity of crystalline complexes of pyridine-2,6-dicarboxylic acid and 8-hydroxyquinoline

NASA Astrophysics Data System (ADS)

Çolak, Alper Tolga; Çolak, Ferdağ; Yeşilel, Okan Zafer; Büyükgüngör, Orhan

2009-11-01

Two new compounds (8-H 2Q) 2[M(dipic) 2]·6H 2O (M = Co ( 1) and Ni ( 2), 8-HQ = 8-hydroxyquinoline, dipic = dipicolinate) have been prepared and characterized by elemental analysis, spectral (IR and UV-vis), thermal analyses, magnetic measurements and single-crystal X-ray diffraction techniques. Both 1 and 2 consist two 8-hydroxyquinolinium cations, one bis(dipicolinate)M(II) anion [M = Co(II), Ni(II)] and six uncoordinated water molecules. Both 1 and 2 crystallize in the monoclinic space group C2/c. In the compounds anion, each dipic ligand simultaneously exhibits tridentate coordination modes through N atom of pyridine ring and oxygen atoms of the carboxylate groups. The crystal packing of 1 and 2 is a composite of intermolecular hydrogen bonding and C-O⋯π interactions. The in vitro antibacterial and antifungal activities of 1 and 2 were evaluated by the agar well diffusion method by MIC tests. Both new compounds showed the same antimicrobial activity against Gram-positive bacteria and yeast and fungi expect Gram-negative bacteria.

Development of TiO2 containing hardmasks through plasma-enhanced atomic layer deposition

NASA Astrophysics Data System (ADS)

De Silva, Anuja; Seshadri, Indira; Chung, Kisup; Arceo, Abraham; Meli, Luciana; Mendoza, Brock; Sulehria, Yasir; Yao, Yiping; Sunder, Madhana; Truong, Hoa; Matham, Shravan; Bao, Ruqiang; Wu, Heng; Felix, Nelson M.; Kanakasabapathy, Sivananda

2017-04-01

With the increasing prevalence of complex device integration schemes, trilayer patterning with a solvent strippable hardmask can have a variety of applications. Spin-on metal hardmasks have been the key enabler for selective removal through wet strip when active areas need to be protected from dry etch damage. As spin-on metal hardmasks require a dedicated track to prevent metal contamination and are limited in their ability to scale down thickness without compromising on defectivity, there has been a need for a deposited hardmask solution. Modulation of film composition through deposition conditions enables a method to create TiO2 films with wet etch tunability. This paper presents a systematic study on development and characterization of plasma-enhanced atomic layer deposited (PEALD) TiO2-based hardmasks for patterning applications. We demonstrate lithographic process window, pattern profile, and defectivity evaluation for a trilayer scheme patterned with PEALD-based TiO2 hardmask and its performance under dry and wet strip conditions. Comparable structural and electrical performance is shown for a deposited versus a spin-on metal hardmask.

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

NASA Astrophysics Data System (ADS)

You, Xiaofang; Wei, Hengbin; Zhu, Xianchang; Lyu, Xianjun; Li, Lin

2018-07-01

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with -386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.

Statistical correction of atom probe tomography data of semiconductor alloys combined with optical spectroscopy: The case of Al{sub 0.25}Ga{sub 0.75}N

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

Rigutti, L., E-mail: lorenzo.rigutti@univ-rouen.fr; Mancini, L.; Hernández-Maldonado, D.

2016-03-14

The ternary semiconductor alloy Al{sub 0.25}Ga{sub 0.75}N has been analyzed by means of correlated photoluminescence spectroscopy and atom probe tomography (APT). We find that the composition measured by APT is strongly dependent on the surface electric field, leading to erroneous measurements of the alloy composition at high field, due to the different evaporation behaviors of Al and Ga atoms. After showing how a biased measurement of the alloy content leads to inaccurate predictions on the optical properties of the material, we develop a correction procedure which yields consistent transition and localization energies for the alloy photoluminescence.

Composite-Light-Pulse Technique for High-Precision Atom Interferometry

NASA Astrophysics Data System (ADS)

Berg, P.; Abend, S.; Tackmann, G.; Schubert, C.; Giese, E.; Schleich, W. P.; Narducci, F. A.; Ertmer, W.; Rasel, E. M.

2015-02-01

We realize beam splitters and mirrors for atom waves by employing a sequence of light pulses rather than individual ones. In this way we can tailor atom interferometers with improved sensitivity and accuracy. We demonstrate our method of composite pulses by creating a symmetric matter-wave interferometer which combines the advantages of conventional Bragg- and Raman-type concepts. This feature leads to an interferometer with a high immunity to technical noise allowing us to devise a large-area Sagnac gyroscope yielding a phase shift of 6.5 rad due to the Earth's rotation. With this device we achieve a rotation rate precision of 120 nrad s-1 Hz-1 /2 and determine the Earth's rotation rate with a relative uncertainty of 1.2%.

Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

PubMed

Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

2012-05-01

Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Ellis, T.W.

1994-11-29

A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material. 9 figures.

Quantifying Interactions of Nucleobase Atoms with Model Compounds for the Peptide Backbone and Glutamine and Asparagine Side Chains in Water.

PubMed

Cheng, Xian; Shkel, Irina A; Molzahn, Cristen; Lambert, David; Karim, Rezwana; Record, M Thomas

2018-04-17

Alkylureas display hydrocarbon and amide groups, the primary functional groups of proteins. To obtain the thermodynamic information that is needed to analyze interactions of amides and proteins with nucleobases and nucleic acids, we quantify preferential interactions of alkylureas with nucleobases differing in the amount and composition of water-accessible surface area (ASA) by solubility assays. Using an established additive ASA-based analysis, we interpret these thermodynamic results to determine interactions of each alkylurea with five types of nucleobase unified atoms (carbonyl sp 2 O, amino sp 3 N, ring sp 2 N, methyl sp 3 C, and ring sp 2 C). All alkylureas interact favorably with nucleobase sp 2 C and sp 3 C atoms; these interactions become more favorable with an increasing level of alkylation of urea. Interactions with nucleobase sp 2 O are most favorable for urea, less favorable for methylurea and ethylurea, and unfavorable for dialkylated ureas. Contributions to overall alkylurea-nucleobase interactions from interactions with each nucleobase atom type are proportional to the ASA of that atom type with proportionality constant (interaction strength) α, as observed previously for urea. Trends in α-values for interactions of alkylureas with nucleobase atom types parallel those for corresponding amide compound atom types, offset because nucleobase α-values are more favorable. Comparisons between ethylated and methylated ureas show interactions of amide compound sp 3 C with nucleobase sp 2 C, sp 3 C, sp 2 N, and sp 3 N atoms are favorable while amide sp 3 C-nucleobase sp 2 O interactions are unfavorable. Strongly favorable interactions of urea with nucleobase sp 2 O but weakly favorable interactions with nucleobase sp 3 N indicate that amide sp 2 N-nucleobase sp 2 O and nucleobase sp 3 N-amide sp 2 O hydrogen bonding (NH···O═C) interactions are favorable while amide sp 2 N-nucleobase sp 3 N interactions are unfavorable. These favorable amide-nucleobase hydrogen bonding interactions are prevalent in specific protein-nucleotide complexes.

Synthesis, structures and Helicobacter pylori urease inhibitory activity of copper(II) complexes with tridentate aroylhydrazone ligands.

PubMed

Pan, Lin; Wang, Cunfang; Yan, Kai; Zhao, Kedong; Sheng, Guihua; Zhu, Hailiang; Zhao, Xinlu; Qu, Dan; Niu, Fang; You, Zhonglu

2016-06-01

A series of new copper(II) complexes were prepared. They are [CuL(1)(NCS)] (1), [CuClL(1)]·CH3OH (2), [CuClL(2)]·CH3OH (3), [CuL(3)(NCS)]·CH3OH (4), [CuL(4)(NCS)]·0.4H2O (5), and [CuL(5)(bipy)] (6), where L(1), L(2), L(3) and L(4) are the deprotonated form of N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide, 4-bromo-N'-(2-hydroxy-5-methoxybenzylidene)benzohydrazide, N'-(2-hydroxy-5-methoxybenzylidene)-3-methylbenzohydrazide and 2-chloro-N'-(2-hydroxy-5-methoxybenzylidene)benzohydrazide, respectively, L(5) is the dianionic form of N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide, and bipy is 2,2'-bipyridine. The complexes were characterized by infrared and UV-Vis spectra and single crystal X-ray diffraction. The Cu atoms in complexes 1, 2, 3, 4 and 5 are coordinated by the NOO donor set of the aroylhydrazone ligands, and one Cl or thiocyanate N atom, forming square planar coordination. The Cu atom in complex 6 is in a square pyramidal coordination, with the NOO donor set of L(1), and one N atom of bipy defining the basal plane, and with the other N atom of bipy occupying the apical position. Complexes 1, 2, 3, 4 and 5 show effective urease inhibitory activities, with IC50 values of 5.14, 0.20, 4.06, 5.52 and 0.26μM, respectively. Complex 6 has very weak activity against urease, with IC50 value over 100μM. Molecular docking study of the complexes with the Helicobacter pylori urease was performed. The relationship between structures and urease inhibitory activities indicated that copper complexes with square planar coordination are better models for urease inhibition. Copyright © 2016 Elsevier Inc. All rights reserved.

TEMPORAL EVOLUTION OF SUB-NANOMETER COMPOSITIONAL PROFILES ACROSS THE GAMMA/GAMMA' INTERFACE IN A MODEL Ni-Al-Cr SUPERALLOY

NASA Technical Reports Server (NTRS)

Sudbrack, Chantal K.; Noebe, Ronald D.; Seidman, David N.

2005-01-01

Early-stage phase separation in a Ni-5.2 Al-14.2 Cr at.% superalloy, isothermally decomposing at 873 K, is investigated with atom-probe tomography. Sub-nanometer scale compositional profiles across the gamma/gamma'(L12) interfaces demonstrate that both the gamma-matrix and the gamma'-precipitate compositions evolve with time. Observed chemical gradients of Al depletion and Cr enrichment adjacent to the gamma'-precipitates are transient, consistent with well-established model predictions for diffusion-limited growth, and mark the first detailed observation of this phenomenon. Furthermore, it is shown that Cr atoms are kinetically trapped in the growing precipitates.

Lipid composition dictates serum stability of reconstituted high-density lipoproteins: implications for in vivo applications.

PubMed

Gilmore, Sean F; Carpenter, Timothy S; Ingólfsson, Helgi I; Peters, Sandra K G; Henderson, Paul T; Blanchette, Craig D; Fischer, Nicholas O

2018-04-26

Nanolipoprotein particles (NLPs) are reconstituted high-density lipoproteins, consisting of a phospholipid bilayer stabilized by an apolipoprotein scaffold protein. This class of nanoparticle has been a vital tool in the study of membrane proteins, and in recent years has been increasingly used for in vivo applications. Previous work demonstrated that the composition of the lipid bilayer component affects the stability of these particles in serum solutions. In the current study, NLPs assembled with phosphatidylcholine lipids featuring different acyl chain structures were systematically tested to understand the effect that lipid composition has on NLP stability in both neat serum and cell culture media supplemented with 10% serum by volume. The time at which 50% of the particles dissociate, as well as the fraction of the initial population that remains resistant to dissociation, were correlated to key parameters obtained from all-atom simulations of the corresponding lipid bilayers. A significant correlation was observed between the compressibility modulus of the lipid bilayer and particle stability in these complex biological milieu. These results can be used as a reference to tune the stability of these versatile biological nanoparticles for in vitro and in vivo applications.

Predicting protein complex geometries with a neural network.

PubMed

Chae, Myong-Ho; Krull, Florian; Lorenzen, Stephan; Knapp, Ernst-Walter

2010-03-01

A major challenge of the protein docking problem is to define scoring functions that can distinguish near-native protein complex geometries from a large number of non-native geometries (decoys) generated with noncomplexed protein structures (unbound docking). In this study, we have constructed a neural network that employs the information from atom-pair distance distributions of a large number of decoys to predict protein complex geometries. We found that docking prediction can be significantly improved using two different types of polar hydrogen atoms. To train the neural network, 2000 near-native decoys of even distance distribution were used for each of the 185 considered protein complexes. The neural network normalizes the information from different protein complexes using an additional protein complex identity input neuron for each complex. The parameters of the neural network were determined such that they mimic a scoring funnel in the neighborhood of the native complex structure. The neural network approach avoids the reference state problem, which occurs in deriving knowledge-based energy functions for scoring. We show that a distance-dependent atom pair potential performs much better than a simple atom-pair contact potential. We have compared the performance of our scoring function with other empirical and knowledge-based scoring functions such as ZDOCK 3.0, ZRANK, ITScore-PP, EMPIRE, and RosettaDock. In spite of the simplicity of the method and its functional form, our neural network-based scoring function achieves a reasonable performance in rigid-body unbound docking of proteins. Proteins 2010. (c) 2009 Wiley-Liss, Inc.

Alloy with metallic glass and quasi-crystalline properties

DOEpatents

Xing, Li-Qian; Hufnagel, Todd C.; Ramesh, Kaliat T.

2004-02-17

An alloy is described that is capable of forming a metallic glass at moderate cooling rates and exhibits large plastic flow at ambient temperature. Preferably, the alloy has a composition of (Zr, Hf).sub.a Ta.sub.b Ti.sub.c Cu.sub.d Ni.sub.e Al.sub.f, where the composition ranges (in atomic percent) are 45.ltoreq.a.ltoreq.70, 3.ltoreq.b.ltoreq.7.5, 0.ltoreq.c.ltoreq.4, 3.ltoreq.b+c.ltoreq.10, 10.ltoreq.d.ltoreq.30, 0.ltoreq.e.ltoreq.20, 10.ltoreq.d+e.ltoreq.35, and 5.ltoreq.f.ltoreq.15. The alloy may be cast into a bulk solid with disordered atomic-scale structure, i.e., a metallic glass, by a variety of techniques including copper mold die casting and planar flow casting. The as-cast amorphous solid has good ductility while retaining all of the characteristic features of known metallic glasses, including a distinct glass transition, a supercooled liquid region, and an absence of long-range atomic order. The alloy may be used to form a composite structure including quasi-crystals embedded in an amorphous matrix. Such a composite quasi-crystalline structure has much higher mechanical strength than a crystalline structure.

Determining the composition of small features in atom probe: bcc Cu-rich precipitates in an Fe-rich matrix.

PubMed

Morley, A; Sha, G; Hirosawa, S; Cerezo, A; Smith, G D W

2009-04-01

Aberrations in the ion trajectories near the specimen surface are an important factor in the spatial resolution of the atom probe technique. Near the boundary between two phases with dissimilar evaporation fields, ion trajectory overlaps may occur, leading to a biased measurement of composition in the vicinity of this interface. In the case of very small second-phase precipitates, the region affected by trajectory overlaps may extend to the centre of the precipitate prohibiting a direct measurement of composition. A method of quantifying the aberrant matrix contribution and thus estimating the underlying composition is presented. This method is applied to the Fe-Cu-alloy system, where the precipitation of low-nanometre size Cu-rich precipitates is of considerable technical importance in a number of materials applications. It is shown definitively that there is a non-zero underlying level of Fe within precipitates formed upon thermal ageing, which is augmented and masked by trajectory overlaps. The concentration of Fe in the precipitate phase is shown to be a function of ageing temperature. An estimate of the underlying Fe level is made, which is at lower levels than commonly reported by atom probe investigations.

A model Ni-Al-Mo superalloy studied by ultraviolet pulsed-laser-assisted local-electrode atom-probe tomography.

PubMed

Tu, Yiyou; Plotnikov, Elizaveta Y; Seidman, David N

2015-04-01

This study investigates the effects of the charge-state ratio of evaporated ions on the accuracy of local-electrode atom-probe (LEAP) tomographic compositional and structural analyses, which employs a picosecond ultraviolet pulsed laser. Experimental results demonstrate that the charge-state ratio is a better indicator of the best atom-probe tomography (APT) experimental conditions compared with laser pulse energy. The thermal tails in the mass spectra decrease significantly, and the mass resolving power (m/Δm) increases by 87.5 and 185.7% at full-width half-maximum and full-width tenth-maximum, respectively, as the laser pulse energy is increased from 5 to 30 pJ/pulse. The measured composition of this alloy depends on the charge-state ratio of the evaporated ions, and the most accurate composition is obtained when Ni2+/Ni+ is in the range of 0.3-20. The γ(f.c.c.)/γ'(L12) interface is quantitatively more diffuse when determined from the measured concentration profiles for higher laser pulse energies. Conclusions of the APT compositional and structural analyses utilizing the same suitable charge-state ratio are more comparable than those collected with the same laser pulse energy.

Tuning near-gap electronic structure, interface charge transfer and visible light response of hybrid doped graphene and Ag3PO4 composite: Dopant effects

PubMed Central

He, Chao-Ni; Huang, Wei-Qing; Xu, Liang; Yang, Yin-Cai; Zhou, Bing-Xin; Huang, Gui-Fang; Peng, P.; Liu, Wu-Ming

2016-01-01

The enhanced photocatalytic performance of doped graphene (GR)/semiconductor nanocomposites have recently been widely observed, but an understanding of the underlying mechanisms behind it is still out of reach. As a model system to study the dopant effects, we investigate the electronic structures and optical properties of doped GR/Ag3PO4 nanocomposites using the first-principles calculations, demonstrating that the band gap, near-gap electronic structure and interface charge transfer of the doped GR/Ag3PO4(100) composite can be tuned by the dopants. Interestingly, the doping atom and C atoms bonded to dopant become active sites for photocatalysis because they are positively or negatively charged due to the charge redistribution caused by interaction. The dopants can enhance the visible light absorption and photoinduced electron transfer. We propose that the N atom may be one of the most appropriate dopants for the GR/Ag3PO4 photocatalyst. This work can rationalize the available experimental results about N-doped GR-semiconductor composites, and enriches our understanding on the dopant effects in the doped GR-based composites for developing high-performance photocatalysts. PMID:26923338

Complementary Characterization of Cu(In,Ga)Se₂ Thin-Film Photovoltaic Cells Using Secondary Ion Mass Spectrometry, Auger Electron Spectroscopy, and Atom Probe Tomography.

