The first octahedral cluster complexes with terminal formate ligands: synthesis, structure, and properties of K4[Re6S8(HCOO)6] and Cs4[Re6S8(HCOO)6].

PubMed

Brylev, Konstantin A; Mironov, Yuri V; Kozlova, Svetlana G; Fedorov, Vladimir E; Kim, Sung-Jin; Pietzsch, Hans-Jürgen; Stephan, Holger; Ito, Akitaka; Ishizaka, Shoji; Kitamura, Noboru

2009-03-02

The hexarhenium anionic cluster complex with terminal formate ligands [Re6S8(HCOO)6]4- was obtained by the room-temperature reaction between [Re6S8(OH)6]4- and formic acid in an aqueous solution. The cluster was crystallized as a potassium or cesium salt and characterized by X-ray single-crystal diffraction and elemental analyses, IR, 1H NMR, UV/vis, and luminescence spectroscopies. In particular, the emission quantum yield of the potassium salt of the Re6 cluster anion in the solid phase was determined for the first time. The electronic structures of [Re6S8(HCOO)6]4- and [Re6S8(OH)6]4- were also elucidated by DFT calculations.

Novel Methods in Terminal Ballistics and Mechanochemistry of Damage 2. Phenomenological Mechanochemistry of Damage in Solid Brittle Dielectrics

DTIC Science & Technology

2015-09-01

Phenomenological Mechanochemistry of Damage in Solid Brittle Dielectrics by MA Grinfeld Approved for public release...Army Research Laboratory Novel Methods in Terminal Ballistics and Mechanochemistry of Damage 2. Phenomenological Mechanochemistry of Damage...2. Phenomenological Mechanochemistry of Damage in Solid Brittle Dielectrics 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER

2-Octyl thiophene based three ring mesogens: solid state (13)C NMR and XRD investigations.

PubMed

Veeraprakash, B; Lobo, Nitin P; Narasimhaswamy, T; Mandal, A B

2015-08-14

2-Octyl thiophene based three-ring mesogens namely 4-n-alkoxyphenyl 4-(5-n-octyl-2-thienyl)benzoates are synthesized by employing palladium acetate based direct arylation. The alkoxy terminal is varied with even carbons from C2 to C14 and enantiotropic polymesomorphism is noticed for all the homologs. Accordingly, phase sequence consisting of nematic, smectic A, smectic C and smectic B is seen for mesogens with terminal chains C6, C8, C10 and C12 on cooling the isotropic phase. For mesogens with C2, C4, C8 and C10 terminal alkoxy chains, the mesophase assignment from hot-stage optical microscopy and differential scanning calorimetry is further confirmed by variable temperature powder X-ray diffraction measurements. The appearance of smectic B phase is established by noticing sharp and intense peaks in both small-angle and wide-angle regions. For a representative mesogen, i.e. T10, high-resolution solid-state (13)C NMR investigations are carried out in all the phases, viz. nematic, smectic A, smectic C and smectic B phases. The orientational order parameters calculated from (13)C-(1)H dipolar couplings from 2D SAMPI-4 experiments are found to be 0.44, 0.67, 0.73 and 0.79 in nematic, smectic A, smectic C and smectic B mesophases for the center phenyl ring respectively. Remarkably, the thiophene order parameter in all mesophases is found to be higher than that of phenyl rings and is explained by considering the molecular shape, which has a terminal bend. Further, the mesogens are found to be photoemissive in chloroform solution with an emission band at ∼410 nm.

Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

PubMed

Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

2013-09-01

The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

Ketimine modifications as a route to novel amorphous and derived semicrystalline poly(arylene ether ketone) homo- and copolymers

NASA Technical Reports Server (NTRS)

Mohanty, D. K.; Lowery, R. C.; Lyle, G. D.; Mcgrath, J. E.

1987-01-01

A series of amine terminal amorphous poly(arylene ether ketone) oligomers of controlled molecular weights (2-15 K) were synthesized. These oligomers have been found to undergo 'self-crosslinking' reactions upon heating above 220 C, via the reaction of the terminal amine groups with the in-chain keto carbonyl functionalities. The resulting networks are ductile, chemically resistant, and nonporous. The networks obtained via generated ketimine functionality were characterized by solid state NMR. They have also been found to be remarkably stable toward hydrolysis. Ketimine functional bishalide monomers have also been synthesized. Such monomers have been utilized to synthesize a wide variety of amorphous poly(arylene ether) ketimine polymers. A high molecular weight hydroquinone functional poly(arylene ether) ketimine has been acid treated to regenerate a poly(arylene ether ketone) backbone in solution. This novel procedure thus allows for the synthesis of important matrix resins under relatively mild conditions.

Electrolysis-induced protonation of VO2 thin film transistor for the metal-insulator phase modulation

NASA Astrophysics Data System (ADS)

Katase, Takayoshi; Endo, Kenji; Ohta, Hiromichi

2016-02-01

Compared to state-of-the-art modulation techniques, protonation is the most ideal to control the electrical and optical properties of transition metal oxides (TMOs) due to its intrinsic non-volatile operation. However, the protonation of TMOs is not typically utilized for solid-state devices because of imperative high-temperature annealing treatment in hydrogen source. Although one solution for room temperature (RT) protonation of TMOs is liquid-phase electrochemistry, it is unsuited for practical purposes due to liquid-leakage problem. Herein we demonstrate solid-state RT-protonation of vanadium dioxide (VO2), which is a well-known thermochromic TMO. We fabricated the three terminal thin-film-transistor structure on an insulating VO2 film using a water-infiltrated nanoporous glass, which serves as a solid electrolyte. For gate voltage application, water electrolysis and protonation/deprotonation of VO2 film surface occurred, leading to reversible metal-insulator phase conversion of ~11-nm-thick VO2 layer. The protonation was clearly accompanied by the structural change from an insulating monoclinic to a metallic tetragonal phase. Present results offer a new route for the development of electro-optically active solid-state devices with TMO materials by engineering RT protonation.

Non-equilibrium freezing behaviour of aqueous systems.

PubMed

MacKenzie, A P

1977-03-29

The tendencies to non-equilibrium freezing behaviour commonly noted in representative aqueous systems derive from bulk and surface properties according to the circumstances. Supercooling and supersaturation are limited by heterogeneous nucleation in the presence of solid impurities. Homogeneous nucleation has been observed in aqueous systems freed from interfering solids. Once initiated, crystal growth is ofter slowed and, very frequently, terminated with increasing viscosity. Nor does ice first formed always succeed in assuming its most stable crystalline form. Many of the more significant measurements on a given systeatter permitting the simultaneous representation of thermodynamic and non-equilibrium properties. The diagram incorporated equilibrium melting points, heterogeneous nucleation temperatures, homogeneous nucleation temperatures, glass transition and devitrification temperatures, recrystallization temperatures, and, where appropriate, solute solubilities and eutectic temperatures. Taken together, the findings on modle systems aid the identification of the kinetic and thermodynamic factors responsible for the freezing-thawing survival of living cells.