PubMed

Jang, Yun Jung; Lee, Jihye; Jeong, Jeung-Hyun; Lee, Kang-Bong; Kim, Donghwan; Lee, Yeonhee

2018-05-01

To enhance the conversion performance of solar cells, a quantitative and depth-resolved elemental analysis of photovoltaic thin films is required. In this study, we determined the average concentration of the major elements (Cu, In, Ga, and Se) in fabricated Cu(In,Ga)Se2 (CIGS) thin films, using inductively coupled plasma atomic emission spectroscopy, X-ray fluorescence, and wavelengthdispersive electron probe microanalysis. Depth profiling results for CIGS thin films with different cell efficiencies were obtained using secondary ion mass spectrometry and Auger electron spectroscopy to compare the atomic concentrations. Atom probe tomography, a characterization technique with sub-nanometer resolution, was used to obtain three-dimensional elemental mapping and the compositional distribution at the grain boundaries (GBs). GBs are identified by Na increment accompanied by Cu depletion and In enrichment. Segregation of Na atoms along the GB had a beneficial effect on cell performance. Comparative analyses of different CIGS absorber layers using various analytical techniques provide us with understanding of the compositional distributions and structures of high efficiency CIGS thin films in solar cells.

Scattering of particles in the presence of harmonic confinement perturbed by a complex absorbing potential

NASA Astrophysics Data System (ADS)

Maghari, A.; Kermani, M. M.

2018-04-01

A system of two interacting atoms confined in 1D harmonic trap and perturbed by an absorbing boundary potential is studied using the Lippmann-Schwinger formalism. The atom-atom interaction potential was considered as a nonlocal separable model. The perturbed absorbing boundary potential was also assumed in the form of Scarf II complex absorbing potential. The model is used for the study of 1D optical lattices that support the trapping of a pair atom within a unit cell. Moreover, it allows to describe the scattering particles in a tight smooth trapping surface and to analyze the bound and resonance states. The analytical expressions for wavefunctions and transition matrix as well as the absorption probabilities are calculated. A demonstration of how the complex absorbing potential affecting the bound states and resonances of particles confined in a harmonic trap is described.

Reaction pathways in atomistic models of thin film growth

NASA Astrophysics Data System (ADS)

Lloyd, Adam L.; Zhou, Ying; Yu, Miao; Scott, Chris; Smith, Roger; Kenny, Steven D.

2017-10-01

The atomistic processes that form the basis of thin film growth often involve complex multi-atom movements of atoms or groups of atoms on or close to the surface of a substrate. These transitions and their pathways are often difficult to predict in advance. By using an adaptive kinetic Monte Carlo (AKMC) approach, many complex mechanisms can be identified so that the growth processes can be understood and ultimately controlled. Here the AKMC technique is briefly described along with some special adaptions that can speed up the simulations when, for example, the transition barriers are small. Examples are given of such complex processes that occur in different material systems especially for the growth of metals and metallic oxides.

A theoretical investigation on the neutral Cu(I) phosphorescent complexes with azole-based and phosphine mixed ligand

NASA Astrophysics Data System (ADS)

Ding, Xiao-Li; Shen, Lu; Zou, Lu-Yi; Ma, Ming-Shuo; Ren, Ai-Min

2018-04-01

A theoretical study on a series of neutral heteroleptic Cu(I) complexes with different azole-pyridine-based N^N ligands has been presented to get insight into the effect of various nitrogen atoms in the azole ring on photophysical properties. The results reveal that the highest occupied molecular orbital (HOMO) levels and the emission wavelengths of these complexes are mainly governed by the nitrogen atom number in azole ring. With the increasing number of nitrogen atom , the electron density distribution of HOMO gradually extend from the N^N ligand to the whole molecule, meanwhile, the improved contribution from Cu(d) orbits in HOMO results in an effective mixing of various charge transfermodes, and hence, the fast radiative decay(kr) and the slow non-radiative decay rate(knr) are achieved. The photoluminescence quantum yield (PLQY) show an apparent dependence on the nitrogen atom number in the five-membered nitrogen heterocycles. However, the increasing number of nitrogen atoms is not necessary for increasing PLQY. The complex 3 with 1,2,4-triazole-pyridine-based N^N ligands is considered to be a potential emitter with high phosphorescence efficiency. Finally, we hope that our investigations will contribute to systematical understanding and guiding for material molecular engineering.

In silico carbon molecular beam epitaxial growth of graphene on the h-BN substrate: carbon source effect on van der Waals epitaxy

NASA Astrophysics Data System (ADS)

Lee, Jonghoon; Varshney, Vikas; Park, Jeongho; Farmer, Barry L.; Roy, Ajit K.

2016-05-01

Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested.Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested. Electronic supplementary information (ESI) available: Three movie files: 3mer-physorption.mpg and 3mer-chemisorption.mpg feature examples of the adsorption state sampling of a carbon trimer on the heated h-BN substrate as mentioned in the ``Single Molecule Adsorption Study'' section. In 3mer-film-growth.mpg, an instance of honey comb formation during the initial phase of graphene growth simulation using a carbon trimer beam is captured. An initially sp hybridized carbon atom (red colored) becomes sp2 hybridized as a result of additional covalent bonding with the impinging carbon trimer. As the bond angle around the red carbon changes from 180 degree (sp) to 120 degree (sp2), nearby carbon atoms enclose to form a hexagon structure composed of 6 carbon atoms. See DOI: 10.1039/c6nr01396a

High performance computing in biology: multimillion atom simulations of nanoscale systems

PubMed Central

Sanbonmatsu, K. Y.; Tung, C.-S.

2007-01-01

Computational methods have been used in biology for sequence analysis (bioinformatics), all-atom simulation (molecular dynamics and quantum calculations), and more recently for modeling biological networks (systems biology). Of these three techniques, all-atom simulation is currently the most computationally demanding, in terms of compute load, communication speed, and memory load. Breakthroughs in electrostatic force calculation and dynamic load balancing have enabled molecular dynamics simulations of large biomolecular complexes. Here, we report simulation results for the ribosome, using approximately 2.64 million atoms, the largest all-atom biomolecular simulation published to date. Several other nanoscale systems with different numbers of atoms were studied to measure the performance of the NAMD molecular dynamics simulation program on the Los Alamos National Laboratory Q Machine. We demonstrate that multimillion atom systems represent a 'sweet spot' for the NAMD code on large supercomputers. NAMD displays an unprecedented 85% parallel scaling efficiency for the ribosome system on 1024 CPUs. We also review recent targeted molecular dynamics simulations of the ribosome that prove useful for studying conformational changes of this large biomolecular complex in atomic detail. PMID:17187988

Quantum chemical calculations and experimental investigations on 2-aminobenzoic acid-cyclodiphosph(V)azane derivative and its homo-binuclear Cu(II) complex

NASA Astrophysics Data System (ADS)

El-Gogary, Tarek M.; Alaghaz, Abdel-Nasser M. A.; Ammar, Reda A. A.

2012-03-01

A novel 2-aminobenzoic acid-cyclodiphosph(V)azane ligand H4L and its homo-binuclear Cu(II) complex of the type [Cu2L(H2O)2].2.5 H2O in which L is 1,3-di(-o-pyridyl)-2,4-(dioxo)-2',4'-bis-(2-iminobenzoic acid) cyclodiphosph(V)azane, were synthesized and characterized by different physical techniques. Infrared spectra of the complex indicate deprotonation and coordination of the imine NH and carboxyl COOH groups. It also confirms that nitrogen atom of the pyridine ring contribute to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square-planar geometry for the Cu(II) complex. The elemental analyses and thermogravimetric results have justified the [Cu2L(H2O)2]·2.5H2O composition of the complex. Quantum chemical calculations were utilized to explore the electronic structure and stability of the H4L as well as the binuclear Cu(II) complex. Computational studies have been carried out at the DFT-B3LYP/6-31G(d) level of theory on the structural and spectroscopic properties of H4L and its binuclear Cu(II) complex. Different tautomers and geometrical isomers of the ligand were optimized at the ab initio DFT level. Simulated IR frequencies were scaled and compared with that experimentally measured. TD-DFT method was used to compute the UV-VIS spectra which show good agreement with measured electronic spectra.

Growth, intermixing, and surface phase formation for zinc tin oxide nanolaminates produced by atomic layer deposition

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

Hägglund, Carl, E-mail: carl.hagglund@angstrom.uu.se; Grehl, Thomas; Brongersma, Hidde H.

2016-03-15

A broad and expanding range of materials can be produced by atomic layer deposition at relatively low temperatures, including both oxides and metals. For many applications of interest, however, it is desirable to grow more tailored and complex materials such as semiconductors with a certain doping, mixed oxides, and metallic alloys. How well such mixed materials can be accomplished with atomic layer deposition requires knowledge of the conditions under which the resulting films will be mixed, solid solutions, or laminated. The growth and lamination of zinc oxide and tin oxide is studied here by means of the extremely surface sensitivemore » technique of low energy ion scattering, combined with bulk composition and thickness determination, and x-ray diffraction. At the low temperatures used for deposition (150 °C), there is little evidence for atomic scale mixing even with the smallest possible bilayer period, and instead a morphology with small ZnO inclusions in a SnO{sub x} matrix is deduced. Postannealing of such laminates above 400 °C however produces a stable surface phase with a 30% increased density. From the surface stoichiometry, this is likely the inverted spinel of zinc stannate, Zn{sub 2}SnO{sub 4}. Annealing to 800 °C results in films containing crystalline Zn{sub 2}SnO{sub 4}, or multilayered films of crystalline ZnO, Zn{sub 2}SnO{sub 4}, and SnO{sub 2} phases, depending on the bilayer period.« less

Non-covalent interactions across organic and biological subsets of chemical space: Physics-based potentials parametrized from machine learning

NASA Astrophysics Data System (ADS)

Bereau, Tristan; DiStasio, Robert A.; Tkatchenko, Alexandre; von Lilienfeld, O. Anatole

2018-06-01

Classical intermolecular potentials typically require an extensive parametrization procedure for any new compound considered. To do away with prior parametrization, we propose a combination of physics-based potentials with machine learning (ML), coined IPML, which is transferable across small neutral organic and biologically relevant molecules. ML models provide on-the-fly predictions for environment-dependent local atomic properties: electrostatic multipole coefficients (significant error reduction compared to previously reported), the population and decay rate of valence atomic densities, and polarizabilities across conformations and chemical compositions of H, C, N, and O atoms. These parameters enable accurate calculations of intermolecular contributions—electrostatics, charge penetration, repulsion, induction/polarization, and many-body dispersion. Unlike other potentials, this model is transferable in its ability to handle new molecules and conformations without explicit prior parametrization: All local atomic properties are predicted from ML, leaving only eight global parameters—optimized once and for all across compounds. We validate IPML on various gas-phase dimers at and away from equilibrium separation, where we obtain mean absolute errors between 0.4 and 0.7 kcal/mol for several chemically and conformationally diverse datasets representative of non-covalent interactions in biologically relevant molecules. We further focus on hydrogen-bonded complexes—essential but challenging due to their directional nature—where datasets of DNA base pairs and amino acids yield an extremely encouraging 1.4 kcal/mol error. Finally, and as a first look, we consider IPML for denser systems: water clusters, supramolecular host-guest complexes, and the benzene crystal.

Coordination of XeF2 to calcium and cadmium hexafluorophosphates(V).

PubMed

Bunic, Tina; Tavcar, Gasper; Tramsek, Melita; Zemva, Boris

2006-02-06

[M(XeF2)5](PF6)2 (M = Ca, Cd) complexes were prepared by the reaction of MF2 and XeF2 under pressure of gaseous PF5 in anhydrous HF as solvent. The coordination sphere of the Ca atom consists of nine fluorine atoms: three from two PF6(-) units (one bidentate and one monodentate) and one from each of six XeF2 molecules. The coordination sphere of the Cd atom consists of eight fluorine atoms: one from each of two PF6(-) units and one from each of six XeF2 molecules. Two of the XeF2 ligands about M in each compound are bridging ligands and are each linked to two M, generating infinite (-M-F-Xe-F-M-F-Xe-F-) chains along the b-axis in the Ca salt and along the c-axis in the Cd compound. The Cd2+ cation is smaller and more electronegative than the Ca2+ cation. These differences account for the higher F ligand coordination in the Ca2+ salt and for other structural features that distinguish them. The different stoichiometry of the PF6(-) salts when compared with their AsF6(-) analogues, which have the composition [M(XeF2)4](AsF6)2 (M = Ca, Cd), is in accord with the lower F ligand charge in the AsF6(-) when compared with that in the PF6(-) compound. Indeed, the AsF6(-) ligand charges appear to be similar to those in the XeF2-bridged species.

Ortho-para interconversion in cation-water complexes: The case of V + (H 2 O) and Nb + (H 2 O) clusters

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

Ward, T. B.; Miliordos, E.; Carnegie, P. D.

Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O–H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 1:3 intensity ratios for K = even:odd levels for independent ortho:para nuclearmore » spin states are missing for some complexes. We relied on highly correlated internally contracted Multi-Reference Configuration Interaction (icMRCI) and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to quasi-C2v symmetry with significant probability off the C2 axis, thus explaining the reduced A values. Both vanadium and iobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 sec-1).« less

Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters.

PubMed

Ward, T B; Miliordos, E; Carnegie, P D; Xantheas, S S; Duncan, M A

2017-06-14

Vanadium and niobium cation-water complexes, V + (H 2 O) and Nb + (H 2 O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O-H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 3:1 intensity ratios for K = odd:even levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted multi-reference configuration interaction and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to the quasi-C 2v symmetry with a significant probability off the C 2 axis, thus explaining the reduced A values. Both vanadium and niobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 10 6 s -1 ).

Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters

NASA Astrophysics Data System (ADS)

Ward, T. B.; Miliordos, E.; Carnegie, P. D.; Xantheas, S. S.; Duncan, M. A.

2017-06-01

Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O-H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 3:1 intensity ratios for K = odd:even levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted multi-reference configuration interaction and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to the quasi-C2v symmetry with a significant probability off the C2 axis, thus explaining the reduced A values. Both vanadium and niobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 s-1).

Structural and morphological study of chemically synthesized CdSe thin films

NASA Astrophysics Data System (ADS)

Agrawal, P.; Singh, Randhir; Sharma, Jeewan; Sachdeva, M.; Singh, Anupinder; Bhargava, A.

2018-05-01

Nanocrystalline CdSe thin films were prepared by Chemical Bath Deposition (CBD) method using potassium nitrilo-triacetic acid cadmium complex and sodium selenosulphite. The as deposited films were red in color, uniform and well adherent to the glass substrate. These films were strongly dependent on the deposition parameters such as bath composition, deposition temperature and time. Films were annealed at 350 °C for four hours. The morphological, structural and optical properties were studied using X-ray diffraction (XRD), UV-VIS spectrophotometer measurements, scanning electron microscopy and atomic force microscopy. The XRD analysis confirmed that films are predominantly in hexagonal phase. Scanning electron micrograph shows that the grains are uniformly spread all over the film and each grain contains many nanocrystals with spherical shapes.

High Performance High Temperature Thermoelectric Composites with Metallic Inclusions

NASA Technical Reports Server (NTRS)

Firdosy, Samad A. (Inventor); Kaner, Richard B. (Inventor); Ma, James M. (Inventor); Fleurial, Jean-Pierre (Inventor); Star, Kurt (Inventor); Bux, Sabah K. (Inventor); Ravi, Vilupanur A. (Inventor)

2017-01-01

The present invention provides a composite thermoelectric material. The composite thermoelectric material can include a semiconductor material comprising a rare earth metal. The atomic percent of the rare earth metal in the semiconductor material can be at least about 20%. The composite thermoelectric material can further include a metal forming metallic inclusions distributed throughout the semiconductor material. The present invention also provides a method of forming this composite thermoelectric material.

Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

PubMed

Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

2015-07-28

The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy.

Analytical dependence of effective atomic number on the elemental composition of matter and radiation energy in the range 10-1000 keV

NASA Astrophysics Data System (ADS)

Eritenko, A. N.; Tsvetiansky, A. L.; Polev, A. A.

2018-01-01

In the present paper, a universal analytical dependence of effective atomic number on the composition of matter and radiation energy is proposed. This enables one to consider the case of a strong difference in the elemental composition with respect to their atomic numbers over a wide energy range. The contribution of photoelectric absorption and incoherent and coherent scattering during the interaction between radiation and matter is considered. For energy values over 40 keV, the contribution of coherent scattering does not exceed approximately 10% that can be neglected at a further consideration. The effective atomic numbers calculated on the basis of the proposed relationships are compared to the results of calculations based on other methods considered by different authors on the basis of experimental and tabulated data on mass and atomic attenuation coefficients. The examination is carried out for both single-element (e.g., 6C, 14Si, 28Cu, 56Ba, and 82Pb) and multi-element materials. Calculations are performed for W1-xCux alloys (x = 0.35; x = 0.4), PbO, ther moluminescent dosimetry compounds (56Ba, 48Cd, 41Sr, 20Ca, 12Mg, and 11Na), and SO4 in a wide energy range. A case with radiation energy between the K- and L1-absorption edges is considered for 82Pb, 74W, 56Ba, 48Cd, and 38Sr. This enables to substantially simplify the calculation of the atomic number and will be useful in technical and scientific fields related to the interaction between X-ray/gamma radiation and matter.

Activity Descriptor Identification for Oxygen Reduction on Platinum-Based Bimetallic Nanoparticles: In Situ Observation of the Linear Composition–Strain–Activity Relationship

PubMed Central

2016-01-01

Despite recent progress in developing active and durable oxygen reduction catalysts with reduced Pt content, lack of elegant bottom-up synthesis procedures with knowledge over the control of atomic arrangement and morphology of the Pt–alloy catalysts still hinders fuel cell commercialization. To follow a less empirical synthesis path for improved Pt-based catalysts, it is essential to correlate catalytic performance to properties that can be easily controlled and measured experimentally. Herein, using Pt–Co alloy nanoparticles (NPs) with varying atomic composition as an example, we show that the atomic distribution of Pt-based bimetallic NPs under operating conditions is strongly dependent on the initial atomic ratio by employing microscopic and in situ spectroscopic techniques. The PtxCo/C NPs with high Co content possess a Co concentration gradient such that Co is concentrated in the core and gradually depletes in the near-surface region, whereas the PtxCo/C NPs with low Co content possess a relatively uniform distribution of Co with low Co population in the near-surface region. Despite their different atomic structure, the oxygen reduction reaction (ORR) activity of PtxCo/C and Pt/C NPs is linearly related to the bulk average Pt–Pt bond length (RPt–Pt). The RPt–Pt is further shown to contract linearly with the increase in Co/Pt composition. These linear correlations together demonstrate that (i) the improved ORR activity of PtxCo/C NPs over pure Pt NPs originates predominantly from the compressive strain and (ii) the RPt–Pt is a valid strain descriptor that bridges the activity and atomic composition of Pt-based bimetallic NPs. PMID:25559440

Superfluid transition temperature in a trapped gas of Fermi atoms with a Feshbach resonance

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

Ohashi, Y.; Institute of Physics, University of Tsukuba, Ibaraki 305; Griffin, A.