Effect of Ge surface termination on oxidation behavior

NASA Astrophysics Data System (ADS)

Lee, Younghwan; Park, Kibyung; Cho, Yong Soo; Lim, Sangwoo

2008-09-01

Sulfur-termination was formed on the Ge(1 0 0) surface using (NH 4) 2S solution. Formation of Ge-S and the oxidation of the S-terminated Ge surface were monitored with multiple internal reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. In the 0.5, 5, or 20% (NH 4) 2S solution, H-termination on the Ge(1 0 0) surface was substituted with S-termination in 1 min. When the S-terminated Ge(1 0 0) surface was exposed in air ambient, the oxidation was retarded for about 3600 min. The preservation time of the oxide layer up to one monolayer of S-terminated Ge(1 0 0) surface was about 120 times longer than for the H-terminated Ge(1 0 0) surface. However, the oxidation of S-terminated Ge(1 0 0) surface drastically increased after the threshold time. There was no significant difference in threshold time between S-terminations formed in 0.5, 5, and 20% (NH 4) 2S solutions. With the surface oxidation, desorption of S on the Ge surface was observed. The desorption behavior of sulfur on the S-terminated Ge(1 0 0) surface was independent of the concentration of the (NH 4) 2S solution that forms S-termination. Non-ideal S-termination on Ge surfaces may be related to drastic oxidation of the Ge surface. Finally, with the desulfurization on the S-terminated Ge(1 0 0) surface, oxide growth is accelerated.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-07-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Thermodynamic Optimization of the Ag-Bi-Cu-Ni Quaternary System: Part I, Binary Subsystems

NASA Astrophysics Data System (ADS)

Wang, Jian; Cui, Senlin; Rao, Weifeng

2018-05-01

A comprehensive literature review and thermodynamic optimization of the phase diagrams and thermodynamic properties of the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary systems are presented. CALculation of PHAse Diagrams (CALPHAD)-type thermodynamic optimization was carried out to reproduce all available and reliable experimental phase equilibrium and thermodynamic data. The modified quasichemical model was used to model the liquid solution. The compound energy formalism was utilized to describe the Gibbs energies of all terminal solid solutions and intermetallic compounds. A self-consistent thermodynamic database for the Ag-Bi, Ag-Cu, Ag-Ni, Bi-Cu, and Bi-Ni binary subsystems of the Ag-Bi-Cu-Ni quaternary system was developed. This database can be used as a guide for research and development of lead-free solders.

Terminal attractors for addressable memory in neural networks

NASA Technical Reports Server (NTRS)

Zak, Michail

1988-01-01

A new type of attractors - terminal attractors - for an addressable memory in neural networks operating in continuous time is introduced. These attractors represent singular solutions of the dynamical system. They intersect (or envelope) the families of regular solutions while each regular solution approaches the terminal attractor in a finite time period. It is shown that terminal attractors can be incorporated into neural networks such that any desired set of these attractors with prescribed basins is provided by an appropriate selection of the weight matrix.

On the occurrence of polyproline II structure in elastin

NASA Astrophysics Data System (ADS)

Martino, M.; Bavoso, A.; Guantieri, V.; Coviello, A.; Tamburro, A. M.

2000-02-01

To shed light on the occurrence of the polyproline II (PP II) structure in the elastomeric protein elastin, the octapeptide sequence ALGGGALG of the N-terminal region of human elastin was studied in its monomeric and polymeric form, both in solution and in the solid state. Furthermore, the polymer poly(PG), chosen by us as an a priori reference compound for investigating the stability of PP II structure in presence of alternating proline and glycine residues along the polypeptide chain, was studied by circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. Its "monomeric" form Boc-PG-OH, was also analyzed by X-ray diffraction. It was shown that, in the solid state the presence of PG or GGG sequences in polypeptide chains and even in a short peptide as Boc-PG-OH induces the acquisition of the PP II structural motif. However, in solution this conformation appears to be much more unstable even in the case of long polypeptide chains. The finding that at room temperature the PP II structure is always in equilibrium with other conformers suggests that its dynamics could also contribute to the molecular mechanism of elastin elasticity.

Solid state safety jumper cables

DOEpatents

Kronberg, James W.

1993-01-01

Solid state jumper cables for connecting two batteries in parallel, having two bridge rectifiers for developing a reference voltage, a four-input decoder for determining which terminals are to be connected based on a comparison of the voltage at each of the four terminals to the reference voltage, and a pair of relays for effecting the correct connection depending on the determination of the decoder. No connection will be made unless only one terminal of each battery has a higher voltage than the reference voltage, indicating "positive" terminals, and one has a lower voltage than the reference voltage, indicating "negative" terminals, and that, therefore, the two high voltage terminals may be connected and the two lower voltage terminals may be connected. Current flows once the appropriate relay device is closed. The relay device is preferably a MOSFET (metal oxide semiconductor field effect transistor) combined with a series array of photodiodes that develop MOSFET gate-closing potential when the decoder output causes an LED to light.

Solid state safety jumper cables

DOEpatents

Kronberg, J.W.

1993-02-23

Solid state jumper cables for connecting two batteries in parallel, having two bridge rectifiers for developing a reference voltage, a four-input decoder for determining which terminals are to be connected based on a comparison of the voltage at each of the four terminals to the reference voltage, and a pair of relays for effecting the correct connection depending on the determination of the decoder. No connection will be made unless only one terminal of each battery has a higher voltage than the reference voltage, indicating positive'' terminals, and one has a lower voltage than the reference voltage, indicating negative'' terminals, and that, therefore, the two high voltage terminals may be connected and the two lower voltage terminals may be connected. Current flows once the appropriate relay device is closed. The relay device is preferably a MOSFET (metal oxide semiconductor field effect transistor) combined with a series array of photodiodes that develop MOSFET gate-closing potential when the decoder output causes an LED to light.

Closed-form solutions for a class of optimal quadratic regulator problems with terminal constraints

NASA Technical Reports Server (NTRS)

Juang, J.-N.; Turner, J. D.; Chun, H. M.

1984-01-01

Closed-form solutions are derived for coupled Riccati-like matrix differential equations describing the solution of a class of optimal finite time quadratic regulator problems with terminal constraints. Analytical solutions are obtained for the feedback gains and the closed-loop response trajectory. A computational procedure is presented which introduces new variables for efficient computation of the terminal control law. Two examples are given to illustrate the validity and usefulness of the theory.

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Synthesis, spectroscopic and thermal studies of the copper(II) aspartame chloride complex

NASA Astrophysics Data System (ADS)

Çakır, S.; Coşkun, E.; Naumov, P.; Biçer, E.; Bulut, İ.; İçbudak, H.; Çakır, O.

2002-08-01

Aspartame adduct of copper(II) chloride Cu(Asp) 2Cl 2·2H 2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions.

An Efficient Method to Design Premature End-of-Life Trajectories: A Hypothetical Alternate Fate for Cassini

NASA Technical Reports Server (NTRS)

Vaquero, Mar; Senent, Juan

2015-01-01

What would happen if, hypothetically, the highly successful Cassini mission were to end prematurely due to lack of propellant or sudden subsystem failure? A solid plan to quickly produce a solution for any given scenario, regardless of where the spacecraft is along its reference path, must be in place to safely dispose of the spacecraft and meet all planetary protection requirements. As a contingency plan for this hypothetical situation, a method to design viable high-fidelity terminating trajectories based on a hybrid approach that exploits two-body and three-body flyby transfers combined with a numerical optimization scheme is detailed in this paper.

Preparation of Multiwalled Carbon Nanotubes/Hydroxyl-Terminated Silicone Oil Fiber and Its Application to Analysis of Crude Oils

PubMed Central

Tong, Ting; Zhang, Wanfeng; Dai, Wei; He, Sheng; Chang, Zhenyang; Gao, Xuanbo

2014-01-01

A simple and efficient method to analyze the volatile and semivolatile organic compounds in crude oils has been developed based on direct immersion solid-phase microextraction coupled to comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (DI-SPME-GC × GC/TOFMS). A novel fiber, multiwalled carbon nanotubes/hydroxyl-terminated silicone oil (MWNTs-TSO-OH), was prepared by sol-gel technology. Using standard solutions, the extraction conditions were optimized such as extraction mode, extraction temperature, extraction time, and salts effect. With the optimized conditions, a real crude oil sample was extracted and then analyzed in detail. It shows that the proposed method is very effective in simultaneously analyzing the normal and branched alkanes, cycloalkanes, aromatic hydrocarbons, and biomarkers of crude oil such as steranes and terpanes. Furthermore, the method showed good linearity (r > 0.999), precision (RSD < 8%), and detection limits ranging from 0.2 to 1.6 ng/L. PMID:24578659

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

Anasori, Babak; Lukatskaya, Maria R.; Gogotsi, Yury

The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti 3C 2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. Furthermore, the availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenesmore » allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. Here, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research.« less

2D metal carbides and nitrides (MXenes) for energy storage

DOE PAGES

Anasori, Babak; Lukatskaya, Maria R.; Gogotsi, Yury

2017-01-17

The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti 3C 2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. Furthermore, the availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenesmore » allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. Here, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research.« less

Hybrid proline-rich proteins: novel players in plant cell elongation?

PubMed Central

Dvořáková, Lenka; Srba, Miroslav; Opatrny, Zdenek; Fischer, Lukas

2012-01-01

Background and Aims Hybrid proline-rich proteins (HyPRPs) represent a large family of putative cell-wall proteins characterized by the presence of a variable N-terminal domain and a conserved C-terminal domain that is related to non-specific lipid transfer proteins. The function of HyPRPs remains unclear, but their widespread occurrence and abundant expression patterns indicate that they may be involved in a basic cellular process. Methods To elucidate the cellular function of HyPRPs, we modulated the expression of three HyPRP genes in tobacco (Nicotiana tabacum) BY-2 cell lines and in potato (Solanum tuberosum) plants. Key Results In BY-2 lines, over-expression of the three HyPRP genes with different types of N-terminal domains resulted in similar phenotypic changes, namely increased cell elongation, both in suspension culture and on solid media where the over-expression resulted in enhanced calli size. The over-expressing cells showed increased plasmolysis in a hypertonic mannitol solution and accelerated rate of protoplast release, suggesting loosening of the cell walls. In contrast to BY-2 lines, no phenotypic changes were observed in potato plants over-expressing the same or analogous HyPRP genes, presumably due to more complex compensatory mechanisms in planta. Conclusions Based on the results from BY-2 lines, we propose that HyPRPs, more specifically their C-terminal domains, represent a novel group of proteins involved in cell expansion. PMID:22028464

Terminal attractors in neural networks

NASA Technical Reports Server (NTRS)

Zak, Michail

1989-01-01

A new type of attractor (terminal attractors) for content-addressable memory, associative memory, and pattern recognition in artificial neural networks operating in continuous time is introduced. The idea of a terminal attractor is based upon a violation of the Lipschitz condition at a fixed point. As a result, the fixed point becomes a singular solution which envelopes the family of regular solutions, while each regular solution approaches such an attractor in finite time. It will be shown that terminal attractors can be incorporated into neural networks such that any desired set of these attractors with prescribed basins is provided by an appropriate selection of the synaptic weights. The applications of terminal attractors for content-addressable and associative memories, pattern recognition, self-organization, and for dynamical training are illustrated.

Substituent effects that control conjugated oligomer conformation through non-covalent interactions

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

Sharber, Seth A.; Baral, Rom Nath; Frausto, Fanny

Although understanding the conformations and arrangements of conjugated materials as solids is key to their prospective applications, predictive power over these structural factors remains elusive. In this work, substituent effects tune non-covalent interactions between side-chain fluorinated benzyl esters and main-chain terminal arenes, in turn controlling the conformations and interchromophore aggregation of three-ring phenylene-ethynylenes (PEs). Cofacial fluoroarene–arene (ArF–ArH) interactions cause twisting in the PE backbone, interrupting intramolecular conjugation as well as blocking chromophore aggregation, both of which prevent the typically observed bathochromic shift observed upon transitioning PEs from solution to solid. This work highlights two structural factors that determine whether themore » ArF–ArH interactions, and the resulting twisted, unaggregated chromophores, occur in these solids: (i) the electron-releasing characteristic of substituents on ArH, with more electron-releasing character favoring ArF–ArH interactions, and (ii) the fluorination pattern of the ArF ring, with 2,3,4,5,6-pentafluorophenyl favoring ArF–ArH interactions over 2,4,6-trifluorophenyl. Furthermore, these trends indicate that considerations of electrostatic complementarity, whether through a polar-π or substituent–substituent mechanism, can serve as an effective design principle in controlling the interaction strengths, and therefore the optoelectronic properties, of these molecules as solids.« less

Substituent effects that control conjugated oligomer conformation through non-covalent interactions

DOE PAGES

Sharber, Seth A.; Baral, Rom Nath; Frausto, Fanny; ...

2017-03-31

Although understanding the conformations and arrangements of conjugated materials as solids is key to their prospective applications, predictive power over these structural factors remains elusive. In this work, substituent effects tune non-covalent interactions between side-chain fluorinated benzyl esters and main-chain terminal arenes, in turn controlling the conformations and interchromophore aggregation of three-ring phenylene-ethynylenes (PEs). Cofacial fluoroarene–arene (ArF–ArH) interactions cause twisting in the PE backbone, interrupting intramolecular conjugation as well as blocking chromophore aggregation, both of which prevent the typically observed bathochromic shift observed upon transitioning PEs from solution to solid. This work highlights two structural factors that determine whether themore » ArF–ArH interactions, and the resulting twisted, unaggregated chromophores, occur in these solids: (i) the electron-releasing characteristic of substituents on ArH, with more electron-releasing character favoring ArF–ArH interactions, and (ii) the fluorination pattern of the ArF ring, with 2,3,4,5,6-pentafluorophenyl favoring ArF–ArH interactions over 2,4,6-trifluorophenyl. Furthermore, these trends indicate that considerations of electrostatic complementarity, whether through a polar-π or substituent–substituent mechanism, can serve as an effective design principle in controlling the interaction strengths, and therefore the optoelectronic properties, of these molecules as solids.« less

SPM analysis of fibrinogen adsorption on solid surfaces

NASA Astrophysics Data System (ADS)

Choukourov, A.; Grinevich, A.; Saito, N.; Takai, O.