2003-03-01

We investigate strong-coupling effects on the superfluid phase transition in a gas of Fermi atoms with a Feshbach resonance. The Feshbach resonance describes a composite quasiboson that can give rise to an additional pairing interaction between the Fermi atoms. This attractive interaction becomes stronger as the threshold energy 2{nu} of the Feshbach resonance two-particle bound state is lowered. In a recent paper, we showed that in the uniform Fermi gas, this tunable pairing interaction naturally leads to a crossover from a BCS state to a Bose-Einstein condensate (BEC) of the Nozieres and Schmitt-Rink kind, in which the BCS-type superfluid phasemore » transition continuously changes into the BEC type as the threshold energy is decreased. In this paper, we extend our previous work by including the effect of a harmonic trap potential, treated within the local-density approximation. We also give results for both weak and strong coupling to the Feshbach resonance. We show that the BCS-BEC crossover phenomenon strongly modifies the shape of the atomic density profile at the superfluid phase-transition temperature T{sub c}, reflecting the change of the dominant particles going from Fermi atoms to composite bosons. In the BEC regime, these composite bosons are shown to first appear well above T{sub c}. We also discuss the 'phase diagram' above T{sub c} as a function of the tunable threshold energy 2{nu}. We introduce a characteristic temperature T*(2{nu}) describing the effective crossover in the normal phase from a Fermi gas of atoms to a gas of stable molecules.« less

Structural and magnetic evolution of bimetallic MnAu clusters driven by asymmetric atomic migration.

PubMed

Wei, Xiaohui; Zhou, Rulong; Lefebvre, Williams; He, Kai; Le Roy, Damien; Skomski, Ralph; Li, Xingzhong; Shield, Jeffrey E; Kramer, Matthew J; Chen, Shuang; Zeng, Xiao Cheng; Sellmyer, David J

2014-03-12

The nanoscale structural, compositional, and magnetic properties are examined for annealed MnAu nanoclusters. The MnAu clusters order into the L1(0) structure, and monotonic size-dependences develop for the composition and lattice parameters, which are well reproduced by our density functional theory calculations. Simultaneously, Mn diffusion forms 5 Å nanoshells on larger clusters inducing significant magnetization in an otherwise antiferromagnetic system. The differing atomic mobilities yield new cluster nanostructures that can be employed generally to create novel physical properties.

Cobalt dipicolinate complexes with nicotinamide and isonicotinamide ligands: Syntheses, crystal structures, spectroscopic, thermal and voltammetric studies

NASA Astrophysics Data System (ADS)

Uçar, İbrahim; Bulut, Ahmet; Karadağ, Ahmet; Kazak, Canan

2007-06-01

Two new dipicolinate complexes of cobalt, [Co(dpc)(na)(H 2O) 2]·H 2O ( 1) and [Co(dpc)(ina)(H 2O) 2] ( 2) [dpc is dipicolinate or pyridine-2,6-dicarboxylate, na is nicotinamide and ina is isonicotinamide], have been prepared and characterized by thermal analysis, IR spectroscopy and X-ray diffraction techniques. The complex ( 1) crystallizes in triclinic system, whereas the complex ( 2) crystallizes in monoclinic system. The Co(II) ion in both complexes is bonded to dpc ligand through pyridine N atom together with one O atom of each carboxylate group, two aqua ligands and N pyridine atom of na ( 1) or ina ( 2), forming the distorted octahedral geometry. The complex molecules ( 1) and ( 2) are connected via N sbnd H⋯O and O sbnd H⋯O hydrogen bonds. The voltammetric behaviour of complexes ( 1) and ( 2) was also investigated in DMSO (dimethylsulfoxide) solution by cyclic voltammetry using n-Bu 4NClO 4 supporting electrolyte. The complexes exhibit only metal centered electroactivity in the potential ±1.25 V versus Ag/AgCl reference electrode.

Hydrogen-impurity complexes in III V semiconductors

NASA Astrophysics Data System (ADS)

Ulrici, W.

2004-12-01

This review summarizes the presently available knowledge concerning hydrogen-impurity complexes in III-V compounds. The impurities form shallow acceptors on group III sites (Be, Zn, Cd) and on group V sites (C, Si, Ge) as well as shallow donors on group V sites (S, Se, Te) and on group III sites (Si, Sn). These complexes are mainly revealed by their hydrogen stretching modes. Therefore, nearly all information about their structure and dynamic properties is derived from vibrational spectroscopy. The complexes of shallow impurities with hydrogen have been most extensively investigated in GaAs, GaP and InP. This holds also for Mg-H in GaN. The complexes exhibit a different microscopic structure, which is discussed in detail. The isoelectronic impurity nitrogen, complexed with one hydrogen atom, is investigated in detail in GaAs and GaP. Those complexes can exist in different charge states. The experimental results such as vibrational frequencies, the microscopic structure and the activation energy for reorientation for many of these complexes are in very good agreement with results of ab initio calculations. Different types of oxygen-hydrogen complexes in GaAs and GaP are described, with one hydrogen atom or two hydrogen atoms bonded to oxygen. Three of these complexes in GaAs were found to be electrically active.

Development of new portable miniaturize solid phase microextraction of silver-APDC complex using micropipette tip in-syringe system couple with electrothermal atomic absorption spectrometry.

PubMed

Naeemullah; Kazi, Tasneem Gul; Afridi, Hassan Imran; Shah, Faheem; Arain, Sadaf Sadia; Arain, Salma Aslam; Panhwar, Abdul Haleem; Arain, Mariam Shahzadi; Samoon, Muhammad Kashif

2016-02-05

An innovative and simple miniaturized solid phase microextraction (M-SPME) method, was developed for preconcentration and determination of silver(I) in the fresh and waste water samples. For M-SPME, a micropipette tip packed with activated carbon cloth (ACC) as sorbent, in a syringe system. The size, morphology and elemental composition of ACC before and after adsorption of analyte have been characterized by scanning electron microscopy and energy dispersive spectroscopy. The sample solution treated with a complexing reagent, ammonium pyrrolidine dithiocarbamate (APDC), was drawn into the syringe filled with ACC and dispensed manually for 2 to 10 aspirating/dispensing cycle. Then the Ag- complex sorbed on the ACC in micropipette was quantitatively eluted by drawing and dispensing of different concentrations of acids for 2 to 5 aspirating/dispensing cycles. The extracted Ag ions with modifier were injected directly into the electrothermal atomic absorption spectrometry for analysis. The influence of different variables on the extraction efficiency, including the concentration of ligand, pH, sample volume, eluent type, concentration and volume was investigated. Validity and accuracy of the developed method was checked by the standard addition method. Reliability of the proposed methodology was checked by the relative standard deviation (%RSD), which was found to be <5%. Under the optimized experimental variables, the limits of detection (LOD) and enhancement factors (EF), were obtained to be 0.86 ng L(-1) and 120, respectively. The proposed method was successfully applied for the determination of trace levels of silver ions in fresh and waste water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Mg(1 + x)Ir(1 - x) (x = 0, 0.037 and 0.054), a binary intermetallic compound with a new orthorhombic structure type determined from powder and single-crystal X-ray diffraction.

PubMed

Cerný, Radovan; Renaudin, Guillaume; Favre-Nicolin, Vincent; Hlukhyy, Viktor; Pöttgen, Rainer

2004-06-01

The new binary compound Mg(1 + x)Ir(1 - x) (x = 0-0.054) was prepared by melting the elements in the Mg:Ir ratio 2:3 in a sealed tantalum tube under an argon atmosphere in an induction furnace (single crystals) or by annealing cold-pressed pellets of the starting composition Mg:Ir 1:1 in an autoclave under an argon atmosphere (powder sample). The structure was independently solved from high-resolution synchrotron powder and single-crystal X-ray data: Pearson symbol oC304, space group Cmca, lattice parameters from synchrotron powder data a = 18.46948 (6), b = 16.17450 (5), c = 16.82131 (5) A. Mg(1 + x)Ir(1 - x) is a topologically close-packed phase, containing 13 Ir and 12 Mg atoms in the asymmetric unit, and has a narrow homogeneity range. Nearly all the atoms have Frank-Kasper-related coordination polyhedra, with the exception of two Ir atoms, and this compound contains the shortest Ir-Ir distances ever observed. The solution of a rather complex crystal structure from powder diffraction, which was fully confirmed by the single-crystal method, shows the power of powder diffraction in combination with the high-resolution data and the global optimization method.

Lattice instability and elastic response of metastable Mo1-xSix thin films

NASA Astrophysics Data System (ADS)

Fillon, A.; Jaouen, C.; Michel, A.; Abadias, G.; Tromas, C.; Belliard, L.; Perrin, B.; Djemia, Ph.

2013-11-01

We present a detailed experimental study on Mo1-xSix thin films, an archetypal alloy system combining metallic and semiconductor materials. The correlations between structure and elastic response are comprehensively investigated. We focus on assessing trends for understanding the evolution of elastic properties upon Si alloying in relation to the structural state (crystalline vs amorphous), bonding character (metallic vs covalent), and local atomic environment. By combining picosecond ultrasonics and Brillouin light scattering techniques, a complete set of effective elastic constants and mechanical moduli (B, G, E) is provided in the whole compositional range, covering bcc solid solutions (x < 0.20) and the amorphous phase (0.20 < x < 1.0). A softening of the shear and Young moduli and a concomitant decrease of the Debye temperature is revealed for crystalline alloys, with a significant drop being observed at x ˜ 0.2 corresponding to the limit of crystal lattice stability. Amorphous alloys exhibit a more complex elastic response, related to variations in coordination number, atomic volume, and bonding state, depending on Si content. Finally, distinct evolutions of the G/B ratio as a function of Cauchy pressure are reported for crystalline and amorphous alloys, enabling us to identify signatures of ductility vs brittleness in the features of the local atomic environment. This work paves the way to design materials with improved mechanical properties by appropriate chemical substitution or impurity incorporation during thin-film growth.

Lattice thermal conductivity of multi-component alloys

DOE PAGES

Caro, Magdalena; Béland, Laurent K.; Samolyuk, German D.; ...

2015-06-12

High entropy alloys (HEA) have unique properties including the potential to be radiation tolerant. These materials with extreme disorder could resist damage because disorder, stabilized by entropy, is the equilibrium thermodynamic state. Disorder also reduces electron and phonon conductivity keeping the damage energy longer at the deposition locations, eventually favoring defect recombination. In the short time-scales related to thermal spikes induced by collision cascades, phonons become the relevant energy carrier. In this paper, we perform a systematic study of phonon thermal conductivity in multiple component solid solutions represented by Lennard-Jones (LJ) potentials. We explore the conditions that minimize phonon meanmore » free path via extreme alloy complexity, by varying the composition and the elements (differing in mass, atomic radii, and cohesive energy). We show that alloy complexity can be tailored to modify the scattering mechanisms that control energy transport in the phonon subsystem. Finally, our analysis provides a qualitative guidance for the selection criteria used in the design of HEA alloys with low phonon thermal conductivity.« less

Three-channel false colour AFM images for improved interpretation of complex surfaces: a study of filamentous cyanobacteria.

PubMed

Kurk, Toby; Adams, David G; Connell, Simon D; Thomson, Neil H

2010-05-01

Imaging signals derived from the atomic force microscope (AFM) are typically presented as separate adjacent images with greyscale or pseudo-colour palettes. We propose that information-rich false-colour composites are a useful means of presenting three-channel AFM image data. This method can aid the interpretation of complex surfaces and facilitate the perception of information that is convoluted across data channels. We illustrate this approach with images of filamentous cyanobacteria imaged in air and under aqueous buffer, using both deflection-modulation (contact) mode and amplitude-modulation (tapping) mode. Topography-dependent contrast in the error and tertiary signals aids the interpretation of the topography signal by contributing additional data, resulting in a more detailed image, and by showing variations in the probe-surface interaction. Moreover, topography-independent contrast and topography-dependent contrast in the tertiary data image (phase or friction) can be distinguished more easily as a consequence of the three dimensional colour-space.

Metabolic studies of an orally active platinum anticancer drug by liquid chromatography-electrospray ionization mass spectrometry.

PubMed

Poon, G K; Raynaud, F I; Mistry, P; Odell, D E; Kelland, L R; Harrap, K R; Barnard, C F; Murrer, B A

1995-09-29

Bis(acetato)amminedichloro(cyclohexylamine) platinum(IV) (JM216) is a new orally administered platinum complex with antitumor properties, and is currently undergoing phase II clinical trials. When JM216 was incubated with human plasma ultrafiltrate, 93% of the platinum species were protein-bound and 7% were unbound. The unbound platinum complexes in the ultrafiltrates of human plasma were analysed using a liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) method. Apart from the parent drug, four metabolites were identified and characterised. These include JM118 [amminedichloro(cyclohexylamine) platinum(II)], JM383 [bis(acetato)ammine(cyclohexylamine)dihydroxo platinum(IV)] and the two isomers JM559 and JM518 [bis(acetato)amminechloro(cyclohexylamine) hydroxo platinum(IV)]. Their elemental compositions were determined by accurate mass measurement during the LC analysis, to confirm their identities. Quantitation of these metabolites by off-line LC atomic absorption spectroscopy demonstrated that JM118 is the major metabolite in plasma from patients receiving JM216 treatment.

Structure determination in 55-atom Li-Na and Na-K nanoalloys.

PubMed

Aguado, Andrés; López, José M

2010-09-07

The structure of 55-atom Li-Na and Na-K nanoalloys is determined through combined empirical potential (EP) and density functional theory (DFT) calculations. The potential energy surface generated by the EP model is extensively sampled by using the basin hopping technique, and a wide diversity of structural motifs is reoptimized at the DFT level. A composition comparison technique is applied at the DFT level in order to make a final refinement of the global minimum structures. For dilute concentrations of one of the alkali atoms, the structure of the pure metal cluster, namely, a perfect Mackay icosahedron, remains stable, with the minority component atoms entering the host cluster as substitutional impurities. At intermediate concentrations, the nanoalloys adopt instead a core-shell polyicosahedral (p-Ih) packing, where the element with smaller atomic size and larger cohesive energy segregates to the cluster core. The p-Ih structures show a marked prolate deformation, in agreement with the predictions of jelliumlike models. The electronic preference for a prolate cluster shape, which is frustrated in the 55-atom pure clusters due to the icosahedral geometrical shell closing, is therefore realized only in the 55-atom nanoalloys. An analysis of the electronic densities of states suggests that photoelectron spectroscopy would be a sufficiently sensitive technique to assess the structures of nanoalloys with fixed size and varying compositions.

12. Architectural Floor Plans, 233S, U.S. Atomic Energy Commission, Hanford ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

12. Architectural Floor Plans, 233-S, U.S. Atomic Energy Commission, Hanford Atomic Products Operations, General Electric Company, Dwg. H-2-30464, 1956. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

11. Architectural ELevations & Sections, 233S, U.S. Atomic Energy Commission, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

11. Architectural ELevations & Sections, 233-S, U.S. Atomic Energy Commission, Hanford Atomic Products Operations, General Electric Company, Dwg. No. H-2-30465, 1956. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

Atomic layer deposition and properties of ZrO2/Fe2O3 thin films

PubMed Central

Seemen, Helina; Ritslaid, Peeter; Rähn, Mihkel; Tamm, Aile; Kukli, Kaupo; Kasikov, Aarne; Link, Joosep; Stern, Raivo; Dueñas, Salvador; Castán, Helena; García, Héctor

2018-01-01

Thin solid films consisting of ZrO2 and Fe2O3 were grown by atomic layer deposition (ALD) at 400 °C. Metastable phases of ZrO2 were stabilized by Fe2O3 doping. The number of alternating ZrO2 and Fe2O3 deposition cycles were varied in order to achieve films with different cation ratios. The influence of annealing on the composition and structure of the thin films was investigated. Additionally, the influence of composition and structure on electrical and magnetic properties was studied. Several samples exhibited a measurable saturation magnetization and most of the samples exhibited a charge polarization. Both phenomena were observed in the sample with a Zr/Fe atomic ratio of 2.0. PMID:29441257

Versatile chelating behavior of benzil bis(thiosemicarbazone) in zinc, cadmium, and nickel complexes.

PubMed

López-Torres, Elena; Mendiola, Ma Antonia; Pastor, César J; Pérez, Beatriz Souto

2004-08-23

Reactions of benzil bis(thiosemicarbazone), LH(6), with M(NO(3))(2).nH(2)O (M = Zn, Cd, and Ni), in the presence of LiOH.H(2)O, show the versatile behavior of this molecule. The structure of the ligand, with the thiosemicarbazone moieties on opposite sides of the carbon backbone, changes to form complexes by acting as a chelating molecule. Complexes of these metal ions with empirical formula [MLH(4)] were obtained, although they show different molecular structures depending on their coordinating preferences. The zinc complex is the first example of a crystalline coordination polymer in which a bis(thiosemicarbazone) acts as bridging ligand, through a nitrogen atom, giving a 1D polymeric structure. The coordination sphere is formed by the imine nitrogen and sulfur atoms, and the remaining position, in a square-based pyramid, is occupied by an amine group of another ligand. The cadmium derivative shows the same geometry around the metal ion but consists of a dinuclear structure with sulfur atoms acting as a bridge between the metal ions. However, in the nickel complex LH(6) acts as a N(2)S(2) ligand yielding a planar structure for the nickel atom. The ligand and its complexes have been characterized by X-ray crystallography, microanalysis, mass spectrometry, IR, (1)H, and (13)C NMR spectroscopies and for the cadmium complex by (113)Cd NMR in solution and in the solid state.

Structure of 1:1 complex of 1-naphthylmethyl ester of monensin A with sodium perchlorate studied by X-ray, FT-IR and ab initio methods

NASA Astrophysics Data System (ADS)

Huczyński, Adam; Janczak, Jan; Brzezinski, Bogumil

2012-12-01

A new crystalline complex formed between 1-naphthylmethyl ester of the naturally occurring antibiotic - monensin A (MON8) with sodium perchlorate has been obtained and studied using X-ray crystallography and FT-IR spectroscopy. The X-ray data of the complex show that MON8 forms a pseudo-cyclic structure stabilised by one weak intramolecular hydrogen bond and the sodium cation co-ordinated by two oxygen atoms of hydroxyl groups and four etheric oxygen atoms in the hydrophilic sphere. Within this structure the oxygen atoms of the ester groups are not involved in the coordination of sodium cation. In contrast to the solid state structure of the complex, in acetonitrile solution an equilibrium between two structures, in which the oxygen atom of the carbonyl ester group is either involved or not involved in the complexation of the sodium cation, is found. In acetonitrile this equilibrium is shifted towards the latter structure i.e. the structure existing in the solid state. The gas-phase structure of [MON8sbnd Na]+ cation as shown the ab initio MO calculations is comparable with the crystal one. Three-dimensional molecular electrostatic potential calculated for the neutral MON8 and [MON8sbnd Na]+ molecules is helpful for understanding the structural aspects of the sodium complex formation.

Using advanced electron microscopy for the characterization of catalytic materials

NASA Astrophysics Data System (ADS)

Pyrz, William D.

Catalysis will continue to be vitally important to the advancement and sustainability of industrialized societies. Unfortunately, the petroleum-based resources that currently fuel the energy and consumer product needs of an advancing society are becoming increasingly difficult and expensive to extract as supplies diminish and the quality of sources degrade. Therefore, the development of sustainable energy sources and the improvement of the carbon efficiency of existing chemical processes are critical. Further challenges require that these initiatives are accomplished in an environmentally friendly fashion since the effects of carbon-based emissions are proving to be a serious threat to global climate stability. In this dissertation, materials being developed for sustainable energy and process improvement initiatives are studied. Our approach is to use materials characterization, namely advanced electron microscopy, to analyze the targeted systems at the nano- or Angstrom-scale with the goal of developing useful relationships between structure, composition, crystalline order, morphology, and catalytic performance. One area of interest is the complex Mo-V-M-O (M=Te, Sb, Ta, Nb) oxide system currently being developed for the selective oxidation/ammoxidation of propane to acrylic acid or acrylonitrile, respectively. Currently, the production of acrylic acid and acrylonitrile rely on propylene-based processes, yet significant cost savings could be realized if the olefin-based feeds could be replaced by paraffin-based ones. The major challenge preventing this feedstock replacement is the development of a suitable paraffin-activating catalyst. Currently, the best candidate is the Mo-V-Nb-Te-O complex oxide catalyst that is composed of two majority phases that are commonly referred to as M1 and M2. However, there is a limited understanding of the roles of each component with respect to how they contribute to catalyst stability and the reaction mechanism. Aberration-corrected electron microscopy was used to systematically examine, atomic column by atomic column, the effect of elemental substitution on the long-range crystalline order, atomic coordinates, and site occupancies of the various formulations such that trends could be developed linking these properties to catalytic yields. To accomplish this task, an algorithm was developed that enabled the direct extraction of atomic coordinates and site occupancies from high-angle annular dark-field (HAADF) images to within 1% and 15% uncertainty, respectively. Furthermore, this general method could be applied to various crystalline systems and may dramatically improve the quality of initial structural models used in Rietveld refinements. Improvement in the quality of starting models may increase the structural and chemical complexity of inorganic structures that can be solved by using "powder methods" alone. In addition to the development of these trends, HAADF analyses also revealed the presence of coherent compositional miscibility gaps, rotational twin domains, and structural intergrowths in the complex Mo-V-M-O oxide system. Other catalytic systems that are addressed in this dissertation include Pd, Ag, and bimetallic Pd-Ag catalysts for the selective hydrogenation of acetylene in excess ethylene, alkali and alkaline earth promoted Ru catalysts for the production of clean hydrogen through the decomposition of ammonia, the production of Pt nanoparticles using dendrimer templates, and Pt-Re bimetallic catalysts for the conversion of glycerol to hydrocarbons and syn gas. In each of these studies, electron microscopy was used as a complimentary tool to synthetic and reaction studies to better understand interactions between the nanoparticles and the support/template, to determine the effect of adding various promoters, or to understand the nanoscale structural and chemical changes associated with the formation of bimetallic nanoparticles. A final area addressed in this dissertation is the interaction between the electron beam and the specimen. In one particular study directed toward the characterization of Ni-Bi nanomaterials, it was discovered that exposure to an intense electron beam initiated particle fragmentation that led to the formation of a field of nanoparticles. Subsequent microscopy studies of the resulting nanoparticle field revealed bimetallic nanoparticles, core-shell structures, Angstrom-scale atomic clusters, and individual atoms that decorated the surrounding carbon substrate. The identification of these structures along with the analysis of the parent material enabled the development of a fragmentation mechanism.

Comparison of the Atomic Oxygen Erosion Depth and Cone Height of Various Materials at Hyperthermal Energy

NASA Technical Reports Server (NTRS)

Waters, Deborah L.; Banks, Bruce A.; Thorson, Stephen D.; deGroh, Kim, K.; Miller, Sharon K.

2007-01-01

Atomic oxygen readily reacts with most spacecraft polymer materials exposed to the low Earth orbital (LEO) environment. If the atomic oxygen arrival comes from a fixed angle of impact, the resulting erosion will foster the development of a change in surface morphology as material thickness decreases. Hydrocarbon and halopolymer materials, as well as graphite, are easily oxidized and textured by directed atomic oxygen in LEO at energies of approx.4.5 eV. What has been curious is that the ratio of cone height to erosion depth is quite different for different materials. The formation of cones under fixed direction atomic oxygen attack may contribute to a reduction in material tensile strength in excess of that which would occur if the cone height to erosion depth ratio was very low because of greater opportunities for crack initiation. In an effort to understand how material composition affects the ratio of cone height to erosion depth, an experimental investigation was conducted on 18 different materials exposed to a hyperthermal energy directed atomic oxygen source (approx.70 eV). The materials were first salt-sprayed to provide microscopic local areas that would be protected from atomic oxygen. This allowed erosion depth measurements to be made by scanning microscopy inspection. The polymers were then exposed to atomic oxygen produced by an end Hall ion source that was operated on pure oxygen. Samples were exposed to an atomic oxygen effective fluence of 1.0x10(exp 20) atoms/sq cm based on Kapton H polyimide erosion. The average erosion depth and average cone height were determined using field emission scanning electron microscopy (FESEM). The experimental ratio of average cone height to erosion depth is compared to polymer composition and other properties.

Roles of Vacancy/Interstitial Diffusion and Segregation in the Microchemistry at Grain Boundaries of Irradiated Fe-Cr-Ni alloys

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

Yang, Ying; Field, Kevin G.; Allen, Todd R.

2016-02-23

A detailed analysis of the diffusion fluxes near and at grain boundaries of irradiated Fe–Cr–Ni alloys, induced by preferential atom-vacancy and atom-interstitial coupling, is presented. The diffusion flux equations were based on the Perks model formulated through the linear theory of the thermodynamics of irreversible processes. The preferential atom-vacancy coupling was described by the mobility model, whereas the preferential atom-interstitial coupling was described by the interstitial binding model. The composition dependence of the thermodynamic factor was modeled using the CALPHAD approach. The calculated fluxes up to 10 dpa suggested the dominant diffusion mechanism for chromium and iron is via vacancy,more » while that for nickel can swing from the vacancy to the interstitial dominant mechanism. The diffusion flux in the vicinity of a grain boundary was found to be greatly modified by the segregation induced by irradiation, leading to the oscillatory behavior of alloy compositions in this region.« less

Atomistic investigation of the structural, transport, and mechanical properties of Cu-Zr metallic glasses

NASA Astrophysics Data System (ADS)

Kumar, Mohit

The unique set of mechanical and magnetic properties possessed by metallic glasses has attracted a lot of recent scientific and technological interest. The development of new metallic glass alloys with improved manufacturability, enhanced properties and higher ductility relies on the fundamental understanding of the interconnections between their atomic structure, glass forming ability (GFA), transport properties, and elastic and plastic deformation mechanisms. This thesis is focused on finding these atomic structure-property relationships in Cu-Zr BMGs using molecular dynamics simulations. In the first study described herein, molecular dynamics simulations of the rapid solidification process over the Cu-Zr compositional domain were conducted to explore inter-dependencies of atomic transport and fragility, elasticity and structural ordering, and GFA. The second study investigated the atomic origins of serration events, which is the characteristic plastic deformation behaviour in BMGs. The combined results of this work suggest that GFA and ductility of metallic glasses could be compositionally tuned.

Composition-dependent metallic glass alloys correlate atomic mobility with collective glass surface dynamics.

PubMed

Nguyen, Duc; Zhu, Zhi-Guang; Pringle, Brian; Lyding, Joseph; Wang, Wei-Hua; Gruebele, Martin

2016-06-22

Glassy metallic alloys are richly tunable model systems for surface glassy dynamics. Here we study the correlation between atomic mobility, and the hopping rate of surface regions (clusters) that rearrange collectively on a minute to hour time scale. Increasing the proportion of low-mobility copper atoms in La-Ni-Al-Cu alloys reduces the cluster hopping rate, thus establishing a microscopic connection between atomic mobility and dynamics of collective rearrangements at a glass surface made from freshly exposed bulk glass. One composition, La60Ni15Al15Cu10, has a surface resistant to re-crystallization after three heating cycles. When thermally cycled, surface clusters grow in size from about 5 glass-forming units to about 8 glass-forming units, evidence of surface aging without crystal formation, although its bulk clearly forms larger crystalline domains. Such kinetically stable glass surfaces may be of use in applications where glassy coatings stable against heating are needed.

On the question of fractal packing structure in metallic glasses

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

Ding, Jun; Asta, Mark; Ritchie, Robert O.

2017-07-25

This work addresses the long-standing debate over fractal models of packing structure in metallic glasses (MGs). Through detailed fractal and percolation analyses of MG structures, derived from simulations spanning a range of compositions and quenching rates, we conclude that there is no fractal atomic-level structure associated with the packing of all atoms or solute-centered clusters. The results are in contradiction with conclusions derived from previous studies based on analyses of shifts in radial distribution function and structure factor peaks associated with volume changes induced by pressure and compositional variations. Here in this paper, the interpretation of such shifts is shownmore » to be challenged by the heterogeneous nature of MG structure and deformation at the atomic scale. Moreover, our analysis in the present work illustrates clearly the percolation theory applied to MGs, for example, the percolation threshold and characteristics of percolation clusters formed by subsets of atoms, which can have important consequences for structure–property relationships in these amorphous materials.« less

Nuclear waste solidification

DOEpatents

Bjorklund, William J.

1977-01-01

High level liquid waste solidification is achieved on a continuous basis by atomizing the liquid waste and introducing the atomized liquid waste into a reaction chamber including a fluidized, heated inert bed to effect calcination of the atomized waste and removal of the calcined waste by overflow removal and by attrition and elutriation from the reaction chamber, and feeding additional inert bed particles to the fluidized bed to maintain the inert bed composition.

Atomic-scale visualization of oxide thin-film surfaces.

PubMed

Iwaya, Katsuya; Ohsawa, Takeo; Shimizu, Ryota; Okada, Yoshinori; Hitosugi, Taro

2018-01-01

The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.

Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

PubMed

Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

2017-10-19

An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

PubMed

Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

2015-05-01

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

Elemental depth profiling in transparent conducting oxide thin film by X-ray reflectivity and grazing incidence X-ray fluorescence combined analysis

NASA Astrophysics Data System (ADS)

Rotella, H.; Caby, B.; Ménesguen, Y.; Mazel, Y.; Valla, A.; Ingerle, D.; Detlefs, B.; Lépy, M.-C.; Novikova, A.; Rodriguez, G.; Streli, C.; Nolot, E.

2017-09-01

The optical and electrical properties of transparent conducting oxide (TCO) thin films are strongly linked with the structural and chemical properties such as elemental depth profile. In R&D environments, the development of non-destructive characterization techniques to probe the composition over the depth of deposited films is thus necessary. The combination of Grazing-Incidence X-ray Fluorescence (GIXRF) and X-ray reflectometry (XRR) is emerging as a fab-compatible solution for the measurement of thickness, density and elemental profile in complex stacks. Based on the same formalism, both techniques can be implemented on the same experimental set-up and the analysis can be combined in a single software in order to refine the sample model. While XRR is sensitive to the electronic density profile, GIXRF is sensitive to the atomic density (i. e. the elemental depth profile). The combination of both techniques allows to get simultaneous information about structural properties (thickness and roughness) as well as the chemical properties. In this study, we performed a XRR-GIXRF combined analysis on indium-free TCO thin films (Ga doped ZnO compound) in order to correlate the optical properties of the films with the elemental distribution of Ga dopant over the thickness. The variation of optical properties due to annealing process were probed by spectroscopic ellipsometry measurements. We studied the evolution of atomic profiles before and after annealing process. We show that the blue shift of the band gap in the optical absorption edge is linked to a homogenization of the atomic profiles of Ga and Zn over the layer after the annealing. This work demonstrates that the combination of the techniques gives insight into the material composition and makes the XRR-GIXRF combined analysis a promising technique for elemental depth profiling.

Mass, radius and composition of the outer crust of nonaccreting cold neutron stars

NASA Astrophysics Data System (ADS)

Hempel, Matthias; Schaffner-Bielich, Jürgen

2008-01-01

The properties and composition of the outer crust of nonaccreting cold neutron stars are studied by applying the model of Baym, Pethick and Sutherland, which was extended by including higher order corrections of the atomic binding, screening, exchange and zero-point energy. The most recent experimental nuclear data from the atomic mass table of Audi, Wapstra and Thibault from 2003 are used. Extrapolation to the drip line is utilized by various state-of-the-art theoretical nuclear models (finite range droplet, relativistic nuclear field and non-relativistic Skyrme Hartree Fock parameterizations). The different nuclear models are compared with respect to the mass and radius of the outer crust for different neutron star configurations and the nuclear compositions of the outer crust.

Influence of helium atoms on the shear behavior of the fiber/matrix interphase of SiC/SiC composite

NASA Astrophysics Data System (ADS)

Jin, Enze; Du, Shiyu; Li, Mian; Liu, Chen; He, Shihong; He, Jian; He, Heming

2016-10-01

Silicon carbide has many attractive properties and the SiC/SiC composite has been considered as a promising candidate for nuclear structural materials. Up to now, a computational investigation on the properties of SiC/SiC composite varying in the presence of nuclear fission products is still missing. In this work, the influence of He atoms on the shear behavior of the SiC/SiC interphase is investigated via Molecular Dynamics simulation following our recent paper. Calculations are carried out on three dimensional models of graphite-like PyC/SiC interphase and amorphous PyC/SiC interphase with He atoms in different regions (the SiC region, the interface region and the PyC region). In the graphite-like PyC/SiC interphase, He atoms in the SiC region have little influence on the shear strength of the material, while both the shear strength and friction strength may be enhanced when they are in the PyC region. Low concentration of He atoms in the interface region of the graphite-like PyC/SiC interphase increases the shear strength, while there is a reduction of shear strength when the He concentration is high due to the switch of sliding plane. In the amorphous PyC/SiC interphase, He atoms can cause the reduction of the shear strength regardless of the regions that He atoms are located. The presence of He atoms may significantly alter the structure of SiC/SiC in the interface region. The influence of He atoms in the interface region is the most significant, leading to evident shear strength reduction of the amorphous PyC/SiC interphase with increasing He concentration. The behaviors of the interphases at different temperatures are studied as well. The dependence of the shear strengths of the two types of interphases on temperatures is studied as well. For the graphite-like PyC/SiC interphase, it is found strongly related to the regions He atoms are located. Combining these results with our previous study on pure SiC/SiC system, we expect this work may provide new insight into the mechanism of interphase evolution when SiC/SiC is applied as nuclear materials.

Hydrogen atom distribution and hydrogen induced site depopulation for the La{sub 2-x}Mg{sub x}Ni{sub 7}-H system

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

Guzik, Matylda N., E-mail: Matylda.Guzik@ife.no; Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller; Hauback, Bjorn C.

2012-02-15

La{sub 2-x}Mg{sub x}Ni{sub 7} and its hydrides/deuterides were investigated by high resolution synchrotron powder X-ray and neutron diffraction. Upon deuteration the single phase sample of the intermetallic compound with the refined composition La{sub 1.63}Mg{sub 0.37}Ni{sub 7} (space group: P6{sub 3}/mmc) expands isotropically, in contrast to the Mg free phase. The hydrogen uptake, {approx}9 D/f.u., is higher than in La{sub 2}Ni{sub 7}D{sub 6.5}. The refined composition accounts for La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8} (beta-phase). Rietveld refinements using the neutron and synchrotron diffraction data suggest that deuterium atoms occupy 5 different interstitial sites within both AB{sub 2} and AB{sub 5} slabs, eithermore » in an ordered or a disordered way. All determined D sites have an occupancy >50% and the shortest D-D contact is 1.96(3) A. It is supposed that a competition between the tendency to form directional bonds and repulsive D-D (H-H) interactions is the most important factor that influences the distribution of deuterium atoms in this structure. A hitherto unknown second, alpha-phase with composition La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 0.56}, crystallizing with the same hexagonal symmetry as La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8}, has been discovered. The unit cell parameters for this D-poor phase differ slightly from those of the intermetallic. Alpha-phase displays only one D site (4f, space group: P6{sub 3}/mmc) occupied >50%, which is not populated in the D-rich beta-phase. This hydrogen/deuterium induced site depopulation can be explained by repulsive D-D (H-H) interactions that are likely to influence non-occupancy of certain interstices in metal lattice when absorbing hydrogen. - Graphical abstract: The detailed D atoms arrangement in La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8} differs significantly from the previously reported La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)}. The present model consists of only five deuterium sites as opposed to nine proposed for La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)}. The reported four remaining deuterium atom positions in La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)} were not found in the investigated La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8}. The five Ni atoms have deuterium among their nearest neighbors, which surround them in a way similar to configurations observed in some complex transition metal hydrides and already reported for metallic hydrides. In the presented deuterium-rich phase, deformed tetrahedron, rigid trigonal pyramids as well as disordered and deformed saddle-like configuration are observed. Highlights: Black-Right-Pointing-Pointer Alpha- and beta-phase for La{sub 2-x}Mg{sub x}Ni{sub 7}-H system have been characterized. Black-Right-Pointing-Pointer Five different interstitial sites are occupied by deuterium/hydrogen atoms in the beta-phase. Black-Right-Pointing-Pointer One D/H site has been determined in the alpha-phase. Black-Right-Pointing-Pointer Deuterium/hydrogen induced site depopulation during phase transformation is observed. Black-Right-Pointing-Pointer Ni atoms tend to have tetrahedral-like D/H atom coordination.« less

Overcoming Matrix Effects in a Complex Sample: Analysis of Multiple Elements in Multivitamins by Atomic Absorption Spectroscopy

ERIC Educational Resources Information Center

Arnold, Randy J.; Arndt, Brett; Blaser, Emilia; Blosser, Chris; Caulton, Dana; Chung, Won Sog; Fiorenza, Garrett; Heath, Wyatt; Jacobs, Alex; Kahng, Eunice; Koh, Eun; Le, Thao; Mandla, Kyle; McCory, Chelsey; Newman, Laura; Pithadia, Amit; Reckelhoff, Anna; Rheinhardt, Joseph; Skljarevski, Sonja; Stuart, Jordyn; Taylor, Cassie; Thomas, Scott; Tse, Kyle; Wall, Rachel; Warkentien, Chad

2011-01-01

A multivitamin tablet and liquid are analyzed for the elements calcium, magnesium, iron, zinc, copper, and manganese using atomic absorption spectrometry. Linear calibration and standard addition are used for all elements except calcium, allowing for an estimate of the matrix effects encountered for this complex sample. Sample preparation using…

Unprecedented H-atom transfer from water to ketyl radicals mediated by Cp(2)TiCl.