2007-09-01

The adsorption kinetics, adhesion and orientation of human fibrinogen on solid surfaces have been studied by surface probe microscopy (SPM) and quartz crystal microbalance techniques (QCM). CF 3-, NH 2-terminated organo-silane self-assembled monolayers (SAM) and OH-terminated silicon dioxide have been used as model surfaces. Furthermore, the interaction of fibrinogen with nanocomposite Ti/hydrocarbon plasma polymer films (Ti/ppCH) deposited by dc magnetron sputtering has also been studied.

Low-temperature solution route to macroscopic amounts of hydrogen terminated silicon nanoparticles.

PubMed

Neiner, Doinita; Chiu, Hsiang Wei; Kauzlarich, Susan M

2006-08-30

A new solution route for preparing gram-scale, hydrogen terminated silicon nanoparticles is presented. Dimethoxyethane and diocytl ether have been used to prepare silicon nanoparticles via a solution reaction between sodium silicide and ammonium bromide. The reaction products are isolated as a clear yellow-orange solution and a dark black powder. Both the solution and the powder have been characterized.

Improving the dissolution rate of poorly water soluble drug by solid dispersion and solid solution: pros and cons.

PubMed

Chokshi, Rina J; Zia, Hossein; Sandhu, Harpreet K; Shah, Navnit H; Malick, Waseem A

2007-01-01

The solid dispersions with poloxamer 188 (P188) and solid solutions with polyvinylpyrrolidone K30 (PVPK30) were evaluated and compared in an effort to improve aqueous solubility and bioavailability of a model hydrophobic drug. All preparations were characterized by differential scanning calorimetry, powder X-ray diffraction, intrinsic dissolution rates, and contact angle measurements. Accelerated stability studies also were conducted to determine the effects of aging on the stability of various formulations. The selected solid dispersion and solid solution formulations were further evaluated in beagle dogs for in vivo testing. Solid dispersions were characterized to show that the drug retains its crystallinity and forms a two-phase system. Solid solutions were characterized to be an amorphous monophasic system with transition of crystalline drug to amorphous state. The evaluation of the intrinsic dissolution rates of various preparations indicated that the solid solutions have higher initial dissolution rates compared with solid dispersions. However, after storage at accelerated conditions, the dissolution rates of solid solutions were lower due to partial reversion to crystalline form. The drug in solid dispersion showed better bioavailability in comparison to solid solution. Therefore, considering physical stability and in vivo study results, the solid dispersion was the most suitable choice to improve dissolution rates and hence the bioavailability of the poorly water soluble drug.

General properties of solutions to inhomogeneous Black-Scholes equations with discontinuous maturity payoffs

NASA Astrophysics Data System (ADS)

O, Hyong-Chol; Jo, Jong-Jun; Kim, Ji-Sok

2016-02-01

We provide representations of solutions to terminal value problems of inhomogeneous Black-Scholes equations and study such general properties as min-max estimates, gradient estimates, monotonicity and convexity of the solutions with respect to the stock price variable, which are important for financial security pricing. In particular, we focus on finding representation of the gradient (with respect to the stock price variable) of solutions to the terminal value problems with discontinuous terminal payoffs or inhomogeneous terms. Such terminal value problems are often encountered in pricing problems of compound-like options such as Bermudan options or defaultable bonds with discrete default barrier, default intensity and endogenous default recovery. Our results can be used in pricing real defaultable bonds under consideration of existence of discrete coupons or taxes on coupons.

Two-Dimensional Nb-Based M 4 C 3 Solid Solutions (MXenes)

DOE PAGES

Yang, Jian; Naguib, Michael; Ghidiu, Michael; ...

2015-10-15

Two new two-dimensional Nb 4C 3-based solid solutions (MXenes), (Nb 0.8,Ti 0.2) 4C 3T x and (Nb 0.8,Zr 0.2) 4C 3T x (where T is a surface termination) were synthesizedas confirmed by X-ray diffractionfrom their corresponding MAX phase precursors (Nb 0.8,Ti 0.2) 4AlC 3 and (Nb 0.8,Zr 0.2) 4AlC 3. In our report we discuss Zr-containing MXene. We also studied intercalation of Li ions into these two compositions, and Nb 4C 3T x in order to determine the potential of those materials for energy storage applications. Lithiation and delithiation peaks at 2.26 and 2.35 V, respectively, appeared in the casemore » of Nb 4C 3T x, but were not present in Nb 2CT x. After 20 cycles at a rate of C/4, the specific capacities of (Nb 0.8,Ti 0.2) 4C 3T xand (Nb 0.8,Ti 0.2) 4C 3T x were 158 and 132 mAh/g, respectively, both slightly lower than the capacity of Nb 4C 3T x.« less

Thermodynamic modeling of solid solutions between monosulfate and monochromate 3CaO Bullet Al{sub 2}O{sub 3} Bullet Ca[(CrO{sub 4}){sub x}(SO{sub 4}){sub 1-x}] Bullet nH{sub 2}O

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

Leisinger, Sabine M., E-mail: sabine.leisinger@eawag.ch; Institute of Biogeochemistry and Pollutant Dynamics, ETH, CH-8092 Zurich; Lothenbach, Barbara

2012-01-15

In hydrated cement paste AFm-phases are regarded to play an important role in the binding of the toxic contaminant chromate through isomorphic substitution with sulfate. Solid solutions formation can lower the solubility of the solids, thus reducing chromate leaching concentrations. Solid solutions between monosulfate and monochromate were synthesized and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Based on the measured ion concentrations in solution total solubility products of the solid solution series were determined. For pure monochromate a logK = - 28.4more » {+-} 0.7 was determined. Results from solid and solution analysis showed that limited solid solutions exist. Based on XRD diffractograms a solid solution with a miscibility gap 0.15 < Crx < 0.85 with a dimensionless Guggenheim parameter of 2.43 was proposed.« less

Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

PubMed

Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

2016-08-23

Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.

The donor-supply electrode enhances performance in colloidal quantum dot solar cells.