PubMed

Paradas, Miguel; Campaña, Araceli G; Marcos, Maria Luisa; Justicia, Jose; Haidour, Ali; Robles, Rafael; Cárdenas, Diego J; Oltra, J Enrique; Cuerva, Juan M

2010-10-07

The H-atom transfer (HAT) from water to ketyl radicals, mediated by titanocene(iii) aqua-complexes, can explain the Ti(III)-promoted reduction of ketones in aqueous medium better than the conventional House mechanism. Moreover, we also report novel evidences supporting the existence of these titanocene(iii) aqua-complexes.

Monochloro non-bridged half-metallocene-type zirconium complexes containing phosphine oxide-(thio)phenolate chelating ligands as efficient ethylene polymerization catalysts.

PubMed

Tang, Xiao-Yan; Wang, Yong-Xia; Liu, San-Rong; Liu, Jing-Yu; Li, Yue-Sheng

2013-01-14

A series of novel monochloro half-zirconocene complexes containing phosphine oxide-(thio)phenolate chelating ligands of the type, ClCp'Zr[X-2-R(1)-4-R(2)-6-(Ph(2)P=O)C(6)H(2)](2) (Cp' = C(5)H(5), 2a: X = O, R(1) = Ph, R(2) = H; 2b: X = O, R(1) = F, R(2) = H; 2c: X = O, R(1) = (t)Bu, R(2) = H; 2d: X = O, R(1) = R(2) = (t)Bu; 2e: X = O, R(1) = SiMe(3), R(2) = H; 2f: X = S, R(1) = SiMe(3), R(2) = H; Cp' = C(5)Me(5), 2g: X = O, R(1) = SiMe(3), R(2) = H), have been synthesized in high yields. These complexes were identified by (1)H {(13)C} NMR and elemental analyses. Structures for 2b, 2c and 2f were further confirmed by X-ray crystallography. Structural characterization of these complexes reveals crowded environments around the zirconium. Complexes 2b and 2c adopt six-coordinate, distorted octahedral geometry around the zirconium center, in which the equatorial positions are occupied by three oxygen atoms of two chelating phosphine oxide-bridged phenolate ligands and a chlorine atom. The cyclopentadienyl ring and one oxygen atom of the ligand are coordinated on the axial position. Complex 2f also folds a six-coordinate, distorted octahedral geometry around the Zr center, consisting of a Cp-Zr-O (in P=O) axis [177.16°] and a distorted plane of two sulfur atoms and one oxygen atom of two chelating phosphine oxide-bridged thiophenolate ligands as well as a chlorine atom. When activated by modified methylaluminoxane (MMAO), all the complexes exhibited high activities towards ethylene polymerization at high temperature (75 °C), giving high molecular weight polymers with unimodal molecular weight distribution. The formation of 14-electron, cationic metal alkyl species might come from the Zr-O (in phenol ring) bond cleavage based on the DFT calculations study.

Copper(II) and zinc(II) as metal-carboxylate coordination complexes based on (1-methyl-1H-benzo[d]imidazol-2-yl) methanol derivative: Synthesis, crystal structure, spectroscopy, DFT calculations and antioxidant activity

NASA Astrophysics Data System (ADS)

Benhassine, Anfel; Boulebd, Houssem; Anak, Barkahem; Bouraiou, Abdelmalek; Bouacida, Sofiane; Bencharif, Mustapha; Belfaitah, Ali

2018-05-01

This work presents a combined experimental and theoretical study of two new metal-carboxylate coordination compounds. These complexes were prepared from (1-methyl-1H-benzimidazol-2-yl)methanol under mild conditions. The structures of the prepared compounds were characterized by single-crystal X-ray analysis, FTIR and UV-Vis spectroscopy. In the Cupper complex, the Cu(II) ion is coordinated by two ligands, which act as bidentate chelator through the non-substituted N and O atoms, and two carboxylicg oxygen atoms, displaying a hexa-coordinated compound in a distorted octahedral geometry, while in the Zinc complex the ligand is ligated to the Zn(II) ion in monodentate fashion through the N atom, and the metal ion is also bonded to carboxylic oxygen atoms. The tetra-coordinated compound displays a distorted tetrahedral shape. The density functional theory calculations are carried out for the determination of the optimized structures. The electronic transitions and fundamental vibrational wave numbers are calculated and are in good agreement with experimental. In addition, the ligand and its Cu(II) and Zn(II) complexes were screened and evaluated for their potential as DPPH radical scavenger.

Crystal structures of palladium(II) ternary complexes of 5-x-2-aminobenzoic acid with 1,10-phenanthroline and their interaction with calf thymus DNA (where X=Cl, Br and I).

PubMed

Wang, Yue; Okabe, Nobuo; Odoko, Mamiko

2005-10-01

The crystal structures of a series of three palladium(II) ternary complexes of 5-halogeno-2-aminobenzoic acid (5-X-AB, where X=Cl, Br and I) with 1,10-phenanthroline [Pd(5-Cl-AB)(phen)] (1), [Pd(5-Br-AB)(phen)] (2) and [Pd(5-I-AB)(phen)] (3) have been determined, and their coordination geometries and the crystal architecture characterized. All of the complexes are an isostructure in which each Pd(II) atom has basically similar square planar coordination geometry. The substitute halogen group at 5-position of AB plays an important role in producing the coordination bonds of the carboxylate and amino groups in which the carboxylate O atom and the amino N atom act as the negative monodentate ligand atoms. The coordination bond distances of O-Pd increase in the order 1<2<3, while those of N-Pd decrease in the same order. The binding of the complexes to the calf thymus DNA has also been studied by the fluorescence method. Each of the complexes shows high binding propensity to DNA which can be reflected as the relative order 1<2<3.

10. Architectural Door Details & Plot Plan, 233S, U.S. Atomic ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

10. Architectural Door Details & Plot Plan, 233-S, U.S. Atomic Energy Commission, Hanford Atomic Products Operations, General Electric Company, Dwg. No. H-2-30469, 1956. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

Synthesis, spectroscopic, thermal and antimicrobial studies of neodymium(III) and samarium(III) complexes derived from tetradentate ligands containing N and S donor atoms

NASA Astrophysics Data System (ADS)

Ain, Qurratul; Pandey, S. K.; Pandey, O. P.; Sengupta, S. K.

2015-04-01

Trivalent lanthanide complexes of the type [Ln(L)Cl(H2O)2] (where Ln = Nd(III) or Sm(III) and LH2 = Schiff bases derived by the condensation of 3-(phenyl/substitutedphenyl)-4-amino-5-mercapto-1,2,4-triazole with diacetyl/benzil) have been synthesized by the reactions of anhydrous lanthanide(III) chloride with Schiff bases in methanol. The structures of the complexes have been proposed on the basis of elemental analysis, electrical conductance, magnetic moment, spectroscopic measurements (IR, 1H, 13C NMR and UV-vis spectra) and X-ray diffraction studies. The spectral data reveal that the Schiff base ligands behave as dibasic tetradentate chelating agents having coordination sites at two thiol sulfur atoms and two azomethine nitrogen atoms. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. All the Schiff bases and their metal complexes have also been screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus and antifungal activities against Aspergillus niger, Curvularia pallescens and Colletotrichum capsici.

Remote Sensing of Icy Galilean Moon Surface and Atmospheric Composition Using Low Energy (1 eV-4 keV) Neutral Atom Imaging

NASA Technical Reports Server (NTRS)

Collier, M. R.; Sittler, E.; Chornay, D.; Cooper, J. F.; Coplan, M.; Johnson, R. E.

2004-01-01

We describe a low energy neutral atom imager suitable for composition measurements Europa and other icy Galilean moons in the Jovian magnetosphere. This instrument employs conversion surface technology and is sensitive to either neutrals converted to negative ions, neutrals converted to positive ions and the positive ions themselves depending on the power supply. On a mission such as the Jupiter Icy Moons Orbiter (JIMO), two back-to-back sensors would be flown with separate power supplies fitted to the neutral atom and iodneutral atom sides. This will allow both remote imaging of 1 eV < E < 4 keV neutrals from icy moon surfaces and atmospheres, and in situ measurements of ions at similar energies in the moon ionospheres and Jovian magnetospheric plasma. The instrument provides composition measurements of the neutrals and ions that enter the spectrometer with a mass resolution dependent on the time-of-flight subsystem and capable of resolving molecules. The lower energy neutrals, up to tens of eV, arise from atoms and molecules sputtered off the moon surfaces and out of the moon atmospheres by impacts of more energetic (keV to MeV) ions from the magnetosphere. Direct Simulation Monte Carlo (DSMC) models are used to convert measured neutral abundances to compositional distributions of primary and trace species in the sputtered surfaces and atmospheres. The escaping neutrals can also be detected as ions after photo- or plasma-ionization and pickup. Higher energy, keV neutrals come from charge exchange of magnetospheric ions in the moon atmospheres and provide information on atmospheric structure. At the jovicentric orbits of the icy moons the presence of toroidal gas clouds, as detected at Europa's orbit, provide M e r opportunities to analyze both the composition of neutrals and ions originating from the moon surfaces, and the characteristics of magnetospheric ions interacting with neutral cloud material. Charge exchange of low energy ions near the moons, and directional distributions of the resultant neutrals, allow indirect global mapping of magnetic field structures around the moons. Temporal variation of the magnetic structures can be linked to induced magnetic fields associated with subsurface oceans.

Metal-ligand bond directionality in the M2-NH3 complexes (M = Cu, Ag and Au)

NASA Astrophysics Data System (ADS)

Eskandari, K.; Ebadinejad, F.

2018-05-01

The metal-ligand bonds in the M2-NH3 complexes (M = Au, Ag and Cu) are directional and the M-M-N angles tend to be linear. Natural energy decomposition analysis (NEDA) and localised molecular orbital energy decomposition analysis (LMOEDA) approaches indicate that the metal-ligand bonds in these complexes are mainly electrostatic in nature, however, the electrostatic is not the cause of the linearity of M-M-N arrangements. Instead, NEDA shows that the charge transfer and core repulsion are mainly responsible for the directionality of these bonds. In the LMOEDA point of view, the repulsion term is the main reason for the linearity of these complexes. Interacting quantum atoms (IQA) analysis shows that inter-atomic and inter-fragment interactions favour the nonlinear arrangements; however, these terms are compensated by the atomic self-energies, which stabilise the linear structure.

Light-Curing Volumetric Shrinkage in Dimethacrylate-Based Dental Composites by Nanoindentation and PAL Study.

PubMed

Shpotyuk, Olha; Adamiak, Stanislaw; Bezvushko, Elvira; Cebulski, Jozef; Iskiv, Maryana; Shpotyuk, Oleh; Balitska, Valentina

2017-12-01

Light-curing volumetric shrinkage in dimethacrylate-based dental resin composites Dipol® is examined through comprehensive kinetics research employing nanoindentation measurements and nanoscale atomic-deficient study with lifetime spectroscopy of annihilating positrons. Photopolymerization kinetics determined through nanoindentation testing is shown to be described via single-exponential relaxation function with character time constants reaching respectively 15.0 and 18.7 s for nanohardness and elastic modulus. Atomic-deficient characteristics of composites are extracted from positron lifetime spectra parameterized employing unconstrained x3-term fitting. The tested photopolymerization kinetics can be adequately reflected in time-dependent changes observed in average positron lifetime (with 17.9 s time constant) and fractional free volume of positronium traps (with 18.6 s time constant). This correlation proves that fragmentation of free-volume positronium-trapping sites accompanied by partial positronium-to-positron traps conversion determines the light-curing volumetric shrinkage in the studied composites.

Influence of dislocations on indium diffusion in semi-polar InGaN/GaN heterostructures

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

Yin, Yao; National Institute for Materials Science, Tsukuba, Ibaraki 305-0044; Sun, Huabin

2015-05-15

The spatial distribution of indium composition in InGaN/GaN heterostructure is a critical topic for modulating the wavelength of light emitting diodes. In this letter, semi-polar InGaN/GaN heterostructure stripes were fabricated on patterned GaN/Sapphire substrates by epitaxial lateral overgrowth (ELO), and the spatial distribution of indium composition in the InGaN layer was characterized by using cathodoluminescence. It is found that the indium composition is mainly controlled by the diffusion behaviors of metal atoms (In and Ga) on the surface. The diffusivity of metal atoms decreases sharply as migrating to the region with a high density of dislocations and other defects, whichmore » influences the distribution of indium composition evidently. Our work is beneficial for the understanding of ELO process and the further development of InGaN/GaN heterostructure based devices.« less

Nonlinear structure-composition relationships in the Ge 1-ySn y/Si(100) (y<0.15) system

DOE PAGES

Beeler, R.; Roucka, R.; Chizmeshya, A. V. G.; ...

2011-07-26

The compositional dependence of the cubic lattice parameter in Ge 1-ySn y alloys has been revisited. Large 1000-atom supercell ab initio simulations confirm earlier theoretical predictions that indicate a positive quadratic deviation from Vegard's law, albeit with a somewhat smaller bowing coefficient, θ = 0.047 Å, than found from 64-atom cell simulations (θ = 0.063 Å). On the other hand, measurements from an extensive set of alloy samples with compositions y < 0.15 reveal a negative deviation from Vegard's law. The discrepancy with earlier experimental data, which supported the theoretical results, is traced back to an unexpected compositional dependence ofmore » the residual strain after growth on Si substrates. The experimental bowing parameter for the relaxed lattice constant of the alloys is found to be θ = -0.066 Å. Possible reasons for the disagreement between theory and experiment are discussed in detail.« less

Temperature and composition dependence of Mg-based amorphous-alloy structure factors

NASA Astrophysics Data System (ADS)

From, M.; Muir, W. B.

1992-01-01

Measurements of the x-ray total structure factors for amorphous Mg70Zn30, Ca70Mg30, and Mg85.5Cu14.5 at 9, 150, and 300 K have been made. The composition dependence of the room-temperature structure factors of MgxZn1-x have also been measured for values of x=0.65, 0.70, and 0.75. These compositional changes can be accounted for by the increase in average atomic size as the fraction of the larger Mg atoms increases with x. Also the Perkus-Yevick hard-sphere model is sufficient to calculate the change in structure factor with composition if an experimental structure factor is available from which the sphere diameters and packing fraction can be extracted. The temperature dependence of the structure factors is consistent with the observed thermal expansion and a Debye phonon model with Meisel and Cote's approximation for the multiphonon contribution to the structure factor.

Paclitaxel-loaded poly(lactide-co-glycolide)/poly(ethylene vinyl acetate) composite for stent coating by ultrasonic atomizing spray.

PubMed

Yuk, Soon Hong; Oh, Keun Sang; Park, Jinah; Kim, Soon-Joong; Kim, Jung Ho; Kwon, Il Keun

2012-04-01

The mixture of poly(lactide-co-glycolide) (PLGA) and poly(ethylene vinyl acetate) (PEVA) forms a homogeneous liquid in an organic solvent such as tetrahydrofuran, and a phase-separated PLGA/PEVA composite can be prepared from it by evaporating the organic solvent. Exploiting this phenomenon, we designed a novel method of preparing a drug-loaded PLGA/PEVA composite and used it for coating drug-eluting stents (DESs). Paclitaxel (PTX), an anticancer drug, was chosen as a model drug. PLGA acts as a microdepot for PTX, and PEVA provides mechanical strength to the coating material. The presence of PLGA in the PLGA/PEVA composite suppressed PTX crystallization in the coating material, and PTX showed a sustained release rate over more than 30 days. The mechanical strength of the PLGA/PEVA composite was better than that of PEVA used as a control. After coating the stent with a PLGA/PEVA composite using ultrasonic atomizing spray, the morphology of the coated material was observed by scanning electron microscopy, and the release pattern of PTX was measured by high-performance liquid chromatography.

Paclitaxel-loaded poly(lactide-co-glycolide)/poly(ethylene vinyl acetate) composite for stent coating by ultrasonic atomizing spray

PubMed Central

Yuk, Soon Hong; Oh, Keun Sang; Park, Jinah; Kim, Soon-Joong; Kim, Jung Ho; Kwon, Il Keun

2012-01-01

The mixture of poly(lactide-co-glycolide) (PLGA) and poly(ethylene vinyl acetate) (PEVA) forms a homogeneous liquid in an organic solvent such as tetrahydrofuran, and a phase-separated PLGA/PEVA composite can be prepared from it by evaporating the organic solvent. Exploiting this phenomenon, we designed a novel method of preparing a drug-loaded PLGA/PEVA composite and used it for coating drug-eluting stents (DESs). Paclitaxel (PTX), an anticancer drug, was chosen as a model drug. PLGA acts as a microdepot for PTX, and PEVA provides mechanical strength to the coating material. The presence of PLGA in the PLGA/PEVA composite suppressed PTX crystallization in the coating material, and PTX showed a sustained release rate over more than 30 days. The mechanical strength of the PLGA/PEVA composite was better than that of PEVA used as a control. After coating the stent with a PLGA/PEVA composite using ultrasonic atomizing spray, the morphology of the coated material was observed by scanning electron microscopy, and the release pattern of PTX was measured by high-performance liquid chromatography. PMID:27877483

Paclitaxel-loaded poly(lactide-co-glycolide)/poly(ethylene vinyl acetate) composite for stent coating by ultrasonic atomizing spray

NASA Astrophysics Data System (ADS)

Yuk, Soon Hong; Oh, Keun Sang; Park, Jinah; Kim, Soon-Joong; Kim, Jung Ho; Kwon, Il Keun

2012-04-01

The mixture of poly(lactide-co-glycolide) (PLGA) and poly(ethylene vinyl acetate) (PEVA) forms a homogeneous liquid in an organic solvent such as tetrahydrofuran, and a phase-separated PLGA/PEVA composite can be prepared from it by evaporating the organic solvent. Exploiting this phenomenon, we designed a novel method of preparing a drug-loaded PLGA/PEVA composite and used it for coating drug-eluting stents (DESs). Paclitaxel (PTX), an anticancer drug, was chosen as a model drug. PLGA acts as a microdepot for PTX, and PEVA provides mechanical strength to the coating material. The presence of PLGA in the PLGA/PEVA composite suppressed PTX crystallization in the coating material, and PTX showed a sustained release rate over more than 30 days. The mechanical strength of the PLGA/PEVA composite was better than that of PEVA used as a control. After coating the stent with a PLGA/PEVA composite using ultrasonic atomizing spray, the morphology of the coated material was observed by scanning electron microscopy, and the release pattern of PTX was measured by high-performance liquid chromatography.

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

Carreras, Alejo C., E-mail: acarreras@famaf.unc.edu.ar; Cangiano, María de los A.; Ojeda, Manuel W.

The influence of the amount of complexing agent added to the starting solution on the physicochemical properties of Cu–Ni nanostructured alloys obtained through a chemical route, was studied. For this purpose, three Cu–Ni nanoalloy samples were synthesized by a previously developed procedure, starting from solutions with citric acid to metal molar ratios (C/Me) of 0.73, 1.00 and 1.50. The synthesis technique consisted in preparing a precursor via the citrate-gel method, and carrying out subsequent thermal treatments in controlled atmospheres. Sample characterization was performed by scanning electron microscopy, X-ray microanalysis, X-ray diffraction, transmission electron microscopy, X-ray nanoanalysis and electron diffraction. Inmore » the three cases, copper and nickel formed a solid solution with a Cu/Ni atomic ratio close to 50/50, and free of impurities inside the crystal structure. The citric acid content of the starting solution proved to have an important influence on the morphology, size distribution, porosity, and crystallinity of the Cu–Ni alloy microparticles obtained, but a lesser influence on their chemical composition. The molar ratio C/Me = 1.00 resulted in the alloy with the Cu/Ni atomic ratio closest to 50/50. - Highlights: • We synthesize Cu–Ni nanoalloys by a chemical route based on the citrate-gel method. • We study the influence of the complexing agent content of the starting solution. • We characterize the samples by electron microscopy and X-ray techniques. • Citric acid influences the shape, size, porosity and crystallinity of the alloys.« less

A highly selective and sensitive ultrasonic assisted dispersive liquid phase microextraction based on deep eutectic solvent for determination of cadmium in food and water samples prior to electrothermal atomic absorption spectrometry.

PubMed

Zounr, Rizwan Ali; Tuzen, Mustafa; Deligonul, Nihal; Khuhawar, Muhammad Yar

2018-07-01

A simple, fast, green, sensitive and selective ultrasonic assisted deep eutectic solvent liquid-phase microextraction technique was used for preconcentration and extraction of cadmium (Cd) in water and food samples by electrothermal atomic absorption spectrometry (ETAAS). In this technique, a synthesized reagent (Z)-N-(3,5-diphenyl-1H-pyrrol-2-yl)-3,5-diphenyl-2H-pyrrol-2-imine (Azo) was used as a complexing agent for Cd. The main factors effecting the pre-concentration and extraction of Cd such as effect of pH, type and composition of deep eutectic solvent (DES), volume of DES, volume of complexing agent, volume of tetrahydrofuran (THF) and ultrasonication time have been examined in detail. At optimum conditions the value of pH and molar ratio of DES were found to be 6.0 and 1:4 (ChCl:Ph), respectively. The detection limit (LOD), limit of quantification (LOQ), relative standard deviation (RSD) and preconcentration factor (PF) were observed as 0.023 ng L -1 , 0.161 ng L -1 , 3.1% and 100, correspondingly. Validation of the developed technique was observed by extraction of Cd in certified reference materials (CRMs) and observed results were successfully compared with certified values. The developed procedure was practiced to various food, beverage and water samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

Photochemistry of formaldoxime−nitrous acid complexes in an argon matrix: identification of formaldoxime nitrite.

PubMed

Golec, Barbara; Bil, Andrzej; Mielke, Zofia

2009-08-27

We have studied the structure and photochemistry of the formaldoxime−nitrous acid system (CH2NOH−HONO) by help of FTIR matrix isolation spectroscopy and ab initio methods. The MP2/6-311++G(2d,2p) calculations show stability of six isomeric CH2NOH···HONO complexes. The FTIR spectra evidence formation of two hydrogen bonded complexes in an argon matrix whose structures are determined by comparison of the experimental spectra with the calculated ones for the six stable complexes. In the matrix there is present the most stable cyclic complex with two O−H···N bonds; a strong bond is formed between the OH group of HONO and the N atom of CH2NOH and the weaker one between the OH group of CH2NOH and the N atom of HONO. In the other complex present in the matrix the OH group of formaldoxime is attached to the OH group of HONO forming an O−H···O bond. The irradiation of the CH2NOH···HONO complexes with the filtered output of the mercury lamp (λ > 345 nm) leads to the formation of formaldoxime nitrite, CH2NONO, and its two isomeric complexes with water. The main product is the CH2NONO···H2O complex in which water is hydrogen bonded to the N atom of the C═N group. The identity of the photoproducts is confirmed by both FTIR spectroscopy and MP2 or QCISD(full) calculations with the 6-311++G(2d,2p) basis set. The intermediate in this reaction is iminoxyl radical that is formed by abstraction of hydrogen atom from formaldoxime OH group by an OH radical originating from HONO photolysis.

Evaluation of the novel algorithm of flexible ligand docking with moveable target-protein atoms.

PubMed

Sulimov, Alexey V; Zheltkov, Dmitry A; Oferkin, Igor V; Kutov, Danil C; Katkova, Ekaterina V; Tyrtyshnikov, Eugene E; Sulimov, Vladimir B

2017-01-01

We present the novel docking algorithm based on the Tensor Train decomposition and the TT-Cross global optimization. The algorithm is applied to the docking problem with flexible ligand and moveable protein atoms. The energy of the protein-ligand complex is calculated in the frame of the MMFF94 force field in vacuum. The grid of precalculated energy potentials of probe ligand atoms in the field of the target protein atoms is not used. The energy of the protein-ligand complex for any given configuration is computed directly with the MMFF94 force field without any fitting parameters. The conformation space of the system coordinates is formed by translations and rotations of the ligand as a whole, by the ligand torsions and also by Cartesian coordinates of the selected target protein atoms. Mobility of protein and ligand atoms is taken into account in the docking process simultaneously and equally. The algorithm is realized in the novel parallel docking SOL-P program and results of its performance for a set of 30 protein-ligand complexes are presented. Dependence of the docking positioning accuracy is investigated as a function of parameters of the docking algorithm and the number of protein moveable atoms. It is shown that mobility of the protein atoms improves docking positioning accuracy. The SOL-P program is able to perform docking of a flexible ligand into the active site of the target protein with several dozens of protein moveable atoms: the native crystallized ligand pose is correctly found as the global energy minimum in the search space with 157 dimensions using 4700 CPU ∗ h at the Lomonosov supercomputer.

Crystal structures of dioxonium hexafluorotantalate and dioxonium hexafluoroniobate complexes with tetrabenzo-30-crown-10

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

Furmanova, N. G., E-mail: furm@ns.crys.ras.ru; Rabadanov, M. Kh.; Chernaya, T. S.

2008-03-15

Two isostructural complexes of dioxonium [H{sub 5}O{sub 2}]{sup +} with tetrabenzo-30-crown-10 of the compositions [(tetrabenzo-30-crown-10 . H{sub 5}O{sub 2})][TaF{sub 6}] (I) and [(tetrabenzo-30-crown-10 . H{sub 5}O{sub 2})][NbF{sub 6}] (II) are studied using X-ray diffraction. The complexes crystallize in the monoclinic crystal system (space group C2/c, Z = 4). The unit cell parameters of these compounds are as follows: a = 15.6583(12) A, b = 15.2259(13) A, c = 16.4473(13) A, and {beta} = 99.398(6) deg. for complex I and a = 15.7117(12) A, b = 15.2785(15) A, c = 16.5247(15) A, and {beta} = 99.398(7) deg. for complex II. Thesemore » complexes belong to the ionic type. The dioxonium cation [H{sub 5}O{sub 2}]{sup +} in the form of the two-unit cluster [H{sub 3}O . H{sub 2}O]{sup +} is stabilized by the strong hydrogen bond OH-O [O-O, 2.353(4) A] and encapsulated by the crown ether. Each oxygen atom of the dioxonium cation also forms two oxygen bonds O-O(crown). The crown ether adopts an unusual two-level (pocket-like) conformation, which provides a complete encapsulation of the oxonium associate. The interaction of the cationic complex with the anion in the crystal occurs through contacts of the C-H-F type.« less

Crystal structures of dioxonium hexafluorotantalate and dioxonium hexafluoroniobate complexes with tetrabenzo-30-crown-10

NASA Astrophysics Data System (ADS)

Furmanova, N. G.; Rabadanov, M. Kh.; Chernaya, T. S.; Fonari, M. S.; Simonov, Yu. A.; Ganin, É. V.; Gelmboldt, V. O.; Grigorash, R. Ya.; Kotlyar, S. A.; Kamalov, G. L.

2008-03-01

Two isostructural complexes of dioxonium [H5O2]+ with tetrabenzo-30-crown-10 of the compositions [(tetrabenzo-30-crown-10 · H5O2)][TaF6] ( I) and [(tetrabenzo-30-crown-10 · H5O2)][NbF6] ( II) are studied using X-ray diffraction. The complexes crystallize in the monoclinic crystal system (space group C2/ c, Z = 4). The unit cell parameters of these compounds are as follows: a = 15.6583(12) Å, b = 15.2259(13) Å, c = 16.4473(13) Å, and β = 99.398(6)° for complex I and a = 15.7117(12) Å, b = 15.2785(15) Å, c = 16.5247(15) Å, and β = 99.398(7)° for complex II. These complexes belong to the ionic type. The dioxonium cation [H5O2]+ in the form of the two-unit cluster [H3O · H2O]+ is stabilized by the strong hydrogen bond OH⋯O [O⋯O, 2.353(4) Å] and encapsulated by the crown ether. Each oxygen atom of the dioxonium cation also forms two oxygen bonds O⋯O(crown). The crown ether adopts an unusual two-level (pocket-like) conformation, which provides a complete encapsulation of the oxonium associate. The interaction of the cationic complex with the anion in the crystal occurs through contacts of the C-H⋯F type.

Representing annotation compositionality and provenance for the Semantic Web

PubMed Central

2013-01-01

Background Though the annotation of digital artifacts with metadata has a long history, the bulk of that work focuses on the association of single terms or concepts to single targets. As annotation efforts expand to capture more complex information, annotations will need to be able to refer to knowledge structures formally defined in terms of more atomic knowledge structures. Existing provenance efforts in the Semantic Web domain primarily focus on tracking provenance at the level of whole triples and do not provide enough detail to track how individual triple elements of annotations were derived from triple elements of other annotations. Results We present a task- and domain-independent ontological model for capturing annotations and their linkage to their denoted knowledge representations, which can be singular concepts or more complex sets of assertions. We have implemented this model as an extension of the Information Artifact Ontology in OWL and made it freely available, and we show how it can be integrated with several prominent annotation and provenance models. We present several application areas for the model, ranging from linguistic annotation of text to the annotation of disease-associations in genome sequences. Conclusions With this model, progressively more complex annotations can be composed from other annotations, and the provenance of compositional annotations can be represented at the annotation level or at the level of individual elements of the RDF triples composing the annotations. This in turn allows for progressively richer annotations to be constructed from previous annotation efforts, the precise provenance recording of which facilitates evidence-based inference and error tracking. PMID:24268021

Strengthening behavior of chopped multi-walled carbon nanotube reinforced aluminum matrix composites

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

Shin, S.E.; Bae, D.H., E-mail: donghyun@yonsei.ac.kr

2013-09-15

Strengthening behavior of the aluminum composites reinforced with chopped multi-walled carbon nanotubes (MWCNTs) or aluminum carbide formed during annealing at 500 °C has been investigated. The composites were fabricated by hot-rolling the powders which were ball-milled under various conditions. During the early annealing process, aluminum atoms can cluster inside the tube due to the diffusional flow of aluminum atoms into the tube, providing an increase of the strength of the composite. Further annealing induces the formation of the aluminum carbide phase, leading to an overall drop in the strength of the composites. While the strength of the composites can bemore » evaluated according to the rule of mixture, a particle spacing effect can be additionally imparted on the strength of the composites reinforced with the chopped MWCNTs or the corresponding carbides since the reinforcing agents are smaller than the submicron matrix grains. - Highlights: • Strengthening behavior of chopped CNT reinforced Al-based composites is investigated. • Chopped CNTs have influenced the strength and microstructures of the composites. • Chopped CNTs are created under Ar- 3% H2 atmosphere during mechanical milling. • Strength can be evaluated by the rule of the mixture and a particle spacing effect.« less

Nondestructive atomic compositional analysis of BeMgZnO quaternary alloys using ion beam analytical techniques

NASA Astrophysics Data System (ADS)

Zolnai, Z.; Toporkov, M.; Volk, J.; Demchenko, D. O.; Okur, S.; Szabó, Z.; Özgür, Ü.; Morkoç, H.; Avrutin, V.; Kótai, E.

2015-02-01

The atomic composition with less than 1-2 atom% uncertainty was measured in ternary BeZnO and quaternary BeMgZnO alloys using a combination of nondestructive Rutherford backscattering spectrometry with 1 MeV He+ analyzing ion beam and non-Rutherford elastic backscattering experiments with 2.53 MeV energy protons. An enhancement factor of 60 in the cross-section of Be for protons has been achieved to monitor Be atomic concentrations. Usually the quantitative analysis of BeZnO and BeMgZnO systems is challenging due to difficulties with appropriate experimental tools for the detection of the light Be element with satisfactory accuracy. As it is shown, our applied ion beam technique, supported with the detailed simulation of ion stopping, backscattering, and detection processes allows of quantitative depth profiling and compositional analysis of wurtzite BeZnO/ZnO/sapphire and BeMgZnO/ZnO/sapphire layer structures with low uncertainty for both Be and Mg. In addition, the excitonic bandgaps of the layers were deduced from optical transmittance measurements. To augment the measured compositions and bandgaps of BeO and MgO co-alloyed ZnO layers, hybrid density functional bandgap calculations were performed with varying the Be and Mg contents. The theoretical vs. experimental bandgaps show linear correlation in the entire bandgap range studied from 3.26 eV to 4.62 eV. The analytical method employed should help facilitate bandgap engineering for potential applications, such as solar blind UV photodetectors and heterostructures for UV emitters and intersubband devices.

Li-Ion Localization and Energetics as a Function of Anode Structure.

PubMed

McNutt, Nicholas W; McDonnell, Marshall; Rios, Orlando; Keffer, David J

2017-03-01

In this work, we study the effect of carbon composite anode structure on the localization and energetics of Li-ions. A computational molecular dynamics study is combined with experimental results from neutron scattering experiments to understand the effect of composite density, crystallite size, volume fraction of crystalline carbon, and ion loading on the nature of ion storage in novel, lignin-derived composite materials. In a recent work, we demonstrated that these carbon composites display a fundamentally different mechanism for Li-ion storage than traditional graphitic anodes. The edges of the crystalline and amorphous fragments of aromatic carbon that exist in these composites are terminated by hydrogen atoms, which play a crucial role in adsorption. In this work, we demonstrate how differences in composite structure due to changes in the processing conditions alter the type and extent of the interface between the amorphous and crystalline domains, thus impacting the nature of Li-ion storage. The effects of structural properties are evaluated using a suite of pair distribution functions as well as an original technique to extract archetypal structures, in the form of three-dimensional atomic density distributions, from highly disordered systems. The energetics of Li-ion binding are understood by relating changes in the energy and charge distributions to changes in structural properties. The distribution of Li-ion energies reveals that some structures lead to greater chemisorption, while others have greater physisorption. Carbon composites with a high volume fraction of small crystallites demonstrate the highest ion storage capacity because of the high interfacial area between the crystalline and amorphous domains. At these interfaces, stable H atoms, terminating the graphitic crystallites, provide favorable sites for reversible Li adsorption.

Grain boundary engineering to control the discontinuous precipitation in multicomponent U10Mo alloy

DOE PAGES

Devaraj, Arun; Kovarik, Libor; Kautz, Elizabeth; ...

2018-03-30

Here, we demonstrate here that locally stabilized structure and compositional segregation at grain boundaries in a complex multicomponent alloy can be modified using high temperature homogenization treatment to influence the kinetics of phase transformations initiating from grain boundaries during subsequent low temperature annealing. Using aberration-corrected scanning transmission electron microscopy and atom probe tomography of a model multicomponent metallic alloy —uranium-10 wt% molybdenum (U-10Mo) a nuclear fuel, that is highly relevant to worldwide nuclear non-proliferation efforts, we demonstrate the ability to change the structure and compositional segregation at grain boundary, which then controls the subsequent discontinuous precipitation kinetics during sub-eutectoid annealing.more » A change in grain boundary from one characterized by segregation of Mo and impurities at grain boundary to a phase boundary with a distinct U 2MoSi 2C wetting phase precipitates introducing Ni and Al rich interphase complexions caused a pronounced reduction in area fraction of subsequent discontinuous precipitation. The broader implication of this work is in highlighting the role of grain boundary structure and composition in metallic alloys on dictating the fate of grain boundary initiated phase transformations like discontinuous precipitation or cellular transformation. This work highlights a new pathway to tune the grain boundary structure and composition to tailor the final microstructure of multicomponent metallic alloys.« less

Grain boundary engineering to control the discontinuous precipitation in multicomponent U10Mo alloy

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

Devaraj, Arun; Kovarik, Libor; Kautz, Elizabeth

Here, we demonstrate here that locally stabilized structure and compositional segregation at grain boundaries in a complex multicomponent alloy can be modified using high temperature homogenization treatment to influence the kinetics of phase transformations initiating from grain boundaries during subsequent low temperature annealing. Using aberration-corrected scanning transmission electron microscopy and atom probe tomography of a model multicomponent metallic alloy —uranium-10 wt% molybdenum (U-10Mo) a nuclear fuel, that is highly relevant to worldwide nuclear non-proliferation efforts, we demonstrate the ability to change the structure and compositional segregation at grain boundary, which then controls the subsequent discontinuous precipitation kinetics during sub-eutectoid annealing.more » A change in grain boundary from one characterized by segregation of Mo and impurities at grain boundary to a phase boundary with a distinct U 2MoSi 2C wetting phase precipitates introducing Ni and Al rich interphase complexions caused a pronounced reduction in area fraction of subsequent discontinuous precipitation. The broader implication of this work is in highlighting the role of grain boundary structure and composition in metallic alloys on dictating the fate of grain boundary initiated phase transformations like discontinuous precipitation or cellular transformation. This work highlights a new pathway to tune the grain boundary structure and composition to tailor the final microstructure of multicomponent metallic alloys.« less

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

Jain, Divya; Isheim, Dieter; Seidman, David N.