PubMed

Maraghechi, Pouya; Labelle, André J; Kirmani, Ahmad R; Lan, Xinzheng; Adachi, Michael M; Thon, Susanna M; Hoogland, Sjoerd; Lee, Anna; Ning, Zhijun; Fischer, Armin; Amassian, Aram; Sargent, Edward H

2013-07-23

Colloidal quantum dot (CQD) solar cells combine solution-processability with quantum-size-effect tunability for low-cost harvesting of the sun's broad visible and infrared spectrum. The highest-performing colloidal quantum dot solar cells have, to date, relied on a depleted-heterojunction architecture in which an n-type transparent metal oxide such as TiO2 induces a depletion region in the p-type CQD solid. These devices have, until now, been limited by a modest depletion region depth produced in the CQD solid owing to limitations in the doping available in TiO2. Herein we report a new device geometry-one based on a donor-supply electrode (DSE)-that leads to record-performing CQD photovoltaic devices. Only by employing this new charge-extracting approach do we deepen the depletion region in the CQD solid and thereby extract notably more photocarriers, the key element in achieving record photocurrent and device performance. With the use of optoelectronic modeling corroborated by experiment, we develop the guidelines for building a superior CQD solar cell based on the DSE concept. We confirm that using a shallow-work-function terminal electrode is essential to producing improved charge extraction and enhanced performance.

Single crystal structure analyses of scheelite-powellite CaW1-xMoxO4 solidsolutions and unique occurrence in Jisyakuyama skarn deposits

NASA Astrophysics Data System (ADS)

Yamashita, K.; Yoshiasa, A.; Miyazaki, H.; Tokuda, M.; Tobase, T.; Isobe, H.; Nishiyama, T.; Sugiyama, K.; Miyawaki, R.

2017-12-01

Jisyakuyama skarn deposit, Fukuchi, Fukuoka, Japan, shows a simple occurrenceformed by penetration of hot water into limestone cracks. A unique occurrence of scheelite-powellite CaW1-xMoxO4 minerals is observed in the skarn deposit. Many syntheticexperiments for scheelite-powellite solid solutions have been reported as research onfluorescent materials. In this system it is known that a complete continuous solid solution isformed even at room temperature. In this study, we have carried out the chemical analyses,crystal structural refinements and detail description of occurrence on scheelite-powelliteminerals. We have also attempted synthesis of single crystal of solid solution in a widecomposition range. The chemical compositions were determined by JEOL scanningelectron microscope and EDS, INCA system. We have performed the crystal structurerefinements of the scheelite-powellite CaW1-xMoxO4 solid solutions (x=0.0-1.0) byRIGAKU single-crystal structure analysis system RAPID. The R and S values are around0.0s and 1.03. As the result of structural refinements of natural products and many solidsolutions, we confirm that most large natural single crystals have compositions at bothendmembers, and large solid solution crystals are rare. The lattice constants, interatomicdistances and other crystallographic parameters for the solid solution change uniquely withcomposition and it was confirmed as a continuous solid solution. Single crystals of scheeliteendmember + powellite endmember + solid solution with various compositions form anaggregate in the deposit (Figure 1). Crystal shapes of powellite and scheelite arehypidiomorphic and allotriomorphic, respectively. Many solid solution crystals areaccompanied by scheelite endmember and a compositional gap is observed betweenpowellite and solid-solution crystals. The presence of several penetration solutions withsignificantly different W and Mo contents may be assumed. This research can be expectedto lead to giving restrictive conditions to elucidate the mineralization process. Figure1. Scheelite + Powellite + solid solution aggregate

Synthesis of controlled polymeric cross-linked coatings via iniferter polymerisation in the presence of tetraethyl thiuram disulphide chain terminator.

PubMed

Bossi, A; Whitcombe, M J; Uludag, Y; Fowler, S; Chianella, I; Subrahmanyam, S; Sanchez, I; Piletsky, S A

2010-05-15

A "grafting from" approach has been used for controlled deposition of cross-linked polymers by living radical polymerisation. Borosilicate glass was modified with N,N-diethylaminodithiocarbamoylpropyl(trimethoxy)silane, in order to confine the iniferter reactive groups solely at its surface, then placed in solution with monomers and cross-linker. The polymerisation was initiated by UV irradiation. Formation of the cross-linked polymers was studied in terms of time course of the reaction, type of monomers incorporated and influence of oxygen. Grafted surfaces were characterised by AFM, FT-IR, ellipsometry and contact angle measurements. The ability to control the grafted layer improved dramatically when the chain terminator agent, N,N-N',N'-tetraethyl thiuram disulphide (TED) was added. Upon irradiation TED increases the concentration of passive capping radicals and decreases the possibility of recombination of active macro-radicals, thus prolonging their lifetime. In the absence of TED the thickness of produced coatings was below 10 nm. TED added at different concentrations assisted in the formation of grafted layers of 10-130 nm thickness. Iniferter chemistry in the presence of TED can be used for growing nanometre-scale polymer layers on solid supports. It constitutes a robust general platform for controlled grafting and offer a general solution to address the needs of surface derivatisation in sensors technology. 2010 Elsevier B.V. All rights reserved.

Détermination des densités de charge d'espace dans les isolants solides par la méthode de l'onde thermique

NASA Astrophysics Data System (ADS)

Toureille, A.; Reboul, J.-P.; Merle, P.

1991-01-01

A non-destructive method for the measurement of space charge densities in solid insulating materials is described. This method called “ the thermal step technique ” is concerned with the diffusion of a step of heat applied to one side of the sample and with the resulting nonuniform thermal expansion. From the solution of the equation of heat, we have set up the relations between the measured current and the space charge densities. The deconvolution procedure leading to these charge densities is presented. Some results obtained with this method on XLPE and polypropylene slabs are given. Une nouvelle méthode non destructive, pour la mesure des densités de charges d'espace dans les isolants solides, est décrite. Cette méthode, dite de “ l'onde thermique ” est basée sur la diffusion d'un front de chaleur appliqué à une des faces de l'éprouvette et sur la dilatation non uniforme qui en résulte. A partir de la résolution de l'équation de la chaleur, nous avons établi les relations entre le courant mesuré et les densités de charges. Nous indiquons ensuite un procédé de déconvolution permettant de calculer ces densités de charge. Quelques résultats obtenus par cette méthode, sur des plaques de polyéthylène réticulé et polypropylène sont donnés.

Dehydrogenation of n-Alkanes by Solid-Phase Molecular Pincer-Iridium Catalysts. High Yields of α-Olefin Product.

PubMed

Kumar, Akshai; Zhou, Tian; Emge, Thomas J; Mironov, Oleg; Saxton, Robert J; Krogh-Jespersen, Karsten; Goldman, Alan S

2015-08-12

We report the transfer-dehydrogenation of gas-phase alkanes catalyzed by solid-phase, molecular, pincer-ligated iridium catalysts, using ethylene or propene as hydrogen acceptor. Iridium complexes of sterically unhindered pincer ligands such as (iPr4)PCP, in the solid phase, are found to give extremely high rates and turnover numbers for n-alkane dehydrogenation, and yields of terminal dehydrogenation product (α-olefin) that are much higher than those previously reported for solution-phase experiments. These results are explained by mechanistic studies and DFT calculations which jointly lead to the conclusion that olefin isomerization, which limits yields of α-olefin from pincer-Ir catalyzed alkane dehydrogenation, proceeds via two mechanistically distinct pathways in the case of ((iPr4)PCP)Ir. The more conventional pathway involves 2,1-insertion of the α-olefin into an Ir-H bond of ((iPr4)PCP)IrH2, followed by 3,2-β-H elimination. The use of ethylene as hydrogen acceptor, or high pressures of propene, precludes this pathway by rapid hydrogenation of these small olefins by the dihydride. The second isomerization pathway proceeds via α-olefin C-H addition to (pincer)Ir to give an allyl intermediate as was previously reported for ((tBu4)PCP)Ir. The improved understanding of the factors controlling rates and selectivity has led to solution-phase systems that afford improved yields of α-olefin, and provides a framework required for the future development of more active and selective catalytic systems.

Mixed oxide solid solutions

DOEpatents

Magno, Scott; Wang, Ruiping; Derouane, Eric

2003-01-01

The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

Capillary zone electrophoresis-mass spectrometer interface

DOEpatents

D`Silva, A.

1996-08-06

A device for providing equal electrical potential between two loci unconnected by solid or liquid electrical conductors is provided. The device comprises a first electrical conducting terminal, a second electrical conducting terminal connected to the first terminal by a rigid dielectric structure, and an electrically conducting gas contacting the first and second terminals. This device is particularly suitable for application in the electrospray ionization interface between a capillary zone electrophoresis apparatus and a mass spectrometer. 1 fig.

Capillary zone electrophoresis-mass spectrometer interface

DOEpatents

D'Silva, Arthur

1996-08-06

A device for providing equal electrical potential between two loci unconnected by solid or liquid electrical conducts is provided. The device comprises a first electrical conducting terminal, a second electrical conducting terminal connected to the first terminal by a rigid dielectric structure, and an electrically conducting gas contacting the first and second terminals. This device is particularly suitable for application in the electrospray ionization interface between a capillary zone electrophoresis apparatus and a mass spectrometer.

Effects of protein inter-layers on cell-diamond FET characteristics.

PubMed

Rezek, Bohuslav; Krátká, Marie; Kromka, Alexander; Kalbacova, Marie

2010-12-15

Diamond is recognized as an attractive material for merging solid-state and biological systems. The advantage of diamond field-effect transistors (FET) is that they are chemically resistant, bio-compatible, and can operate without gate oxides. Solution-gated FETs based on H-terminated nanocrystalline diamond films exhibiting surface conductivity are employed here for studying effects of fetal bovine serum (FBS) proteins and osteoblastic SAOS-2 cells on diamond electronic properties. FBS proteins adsorbed on the diamond FETs permanently decrease diamond conductivity as reflected by the -45 mV shift of the FET transfer characteristics. Cell cultivation for 2 days results in a further shift by another -78 mV. We attribute it to a change of diamond material properties rather than purely to the field-effect. Increase in gate leakage currents (by a factor of 4) indicates that the FBS proteins also decrease the diamond-electrolyte electronic barrier induced by C-H surface dipoles. We propose a model where the proteins replace ions in the very vicinity of the H-terminated diamond surface. Copyright © 2010 Elsevier B.V. All rights reserved.

Ultra Small Aperture Terminal for Ka-Band SATCOM

NASA Technical Reports Server (NTRS)

Acosta, Roberto; Reinhart, Richard; Lee, Richard; Simons, Rainee

1997-01-01

An ultra small aperture terminal (USAT) at Ka-band frequency has been developed by Lewis Research Center (LeRC) for data rates up to 1.5 Mbps in the transmit mode and 40 Mbps in receive mode. The terminal consists of a 35 cm diameter offset-fed parabolic antenna which is attached to a solid state power amplifier and low noise amplifier. A single down converter is used to convert the Ka-band frequency to 70 MHz intermediate frequency (IF). A variable rate (9.6 Kbps to 10 Mbps) commercial modem with a standard RS-449/RS-232 interface is used to provide point-to-point digital services. The terminal has been demonstrated numerous times using the Advanced Communications Technology Satellite (ACTS) and the 4.5 in Link Evaluation Terminal (LET) in Cleveland. A conceptual design for an advanced terminal has also been developed. This advanced USAT utilizes Microwave Monolithic Integrated Circuit (MMIC) and flat plate array technologies. This terminal will be self contained in a single package which will include a 1 watt solid state amplifier (SSPA), low noise amplifier (LNA) and a modem card located behind the aperture of the array. The advanced USAT will be light weight, transportable, low cost and easy to point to the satellite. This paper will introduce designs for the reflector based and array based USAT's.

Inhibited solid propellant composition containing beryllium hydride

NASA Technical Reports Server (NTRS)

Thompson, W. W. (Inventor)

1978-01-01

An object of this invention is to provide a composition of beryllium hydride and carboxy-terminated polybutadiene which is stable. Another object of this invention is to provide a method for inhibiting the reactivity of beryllium hydride toward carboxy-terminated polybutadiene. It was found that a small amount of lecithin inhibits the reaction of beryllium hydride with the acid groups in carboxy terminated polybutadiene.

Structural, thermodynamic, and mechanical properties of WCu solid solutions

NASA Astrophysics Data System (ADS)

Liang, C. P.; Wu, C. Y.; Fan, J. L.; Gong, H. R.

2017-11-01

Various properties of Wsbnd Cu solid solutions are systematically investigated through a combined use of first-principles calculation, cluster expansion, special quasirandom structures (SQS), and lattice dynamics. It is shown that SQS are effective to unravel the intrinsic nature of solid solutions, and that BCC and FCC W100-xCux solid solutions are energetically more stable when 0 ≤ x ≤ 70 and 70 < x ≤ 100, respectively. Calculations also reveal that the Debye model should be appropriate to derive thermodynamic properties of Wsbnd Cu, and that the coefficients of thermal expansion of W100-xCux solid solutions are much lower than those of corresponding mechanical mixtures. In addition, the G/B values of W100-xCux solid solutions reach a minimum at x = 50, which is fundamentally due to the softening of phonons as well as strong chemical bonding between W and Cu with a mainly metallic feature.

High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

NASA Astrophysics Data System (ADS)

Eric, R. Hurman; Ozok, Hakan

1994-01-01

The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.