HSLA-115 is a newly developed Cu-bearing high-strength low-carbon martensitic steel for use in Naval structural applications. This research provides, for the first time, a comprehensive compositional analysis of carbon redistribution and associated complex phase transformations in an isothermal aging study of HSLA-115 at 823 K (550 °C). Specifically, we characterize carbon segregation at lath boundaries, grain-refining niobium carbonitrides, cementite, and secondary hardening M2C carbides, in addition to copper precipitation, by 3D atom probe tomography (APT). Segregation of carbon (3 to 6 at. pct C) is observed at martensitic lath boundaries in the as-quenched and 0.12-hour aged microstructures. On further aging,more » carbon redistributes itself forming cementite and M2C carbides. Niobium carbonitride precipitates do not dissolve during the austenitizing treatment and are inherited in the as-quenched and aged microstructures; these are characterized along with cementite by synchrotron X-ray diffraction and APT. Sub-nanometer-sized M2C carbide precipitates are observed after the formation of Cu precipitates, co-located with the latter, indicating heterogeneous nucleation of M2C. The temporal evolution of the composition and morphology of M2C carbides at 823 K (550 °C) is described using APT; their precipitation kinetics is intertwined with Cu precipitates, affecting the bulk mechanical properties of HSLA-115. Phase compositions determined by APT are compared with computed compositions at thermodynamic equilibrium using ThermoCalc.« less

Platinum atomic wire encapsulated in gold nanotubes: A first principle study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib; Sahoo, Suman K.

2014-04-24

The nanotubes of gold incorporated with platinum atomic wire have been investigated by means of firstprinciples density functional theory with plane wave pseudopotential approximation. The structure with zig-zag chain of Pt atoms in side gold is found to be 0.73 eV lower in energy in comparison to straight chain of platinum atoms. The Fermi level of the composite tube was consisting of d-orbitals of Pt atoms. Further interaction of oxygen with these tubes reveals that while tube with zig-zag Pt prefers dissociative adsorption of oxygen molecule, the gold tube with linear Pt wire favors molecular adsorption.

Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

NASA Astrophysics Data System (ADS)

Shin, H.-C.; Ahn, S. J.; Kim, H. W.; Moon, Y.; Rai, K. B.; Woo, S. H.; Ahn, J. R.

2016-08-01

Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalated at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.

Processing of AlCoCrFeNiTi high entropy alloy by atmospheric plasma spraying

NASA Astrophysics Data System (ADS)

Löbel, M.; Lindner, T.; Kohrt, C.; Lampke, T.

2017-03-01

High Entropy Alloys (HEA) are gaining increasing interest due to their unique combination of properties. Especially the combination of high mechanical strength and hardness with distinct ductility makes them attractive for numerous applications. One interesting alloy system that exhibits excellent properties in bulk state is AlCoCrFeNiTi. A high strength, wear resistance and high-temperature resistance are the necessary requirements for the application in surface engineering. The suitability of blended, mechanically ball milled and inert gas atomized feedstock powders for the development of atmospheric plasma sprayed (APS) coatings is investigated in this study. The ball milled and inert gas atomized powders were characterized regarding their particle morphology, phase composition, chemical composition and powder size distribution. The microstructure and phase composition of the thermal spray coatings produced with different feedstock materials was investigated and compared with the feedstock material. Furthermore, the Vickers hardness (HV) was measured and the wear behavior under different tribological conditions was tested in ball-on-disk, oscillating wear and scratch tests. The results show that all produced feedstock materials and coatings exhibit a multiphase composition. The coatings produced with inert gas atomized feedstock material provide the best wear resistance and the highest degree of homogeneity.

Chemical synthesis and structural characterization of small AuZn nanoparticles

NASA Astrophysics Data System (ADS)

Juárez-Ruiz, E.; Pal, U.; Lombardero-Chartuni, J. A.; Medina, A.; Ascencio, J. A.

2007-03-01

In this paper, we report the aqueous synthesis of bimetallic Au-Zn nanoparticles of different compositions by the simultaneous reduction technique. The stability and atomic configuration of the particles are studied through high-resolution transmission electron microscopy (HRTEM) and UV-Vis optical absorption techniques. Depending on the composition, small bimetallic nanoparticles of 1 15 nm in size were obtained. The average size and size distribution of the bimetallic nanoparticles are seen to be critically dependent on the atomic ratio of the constituting elements Au and Zn. While a 1:1 atomic proportion of Au and Zn produced most stable nanoparticles of smallest average size, nanoparticles produced with higher content of either of the component elements are unstable, inducing agglomeration and coalescence to form elongated structures with uneven morphologies. Au3Zn1 nanoparticles followed a directional growth pattern, producing bimetallic nanorods with multiple crystalline domains. Interestingly, in these rod-like nanostructures, the domains are in well array of solid solution-like bimetallic and pure mono-metallic regions alternatively. Such nanostructures with uneven morphology and compositions might show distinct catalytic selectivity in chemical reactions.

Atom Probe Tomography Characterization of the Solute Distributions in a Neutron-Irradiated and Annealed Pressure Vessel Steel Weld

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

Miller, M.K.

2001-01-30

A combined atom probe tomography and atom probe field ion microscopy study has been performed on a submerged arc weld irradiated to high fluence in the Heavy-Section Steel irradiation (HSSI) fifth irradiation series (Weld 73W). The composition of this weld is Fe - 0.27 at. % Cu, 1.58% Mn, 0.57% Ni, 0.34% MO, 0.27% Cr, 0.58% Si, 0.003% V, 0.45% C, 0.009% P, and 0.009% S. The material was examined after five conditions: after a typical stress relief treatment of 40 h at 607 C, after neutron irradiation to a fluence of 2 x 10{sup 23} n m{sup {minus}2} (Emore » > 1 MeV), and after irradiation and isothermal anneals of 0.5, 1, and 168 h at 454 C. This report describes the matrix composition and the size, composition, and number density of the ultrafine copper-enriched precipitates that formed under neutron irradiation and the change in these parameters with post-irradiation annealing treatments.« less

Direct comparison of Fe-Cr unmixing characterization by atom probe tomography and small angle scattering

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

Couturier, Laurent, E-mail: laurent.couturier55@ho

The fine microstructure obtained by unmixing of a solid solution either by classical precipitation or spinodal decomposition is often characterized either by small angle scattering or atom probe tomography. This article shows that a common data analysis framework can be used to analyze data obtained from these two techniques. An example of the application of this common analysis is given for characterization of the unmixing of the Fe-Cr matrix of a 15-5 PH stainless steel during long-term ageing at 350 °C and 400 °C. A direct comparison of the Cr composition fluctuations amplitudes and characteristic lengths obtained with both techniquesmore » is made showing a quantitative agreement for the fluctuation amplitudes. The origin of the discrepancy remaining for the characteristic lengths is discussed. - Highlights: •Common analysis framework for atom probe tomography and small angle scattering •Comparison of same microstructural characteristics obtained using both techniques •Good correlation of Cr composition fluctuations amplitudes from both techniques •Good correlation of Cr composition fluctuations amplitudes with classic V parameter.« less

Ab initio study of single-crystalline and polycrystalline elastic properties of Mg-substituted calcite crystals.

PubMed

Zhu, L-F; Friák, M; Lymperakis, L; Titrian, H; Aydin, U; Janus, A M; Fabritius, H-O; Ziegler, A; Nikolov, S; Hemzalová, P; Raabe, D; Neugebauer, J

2013-04-01

We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

If Only We Could Account For Every Atom (LBNL Summer Lecture Series)

ScienceCinema

Kisielowski, Christian [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Science Division

2018-02-16

Christian Kisielowski, an expert in electron microscopy at Lawrence Berkeley National Laboratory, investigates ways to allow studies of single atoms using sophisticated microscopes and imaginative techniques. His goal is to account for every atom in the interior of both simple and complex materials. Find out how he and his colleagues are breaking the barriers to account for every atom.

The adsorption of helium atoms on coronene cations

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

Kurzthaler, Thomas; Rasul, Bilal; Kuhn, Martin

2016-08-14

We report the first experimental study of the attachment of multiple foreign atoms to a cationic polycyclic aromatic hydrocarbon (PAH). The chosen PAH was coronene, C{sub 24}H{sub 12}, which was added to liquid helium nanodroplets and then subjected to electron bombardment. Using mass spectrometry, coronene cations decorated with helium atoms were clearly seen and the spectrum shows peaks with anomalously high intensities (“magic number” peaks), which represent ion-helium complexes with added stability. The data suggest the formation of a rigid helium layer consisting of 38 helium atoms that completely cover both faces of the coronene ion. Additional magic numbers canmore » be seen for the further addition of 3 and 6 helium atoms, which are thought to attach to the edge of the coronene. The observation of magic numbers for the addition of 38 and 44 helium atoms is in good agreement with a recent path integral Monte Carlo prediction for helium atoms on neutral coronene. An understanding of how atoms and molecules attach to PAH ions is important for a number of reasons including the potential role such complexes might play in the chemistry of the interstellar medium.« less

Synthesis and crystal structures of coordination compounds of pyridoxine with zinc and cadmium sulfates

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

Furmanova, N. G., E-mail: furm@ns.crys.ras.ru; Berdalieva, Zh. I., E-mail: kakin@inbox.ru; Chernaya, T. S.

2009-03-15

The pyridoxine complexes with zinc and cadmium sulfates are synthesized. The IR absorption spectra and thermal behavior of the synthesized compounds are described. Crystals of the [M(C{sub 8}H{sub 11}O{sub 3}N){sub 2}(H{sub 2}O){sub 2}]SO{sub 4} . 3H{sub 2}O (M = Zn, Cd) compounds are investigated using X-ray diffraction. In the structures of both compounds, the M atoms are coordinated by the oxygen atoms of the deprotonated OH group and the CH{sub 2}OH group retaining its own hydrogen atom, as well as by two H{sub 2}O molecules, and have an octahedral coordination. The nitrogen atom of the heterocycle is protonated, so thatmore » the heterocycle acquires a pyridinium character. The cationic complexes form layers separated by the anions and crystallization water molecules located in between. The structural units of the crystals are joined together by a complex system of hydrogen bonds.« less

The Discovery of Crown Ethers

NASA Astrophysics Data System (ADS)

Pedersen, Charles J.

1988-07-01

The discovery of the crown ethers stemmed from efforts to control the catalytic activity of vanadium and copper by complexation with multidentate ligands. The first crown ether, 2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoxacyclo-octadeca-2,11-diene, was obtained in 0.4% yield during an attempt to prepare a phenolic ligand from catechol and bis(2-chloroethyl)ether. This compound, which complexed with the sodium cation, was the first compound known to display such activity and became known as dibenzo-18-crown-6, an 18-atom heterocycle containing 6 oxygen atoms. Some 60 related compounds were made involving heterocyclic rings containing 12 to 60 atoms including 4 and 10 oxygen atoms. There are optimum polyether ring sizes for the different alkali metal cations: 15 to 18 for sodium, 18 for potassium, and 18 to 21 for cesium. Complexes having polyether to cation ratios of 1:1, 3:2, and 2:1 were prepared. Solubilization of inorganic salts in aprotic solvents, especially by saturated crown ethers, was demonstrated.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

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

Zhang, Fuxiang; Tong, Yang; Jin, Ke

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

DOE PAGES

Zhang, Fuxiang; Tong, Yang; Jin, Ke; ...

2018-06-16

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Dipotassium tetra­kis­(thio­cyanato-κS)palladate(II)–(2,2′-bipyrimidine-κ2 N 1,N 1′)bis­(thio­cyanato-κS)palladium(II) (1/2)

PubMed Central

Ha, Kwang

2012-01-01

The asymmetric unit of the title compound, K2[Pd(NCS)4]·2[Pd(NCS)2(C8H6N4)], contains two crystallographically independent half-mol­ecules of the anionic PdII complex, two K+ cations and two independent neutral PdII complexes; an inversion centre is located at the centroid of each anionic complex. In the anionic complexes, each PdII ion is four-coordinated in an almost regular square-planar environment by four S atoms from four SCN− anions, and the PdS4 unit is exactly planar. In the neutral complexes, the PdII ion has a slightly distorted square-planar coordination environment defined by two pyrimidine N atoms derived from a chelating 2,2′-bipyrimidine ligand and two mutually cis S atoms from two SCN− anions. Both 2,2′-bipyrimidine ligands are almost planar [dihedral angle between the rings = 3.98 (16) and 4.57 (17)°] and also chelate to a potassium ion from their other two N atoms. In the crystal, the K+ ions inter­act with various S and N atoms of the ligands, forming a three-dimensional polymeric network, in which the shortest K⋯K contacts between the KN7S polyhedra are 4.4389 (17) and 4.4966 (18) Å. Intra- and inter­molecular C—H⋯S and C—H⋯N hydrogen bonds are also observed. PMID:22590117

Structural materials for space applications

NASA Technical Reports Server (NTRS)

Tenney, Darrel R.

1989-01-01

The long-term performance of structural materials in the space environment is a key research activity within NASA. The primary concerns for materials in low Earth orbit (LEO) are atomic oxygen erosion and space debris impact. Atomic oxygen studies have included both laboratory exposures in atomic oxygen facilities and flight exposures using the Shuttle. Characterization of atomic oxygen interaction with materials has included surface recession rates, residual mechanical properties, optical property measurements, and surface analyses to establish chemical changes. The Long Duration Exposure Facility (LDEF) is scheduled to be retrieved in 1989 and is expected to provide a wealth of data on atomic oxygen erosion in space. Hypervelocity impact studies have been conducted to establish damage mechanisms and changes in mechanical properties. Samples from LDEF will be analyzed to determine the severity of space debris impact on coatings, films, and composites. Spacecraft placed in geosynchronous Earth orbit (GEO) will be subjected to high doses of ionizing radiation which for long term exposures will exceed the damage threshold of many polymeric materials. Radiation interaction with polymers can result in chain scission and/or cross-linking. The formation of low molecular weight products in the epoxy plasticize the matrix at elevated temperatures and embrittle the matrix at low temperatures. This affects both the matrix-dominated mechanical properties and the dimensional stability of the composite. Embrittlement of the matrix at low temperatures results in enhanced matrix microcracking during thermal cycling. Matrix microcracking changes the coefficient of thermal expansion (CTE) of composite laminates and produces permanent length changes. Residual stress calculations were performed to estimate the conditions necessary for microcrack development in unirradiated and irradiated composites. The effects of UV and electron exposure on the optical properties of transparent polymer films were also examined to establish the optimum chemical structure for good radiation resistance. Thoughts on approaches to establishing accelerated testing procedures are discussed.

2D polymeric cadmium(II) complexes containing 1,3-imidazolidine-2-thione (Imt) ligand, [Cd(Imt)(H2O)2(SO4)]n and [Cd(Imt)2(N3)2]n

NASA Astrophysics Data System (ADS)

Mahmood, Rashid; Ahmad, Saeed; Fettouhi, Mohammed; Roisnel, Thierry; Gilani, Mazhar Amjad; Mehmood, Kashif; Murtaza, Ghulam; Isab, Anvarhusein A.

2018-03-01

The present study aims at preparing and carrying out the structural investigation of two polymeric cadmium(II) complexes of imidazolidine-2-thione (Imt) based on sulfate or azide ions, [Cd(Imt)(H2O)2(SO4)]n (1) and [Cd(Imt)2(N3)2]n (2). The structures of the complexes were determined by single crystal X-ray analysis. Both compounds, 1 and 2 crystallize in the form of 2D coordination polymers and the cadmium(II) ion is six-coordinate having a distorted octahedral geometry in each compound. In 1, the metal ion is bonded to one sulfur atom of Imt and five oxygen atoms with two from water and three of bridging sulfate ions. In 2, the cadmium coordination sphere is completed by two Imt molecules binding through the sulfur atoms and four nitrogen atoms of bridging azide ions. The crystal structures are stabilized by intra and intermolecular hydrogen bonding interactions. The complexes were also characterized by IR and NMR spectroscopy and the spectroscopic data is consistent with the binding of the ligands.

Crystal structure of fac-tri-carbonyl-chlorido-bis-(4-hy-droxy-pyridine)-rhenium(I)-pyridin-4(1H)-one (1/1).

PubMed

Argibay-Otero, Saray; Carballo, Rosa; Vázquez-López, Ezequiel M

2017-10-01

The asymmetric unit of the title compound, [ReCl(C 5 H 5 NO) 2 (CO) 3 ]·C 5 H 5 NO, contains one mol-ecule of the complex fac -[ReCl(4-pyOH) 2 (CO) 3 ] (where 4-pyOH represents 4-hy-droxy-pyridine) and one mol-ecule of pyridin-4(1 H )-one (4-HpyO). In the mol-ecule of the complex, the Re atom is coordinated to two N atoms of the two 4-pyOH ligands, three carbonyl C atoms, in a facial configuration, and the Cl atom. The resulting geometry is slightly distorted octa-hedral. In the crystal structure, both fragments are associated by hydrogen bonds; two 4-HpyO mol-ecules bridge between two mol-ecules of the complex using the O=C group as acceptor for two different HO- groups of coordinated 4-pyOH from two neighbouring metal complexes. The resulting square arrangements are extented into infinite chains by hydrogen bonds involving the N-H groups of the 4-HpyO mol-ecule and the chloride ligands. The chains are further stabilized by π-stacking inter-actions.

Molecular, crystal, and electronic structure of the cobalt(II) complex with 10-(2-benzothiazolylazo)-9-phenanthrol

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

Linko, R. V., E-mail: rlinko@mail.ru; Sokol, V. I.; Polyanskaya, N. A.

2013-05-15

The reaction of 10-(2-benzothiazolylazo)-9-phenanthrol (HL) with cobalt(II) acetate gives the coordination compound [CoL{sub 2}] {center_dot} CHCl{sub 3} (I). The molecular and crystal structure of I is determined by X-ray diffraction. The coordination polyhedron of the Co atom in complex I is an octahedron. The anion L acts as a tridentate chelating ligand and is coordinated to the Co atom through the phenanthrenequinone O1 atom and the benzothiazole N1 atom of the moieties L and the N3 atom of the azo group to form two five-membered metallocycles. The molecular and electronic structures of the compounds HL, L, and CoL{sub 2} aremore » studied at the density functional theory level. The results of the quantum-chemical calculations are in good agreement with the values determined by X-ray diffraction.« less

Ab-initio atomic level stress and role of d-orbitals in CuZr, CuZn and CuY

NASA Astrophysics Data System (ADS)

Ojha, Madhusudan; Nicholson, Don M.; Egami, Takeshi

2015-03-01

Atomic level stress offers a new tool to characterize materials within the local approximation to density functional theory (DFT). Ab-initio atomic level stresses in B2 structures of CuZr, CuZn and CuY are calculated and results are explained on the basis of d-orbital contributions to Density of States (DOS). The overlap of d-orbital DOS plays an important role in the relative magnitude of atomic level stresses in these structures. The trends in atomic level stresses that we observed in these simple B2 structures are also seen in complex structures such as liquids, glasses and solid solutions. The stresses are however modified by the different coordination and relaxed separation distances in these complex structures. We used the Locally Self-Consistent Multiple Scattering (LSMS) code and Vienna Ab-initio Simulation Package (VASP) for ab-initio calculations.