Anticancer Activity Expressed by a Library of 2,9-Diazaperopyrenium Dications

PubMed Central

2016-01-01

Polyaromatic compounds are well-known to intercalate DNA. Numerous anticancer chemotherapeutics have been developed upon the basis of this recognition motif. The compounds have been designed such that they interfere with the role of the topoisomerases, which control the topology of DNA during the cell-division cycle. Although many promising chemotherapeutics have been developed upon the basis of polyaromatic DNA intercalating systems, these candidates did not proceed past clinical trials on account of their dose-limiting toxicity. Herein, we discuss an alternative, water-soluble class of polyaromatic compounds, the 2,9-diazaperopyrenium dications, and report in vitro cell studies for a library of these dications. These investigations reveal that a number of 2,9-diazaperopyrenium dications show similar activities as doxorubicin toward a variety of cancer cell lines. Additionally, we report the solid-state structures of these dications, and we relate their tendency to aggregate in solution to their toxicity profiles. The addition of bulky substituents to these polyaromatic dications decreases their tendency to aggregate in solution. The derivative substituted with 2,6-diisopropylphenyl groups proved to be the most cytotoxic against the majority of the cell lines tested. In the solid state, the 2,6-diisopropylphenyl-functionalized derivative does not undergo π···π stacking, while in aqueous solution, dynamic light scattering reveals that this derivative forms very small (50–100 nm) aggregates, in contrast with the larger ones formed by dications with less bulky substituents. Alteration of the aromaticitiy in the terminal heterocycles of selected dications reveals a drastic change in the toxicity of these polyaromatic species toward specific cell lines. PMID:25555133

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

Synthesis of high quality phosphorothioate oligonucleotides as antisense drugs. Use of I-linker in the elimination of 3'-terminal phosphorothioate monoesters.

PubMed

Ravikumar, Vasulinga T; Kumar, R Krishna; Capaldi, Daniel C; Cole, Douglas L

2003-01-01

Detritylation of a 5'-O-DMT-2'-deoxyadenosine moiety attached to solid support under acidic condition leads to depurination during oligonucleotide synthesis. Deprotection followed by reversed phase HPLC purification leads to desired oligonucleotide contaminated with significant levels of 3'-terminal phosphorothiaote (3'-TPT) monoester (n-1)-mer. However, it is demonstrated that attachment of dA nucleoside through its exocyclic amino group to solid support leads to substantial reduction of 3'-TPT formation thereby improving the quality of oligonucleotide synthesized.

Stabilization of a supersaturated solution of mefenamic acid from a solid dispersion with EUDRAGIT(®) EPO.

PubMed

Kojima, Taro; Higashi, Kenjirou; Suzuki, Toyofumi; Tomono, Kazuo; Moribe, Kunikazu; Yamamoto, Keiji

2012-10-01

The stabilization mechanism of a supersaturated solution of mefenamic acid (MFA) from a solid dispersion with EUDRAGIT(®) EPO (EPO) was investigated. The solid dispersions were prepared by cryogenic grinding method. Powder X-ray diffractometry, in vitro dissolution test, in vivo oral absorption study, infrared spectroscopy, and solid- and solution-state NMR spectroscopies were used to characterize the solid dispersions. Dissolution tests in acetate buffer (pH 5.5) revealed that solid dispersion showed > 200-fold higher concentration of MFA. Supersaturated solution was stable over 1 month and exhibited improved oral bioavailability of MFA in rats, with a 7.8-fold higher area under the plasma concentration-versus-time curve. Solid-state (1)H spin-lattice relaxation time (T(1)) measurement showed that MFA was almost monomolecularly dispersed in the EPO polymer matrix. Intermolecular interaction between MFA and EPO was indicated by solid-state infrared and (13)C-T(1) measurements. Solution-state (1)H-NMR measurement demonstrated that MFA existed in monomolecular state in supersaturated solution. (1)H-T(1) and difference nuclear Overhauser effect measurements indicated that cross relaxation occurred between MFA and EPO due to the small distance between them. The formation and high stability of the supersaturated solution were attributable to the specifically formed intermolecular interactions between MFA and EPO.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

A cyano-terminated dithienyldiketopyrrolopyrrole dimer as a solution processable ambipolar semiconductor under ambient conditions.

PubMed

Wang, Li; Zhang, Xiaojie; Tian, Hongkun; Lu, Yunfeng; Geng, Yanhou; Wang, Fosong

2013-12-14

A cyano-terminated dimer of dithienyldiketopyrrolopyrrole (TDPP), DPP2-CN, is a solution processable ambipolar semiconductor with field-effect hole and electron mobilities of 0.066 and 0.033 cm(2) V(-1) s(-1), respectively, under ambient conditions.

Single crystals of metal solid solutions

NASA Technical Reports Server (NTRS)

Miller, J. F.; Austin, A. E.; Richard, N.; Griesenauer, N. M.; Moak, D. P.; Mehrabian, M. R.; Gelles, S. H.

1974-01-01

The following definitions were sought in the research on single crystals of metal solid solutions: (1) the influence of convection and/or gravity present during crystallization on the substructure of a metal solid solution; (2) the influence of a magnetic field applied during crystallization on the substructure of a metal solid solution; and (3) requirements for a space flight experiment to verify the results. Growth conditions for the selected silver-zinc alloy system are described, along with pertinent technical and experimental details of the project.

Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

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

Sumner, S.C.J.

1986-01-01

Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemicmore » mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.« less

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

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

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

Building Materials from Colloidal Nanocrystal Assemblies: Molecular Control of Solid/Solid Interfaces in Nanostructured Tetragonal ZrO 2

DOE PAGES

Shaw, Santosh; Silva, Tiago F.; Bobbitt, Jonathan M.; ...

2017-08-28

We describe in this paper a bottom-up approach to control the composition of solid/solid interfaces in nanostructured materials, and we test its effectiveness on tetragonal ZrO 2, an inorganic phase of great technological significance. Colloidal nanocrystals capped with trioctylphosphine oxide (TOPO) or oleic acid (OA) are deposited, and the organic fraction of the ligands is selectively etched with O 2 plasma. The interfaces in the resulting all-inorganic colloidal nanocrystal assemblies are either nearly bare (for OA-capped nanocrystals) or terminated with phosphate groups (for TOPO-capped nanocrystals) resulting from the reaction of phosphine oxide groups with plasma species. The chemical modification ofmore » the interfaces has extensive effects on the thermodynamics and kinetics of the material. Different growth kinetics indicate different rate limiting processes of growth (surface diffusion for the phosphate-terminated surfaces and dissolution for the “bare” surfaces). Phosphate termination led to a higher activation energy of growth, and a 3-fold reduction in interfacial energy, and facilitated significantly the conversion of the tetragonal phase into the monoclinic phase. Finally, films devoid of residual ligands persisted in the tetragonal phase at temperatures as high as 900 °C for 24 h.« less

40 CFR 270.43 - Termination of permits.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 26 2010-07-01 2010-07-01 false Termination of permits. 270.43 Section 270.43 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) EPA ADMINISTERED PERMIT PROGRAMS: THE HAZARDOUS WASTE PERMIT PROGRAM Changes to Permit § 270.43...

40 CFR 270.43 - Termination of permits.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 27 2011-07-01 2011-07-01 false Termination of permits. 270.43 Section 270.43 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) EPA ADMINISTERED PERMIT PROGRAMS: THE HAZARDOUS WASTE PERMIT PROGRAM Changes to Permit § 270.43...

A system structure for predictive relations in penetration mechanics

NASA Astrophysics Data System (ADS)

Korjack, Thomas A.