Tuning negative differential resistance in single-atomic layer boron-silicon sheets

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

Zhou, Ming-Yue; Liu, Chun-Sheng, E-mail: csliu@njupt.edu.cn, E-mail: yanxh@njupt.edu.cn; Key Laboratory of Radio Frequency and Micro-Nano Electronics of Jiangsu Province, Nanjing 210023, Jiangsu

2015-03-21

Using density functional theory and nonequilibrium Green's function formalism for quantum transport calculation, we have quantified the ballistic transport properties along different directions in two-dimensional boron-silicon (B-Si) compounds, as well as the current response to bias voltage. The conductance of the most B-Si devices is higher than the conductance of one-atom-thick boron and silicene. Furthermore, the negative differential resistance phenomenon can be found at certain B-Si stoichiometric composition, and it occurs at various bias voltages. Also, the peak-to-valley ratio is sensitive to the B-Si composition and dependent of the direction considered for B-Si monolayers. The present findings could be helpfulmore » for applications of the single-atomic layer B-Si sheets in the field of semiconductor devices or low-dimensional electronic devices.« less

A rapid and rational approach to generating isomorphous heavy-atom phasing derivatives

PubMed Central

Lu, Jinghua; Sun, Peter D.

2014-01-01

In attempts to replace the conventional trial-and-error heavy-atom derivative search method with a rational approach, we previously defined heavy metal compound reactivity against peptide ligands. Here, we assembled a composite pH and buffer-dependent peptide reactivity profile for each heavy metal compound to guide rational heavy-atom derivative search. When knowledge of the best-reacting heavy-atom compound is combined with mass spectrometry-assisted derivatization, and with a quick-soak method to optimize phasing, it is likely that the traditional heavy-atom compounds could meet the demand of modern high-throughput X-ray crystallography. As an example, we applied this rational heavy-atom phasing approach to determine a previously unknown mouse serum amyloid A2 crystal structure. PMID:25040395

Embedded-atom-method study of structural, thermodynamic, and atomic-transport properties of liquid Ni-Al alloys

NASA Astrophysics Data System (ADS)

Asta, Mark; Morgan, Dane; Hoyt, J. J.; Sadigh, Babak; Althoff, J. D.; de Fontaine, D.; Foiles, S. M.

1999-06-01

Structural, thermodynamic, and atomic-transport properties of liquid Ni-Al alloys have been studied by Monte Carlo and molecular-dynamics simulations based upon three different embedded-atom method (EAM) interatomic potentials, namely those due to Foiles and Daw (FD) [J. Mater. Res. 2, 5 (1987)], Voter and Chen (VC) [in Characterization of Defects in Materials, edited by R. W. Siegel et al. MRS Symposia Proceedings. No. 82 (Materials Research Society, Pittsburgh, 1987), p.175] and Ludwig and Gumbsch (LG) [Model. Simul. Mater. Sci. Eng. 3, 533 (1995)]. We present detailed comparisons between calculated results and experimental data for structure factors, atomic volumes, enthalpies of mixing, activities, and viscosities. Calculated partial structure factors are found to be in semiquantitative agreement with published neutron scattering measurements for Ni20Al80 alloys, indicating that short-range order in the liquid phase is qualitatively well described. Calculated thermodynamic properties of mixing are found to agree very well with experimental data for Ni compositions greater than 75 atomic %, while for alloys richer in Al the magnitudes of the enthalpies and entropies of mixing are significantly underestimated. The VC and LG potentials give atomic densities and viscosities in good agreement with experiment for Ni-rich compositions, while FD potentials consistently underestimate both properties at all concentrations. The results of this study demonstrate that VC and LG potentials provide a realistic description of the thermodynamic and atomic transport properties for NixAl1-x liquid alloys with x>=0.75, and point to the limitations of EAM potentials for alloys richer in Al.

Atomic Precision Plasma Processing - Modeling Investigations

NASA Astrophysics Data System (ADS)

Rauf, Shahid

2016-09-01

Sub-nanometer precision is increasingly being required of many critical plasma processes in the semiconductor industry. Some of these critical processes include atomic layer etch and plasma enhanced atomic layer deposition. Accurate control over ion energy and ion / radical composition is needed during plasma processing to meet the demanding atomic-precision requirements. While improvements in mainstream inductively and capacitively coupled plasmas can help achieve some of these goals, newer plasma technologies can expand the breadth of problems addressable by plasma processing. Computational modeling is used to examine issues relevant to atomic precision plasma processing in this paper. First, a molecular dynamics model is used to investigate atomic layer etch of Si and SiO2 in Cl2 and fluorocarbon plasmas. Both planar surfaces and nanoscale structures are considered. It is shown that accurate control of ion energy in the sub-50 eV range is necessary for atomic scale precision. In particular, if the ion energy is greater than 10 eV during plasma processing, several atomic layers get damaged near the surface. Low electron temperature (Te) plasmas are particularly attractive for atomic precision plasma processing due to their low plasma potential. One of the most attractive options in this regard is energetic-electron beam generated plasma, where Te <0.5 eV has been achieved in plasmas of molecular gases. These low Te plasmas are computationally examined in this paper using a hybrid fluid-kinetic model. It is shown that such plasmas not only allow for sub-5 eV ion energies, but also enable wider range of ion / radical composition. Coauthors: Jun-Chieh Wang, Jason Kenney, Ankur Agarwal, Leonid Dorf, and Ken Collins.

The impact of atomization on the surface composition of spray-dried milk droplets.

PubMed

Foerster, Martin; Gengenbach, Thomas; Woo, Meng Wai; Selomulya, Cordelia

2016-04-01

The dominant presence of fat at the surface of spray-dried milk powders has been widely reported in the literature and described as resulting in unfavourable powder properties. The mechanism(s) causing this phenomenon are yet to be clearly identified. A systematic investigation of the component distribution in atomized droplets and spray-dried particles consisting of model milk systems with different fat contents demonstrated that atomization strongly influences the final surface composition. Cryogenic flash-freezing of uniform droplets from a microfluidic jet nozzle directly after atomization helped to distinguish the influence of the atomization stage from the drying stage. It was confirmed that the overrepresentation of fat on the surface is independent of the atomization technique, including a pressure-swirl single-fluid spray nozzle and a pilot-scale rotary disk spray dryer commonly used in industry. It is proposed that during the atomization stage a disintegration mechanism along the oil-water interface of the fat globules causes the surface predominance of fat. X-ray photoelectron spectroscopic measurements detected the outermost fat layer and some adjacent protein present on both atomized droplets and spray-dried particles. Confocal laser scanning microscopy gave a qualitative insight into the protein and fat distribution throughout the cross-sections, and confirmed the presence of a fat film along the particle surface. The film remained on the surface in the subsequent drying stage, while protein accumulated underneath, driven by diffusion. The results demonstrated that atomization induces component segregation and fat-rich surfaces in spray-dried milk powders, and thus these cannot be prevented by adjusting the spray drying conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Group 6 metal pentacarbonyl complexes of air-stable primary, secondary, and tertiary ferrocenylethylphosphines.

PubMed

Rabiee Kenaree, Amir; Sauvé, Ethan R; Ragogna, Paul J; Gilroy, Joe B

2016-02-21

The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the atomic radii of the Group 6 metals involved. UV-Vis absorption spectroscopy and cyclic voltammetry highlighted characteristics consistent with electronically isolated ferrocene units including wavelengths of maximum absorption between 435 and 441 nm and reversible one-electron (per ferrocene unit) oxidation waves between 10 and -5 mV relative to the ferrocene/ferrocenium redox couple. IR spectroscopy confirmed that the σ donating ability of the phosphines increased as ferrocenylethyl substituents were introduced and that the tertiary phosphine ligand described is a stronger σ donor than PPh3 and a weaker σ donor than PEt3, respectively.

Hydrodynamical instabilities induced by atomic diffusion in F and A stars : Impact on the opacity profile and asteroseimic age determination

NASA Astrophysics Data System (ADS)

Deal, M.; Richard, O.; Vauclair, S.

2017-12-01

Atomic diffusion, including the effect of radiative accelerations on individual elements, leads to important variations of the chemical composition inside the stars. The accumulation in specific layers of the elements, which are the main contributors of the local opacity, leads to hydrodynamical instabilities that modify the internal stellar structure and surface abundances. The modification of the initial chemical composition has important effects on the internal stellar mixing and leads to different surface and internal abundances of the elements. These processes also modify the age determination by asteroseismology.

Optimizing isotope substitution in graphene for thermal conductivity minimization by genetic algorithm driven molecular simulations

NASA Astrophysics Data System (ADS)

Davies, Michael; Ganapathysubramanian, Baskar; Balasubramanian, Ganesh

2017-03-01

We present results from a computational framework integrating genetic algorithm and molecular dynamics simulations to systematically design isotope engineered graphene structures for reduced thermal conductivity. In addition to the effect of mass disorder, our results reveal the importance of atomic distribution on thermal conductivity for the same isotopic concentration. Distinct groups of isotope-substituted graphene sheets are identified based on the atomic composition and distribution. Our results show that in structures with equiatomic compositions, the enhanced scattering by lattice vibrations results in lower thermal conductivities due to the absence of isotopic clusters.

Co-axial Electrospun Polyacrylonitrile-Poly(methylmethacrylate) Nanofibers: Atomic Force Microscopy and Compositional Characterization

PubMed Central

Zander, N.E.; Strawhecker, K.E.; Orlicki, J.A.; Rawlett, A.M.; Beebe, T.P.

2011-01-01

Poly(methylmethacrylate) (PMMA)- Polyacrylonitrile (PAN) fibers were prepared using a conventional single-nozzle electrospinning technique. The as-spun fibers exhibited core-shell morphology as verified by transmission electron microscopy (TEM) and atomic force microscopy (AFM). AFM-phase and modulus mapping images of the fiber cross-section and x-ray photoelectron spectroscopy (XPS) analysis indicated PAN formed the shell and PMMA the core material. XPS, thermal gravimetric analysis (TGA), and elemental analysis were used to determine fiber compositional information. Soaking the fibers in solvent demonstrated removal of the core material, generating hollow PAN fibers. PMID:21928836

Comparison of Martian meteorites with earth composition: Study of effective atomic numbers in the energy range 1 keV-100 GeV

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

Ün, Adem, E-mail: ademun25@yahoo.com; Han, İbrahim, E-mail: ibrahimhan25@hotmail.com; Ün, Mümine, E-mail: mun@agri.edu.tr

2016-04-18

Effective atomic (Z{sub eff}) and electron numbers (N{sub eff}) for 24 Martian meteorites have been determined in the energy range from 1 keV to 100 GeV and also for sixteen significant energies of commonly used radioactive sources. The values of Z{sub eff} and N{sub eff} for all sample were obtained from the DirectZeff program. The obtained results for Martian meteorites have been compared with the results for Earth composition and similarities or differences also evaluated.

Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

NASA Astrophysics Data System (ADS)

El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.

2003-02-01

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

Polymer complexes. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes.

PubMed

El-Sonbati, A Z; El-Bindary, A A; Diab, M A

2003-02-01

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [(11)+(12)] in the paper and in mononuclear polymer complexes (1)-(5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX2 and KPtCl4 in the presence of N-heterocyclic base consisting of polymer complexes (9)+(10), and in monouclear compounds (6)-(8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds (13)+(14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

Lanthanide anilido complexes: synthesis, characterization, and use as highly efficient catalysts for hydrophosphonylation of aldehydes and unactivated ketones.

PubMed

Liu, Chengwei; Qian, Qinqin; Nie, Kun; Wang, Yaorong; Shen, Qi; Yuan, Dan; Yao, Yingming

2014-06-14

Lanthanide anilido complexes stabilized by the 2,6-diisopropylanilido ligand have been synthesized and characterized, and their catalytic activity for hydrophosphonylation reaction was explored. A reaction of anhydrous LnCl3 with 5 equivalents of LiNHPh-(I)Pr2-2,6 in THF generated the heterobimetallic lanthanide-lithium anilido complexes (2,6-(I)Pr2PhNH)5LnLi2(THF)2 [Ln = Sm(1), Nd(2), Y(3)] in good isolated yields. These complexes are well characterized by elemental analysis, IR, NMR (for complex ) and single-crystal structure determination. Complexes 1 - 3 are isostructural. In these complexes, the lanthanide metal ion is five-coordinated by five nitrogen atoms from five 2,6-diisopropylanilido ligands to form a distorted trigonal bipyramidal geometry. The lithium ion is coordinated by two nitrogen atoms from two 2,6-diisopropylanilido ligands, and one oxygen atom from a THF molecule. It was found that these simple lanthanide anilido complexes are highly efficient for catalyzing hydrophosphonylation reactions of various aldehydes and unactivated ketones to generate α-hydroxyphosphonates in good to excellent yields (up to 99%) within a short time (5 min for aldehydes, 20 min for ketones). Furthermore, the mechanism of hydrophosphonylation reactions has also been elucidated via(1)H NMR monitoring of reaction.

Energy Landscape of All-Atom Protein-Protein Interactions Revealed by Multiscale Enhanced Sampling

PubMed Central

Moritsugu, Kei; Terada, Tohru; Kidera, Akinori

2014-01-01

Protein-protein interactions are regulated by a subtle balance of complicated atomic interactions and solvation at the interface. To understand such an elusive phenomenon, it is necessary to thoroughly survey the large configurational space from the stable complex structure to the dissociated states using the all-atom model in explicit solvent and to delineate the energy landscape of protein-protein interactions. In this study, we carried out a multiscale enhanced sampling (MSES) simulation of the formation of a barnase-barstar complex, which is a protein complex characterized by an extraordinary tight and fast binding, to determine the energy landscape of atomistic protein-protein interactions. The MSES adopts a multicopy and multiscale scheme to enable for the enhanced sampling of the all-atom model of large proteins including explicit solvent. During the 100-ns MSES simulation of the barnase-barstar system, we observed the association-dissociation processes of the atomistic protein complex in solution several times, which contained not only the native complex structure but also fully non-native configurations. The sampled distributions suggest that a large variety of non-native states went downhill to the stable complex structure, like a fast folding on a funnel-like potential. This funnel landscape is attributed to dominant configurations in the early stage of the association process characterized by near-native orientations, which will accelerate the native inter-molecular interactions. These configurations are guided mostly by the shape complementarity between barnase and barstar, and lead to the fast formation of the final complex structure along the downhill energy landscape. PMID:25340714

Three Co(II) complexes with a sexidentate N2O4-donor bis-Schiff base ligand: Synthesis, crystal structures, DFT studies, urease inhibition and molecular docking studies

NASA Astrophysics Data System (ADS)

Wang, Hu; Zhang, Xia; Zhao, Yu; Zhang, Dongmei; Jin, Fan; Fan, Yuhua

2017-11-01

Three new N2O4-donor bis-Schiff base Co(II) complexes, Co(C36H34N2O8)·2CH3OH (1), Co(C28H34N2O8S2)·H2O (2) and Co(C40H36N4O8)·3CH3OH (3) with distorted octahedral six-coordinate Co(II) centers were synthesized and determined by single crystal X-ray analysis. The X-ray crystallography shows that the metal atoms of three complexes are all six-coordinate with two nitrogen atoms from Cdbnd N groups, two oxygen atoms from ether groups and two carboxylic oxygen atoms in the mono-ligand, forming a distorted octahedral geometry. Theoretical studies of the three complexes were carried out by density functional theory (DFT) Becke's three-parameter hybrid (B3LYP) method employing the 6-31G basis set. The DFT studies indicate that the calculation is in accordance with the experimental results. Moreover, inhibition of jack bean urease by Co(II) complexes 1-3 have also been investigated. At the same time, a docking analysis using a DOCK program was conducted to determine the probable binding mode by inserting the complexes into the active site of jack bean urease. The experimental values and docking simulation exhibited that the complex 3 showed strong inhibitory activity (IC50 = 16.43 ± 2.35 μM) and the structure-activity relationships were further discussed.

Synthesis, characterization and single crystal x-ray analysis of a complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine

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

Kumar, Sandeep; Andotra, Savit; Kaur, Mandeep

2016-09-15

Complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine [((2,4- (CH{sub 3}){sub 2}C{sub 6}H{sub 3}O)2PS2)2Fe(NC{sub 5}H{sub 4}(C{sub 2}H{sub 5})-4){sub 2}] is synthesized and characterized by elemental analysis, magnetic moment, IR spectroscopy and single crystal X-ray analysis. Complex crystallizes in the monoclinic sp. gr. P2{sub 1}/n, Z = 2. Crystal structure consists of mononuclear units with Fe(II) ion chelated by four S atoms of the two diphenyldithiophosphate ligands in bidentate manner. N atoms from two 4-ethylpyridine ligands are axially coordinated to the Fe(II) atom leading to an octahedral geometry.

Effect on magnetic properties of germanium encapsulated C60 fullerene

NASA Astrophysics Data System (ADS)

Umran, Nibras Mossa; Kumar, Ranjan

2013-02-01

Structural and electronic properties of Gen(n = 1-4) doped C60 fullerene are investigated with ab initio density functional theory calculations by using an efficient computer code, known as SIESTA. The pseudopotentials are constructed using a Trouiller-Martins scheme, to describe the interaction of valence electrons with the atomic cores. In endohedral doped embedding of more germanium atoms complexes we have seen that complexes are stable and thereafter cage break down. We have also investigated that binding energy, electronic affinity increases and magnetic moment oscillating behavior as the number of semiconductor atoms in C60 fullerene goes on increasing.

Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

DOEpatents

Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

2016-01-26

Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

Nano-fabricated superconducting radio-frequency composites, method for producing nano-fabricated superconducting rf composites

DOEpatents

Norem, James H.; Pellin, Michael J.

2013-06-11

Superconducting rf is limited by a wide range of failure mechanisms inherent in the typical manufacture methods. This invention provides a method for fabricating superconducting rf structures comprising coating the structures with single atomic-layer thick films of alternating chemical composition. Also provided is a cavity defining the invented laminate structure.