1992-02-01

The availability of a software system yielding quick numerical models to predict ballistic behavior is a requisite for any research laboratory engaged in material behavior. What is especially true about accessibility of rapid prototyping for terminal impaction is the enhancement of a system structure which will direct the specific material and impact situation towards a specific predictive model. This is of particular importance when the ranges of validity are at stake and the pertinent constraints associated with the impact are unknown. Hence, a compilation of semiempirical predictive penetration relations for various physical phenomena has been organized into a data structure for the purpose of developing a knowledge-based decision aided expert system to predict the terminal ballistic behavior of projectiles and targets. The ranges of validity and constraints of operation of each model were examined and cast into a decision tree structure to include target type, target material, projectile types, projectile materials, attack configuration, and performance or damage measures. This decision system implements many penetration relations, identifies formulas that match user-given conditions, and displays the predictive relation coincident with the match in addition to a numerical solution. The physical regimes under consideration encompass the hydrodynamic, transitional, and solid; the targets are either semi-infinite or plate, and the projectiles include kinetic and chemical energy. A preliminary databases has been constructed to allow further development of inductive and deductive reasoning techniques applied to ballistic situations involving terminal mechanics.

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

PubMed Central

2016-01-01

Colloidal semiconductor nanocrystals (NCs) are widely studied as building blocks for novel solid-state materials. Inorganic surface functionalization, used to displace native organic capping ligands from NC surfaces, has been a major enabler of electronic solid-state devices based on colloidal NCs. At the same time, very little is known about the atomistic details of the organic-to-inorganic ligand exchange and binding motifs at the NC surface, severely limiting further progress in designing all-inorganic NCs and NC solids. Taking thiostannates (K4SnS4, K4Sn2S6, K6Sn2S7) as typical examples of chalcogenidometallate ligands and oleate-capped CdSe NCs as a model NC system, in this study we address these questions through the combined application of solution 1H NMR spectroscopy, solution and solid-state 119Sn NMR spectroscopy, far-infrared and X-ray absorption spectroscopies, elemental analysis, and by DFT modeling. We show that through the X-type oleate-to-thiostannate ligand exchange, CdSe NCs retain their Cd-rich stoichiometry, with a stoichiometric CdSe core and surface Cd adatoms serving as binding sites for terminal S atoms of the thiostannates ligands, leading to all-inorganic (CdSe)core[Cdm(Sn2S7)yK(6y-2m)]shell (taking Sn2S76– ligand as an example). Thiostannates SnS44– and Sn2S76– retain (distorted) tetrahedral SnS4 geometry upon binding to NC surface. At the same time, experiments and simulations point to lower stability of Sn2S64– (and SnS32–) in most solvents and its lower adaptability to the NC surface caused by rigid Sn2S2 rings. PMID:25597625

Refraction of Sound Emitted Near Solid Boundaries from a Sheared Jet

NASA Technical Reports Server (NTRS)

Dill, Loren H.; Oyedrian, Ayo A.; Krejsa, Eugene A.

1998-01-01

A mathematical model is developed to describe the sound emitted from an arbitrary point within a turbulent flow near solid boundaries. A unidirectional, transversely sheared mean flow is assumed, and the cross-section of the cold jet is of arbitrary shape. The analysis begins with Lilley's formulation of aerodynamic noise and, depending upon the specific model of turbulence used, leads via Fourier analysis to an expression for the spectral density of the intensity of the far-field sound emitted from a unit volume of turbulence. The expressions require solution of a reduced Green's function of Lilley's equation as well as certain moving axis velocity correlations of the turbulence. Integration over the entire flow field is required in order to predict the sound emitted by the complete flow. Calculations are presented for sound emitted from a plugflow jet exiting a semi-infinite flat duct. Polar plots of the far-field directivity show the dependence upon frequency and source position within the duct. Certain model problems are suggested to investigate the effect of duct termination, duct geometry, and mean flow shear upon the far-field sound.

Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

NASA Astrophysics Data System (ADS)

Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

2018-06-01

The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Anitha, R.; Gupta, Bhavana; Baskar, K.; Singh, Shubra

2016-05-01

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

An added-mass partition algorithm for fluid–structure interactions of compressible fluids and nonlinear solids

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

Banks, J.W., E-mail: banksj3@rpi.edu; Henshaw, W.D., E-mail: henshw@rpi.edu; Kapila, A.K., E-mail: kapila@rpi.edu

We describe an added-mass partitioned (AMP) algorithm for solving fluid–structure interaction (FSI) problems involving inviscid compressible fluids interacting with nonlinear solids that undergo large rotations and displacements. The computational approach is a mixed Eulerian–Lagrangian scheme that makes use of deforming composite grids (DCG) to treat large changes in the geometry in an accurate, flexible, and robust manner. The current work extends the AMP algorithm developed in Banks et al. [1] for linearly elasticity to the case of nonlinear solids. To ensure stability for the case of light solids, the new AMP algorithm embeds an approximate solution of a nonlinear fluid–solidmore » Riemann (FSR) problem into the interface treatment. The solution to the FSR problem is derived and shown to be of a similar form to that derived for linear solids: the state on the interface being fundamentally an impedance-weighted average of the fluid and solid states. Numerical simulations demonstrate that the AMP algorithm is stable even for light solids when added-mass effects are large. The accuracy and stability of the AMP scheme is verified by comparison to an exact solution using the method of analytical solutions and to a semi-analytical solution that is obtained for a rotating solid disk immersed in a fluid. The scheme is applied to the simulation of a planar shock impacting a light elliptical-shaped solid, and comparisons are made between solutions of the FSI problem for a neo-Hookean solid, a linearly elastic solid, and a rigid solid. The ability of the approach to handle large deformations is demonstrated for a problem of a high-speed flow past a light, thin, and flexible solid beam.« less

Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

NASA Astrophysics Data System (ADS)

Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

2018-05-01

The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.

Investigation of compositional segregation during unidirectional solidification of solid solution semiconducting alloys

NASA Technical Reports Server (NTRS)

Wang, J. C.

1982-01-01

Compositional segregation of solid solution semiconducting alloys in the radial direction during unidirectional solidification was investigated by calculating the effect of a curved solid liquid interface on solute concentration at the interface on the solid. The formulation is similar to that given by Coriell, Boisvert, Rehm, and Sekerka except that a more realistic cylindrical coordinate system which is moving with the interface is used. Analytical results were obtained for very small and very large values of beta with beta = VR/D, where V is the velocity of solidification, R the radius of the specimen, and D the diffusivity of solute in the liquid. For both very small and very large beta, the solute concentration at the interface in the solid C(si) approaches C(o) (original solute concentration) i.e., the deviation is minimal. The maximum deviation of C(si) from C(o) occurs for some intermediate value of beta.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Role of lattice distortion on diffuse phase transition temperatures in Bi0.5Na0.5TiO3-BaTiO3 [BNBTO] solid solutions

NASA Astrophysics Data System (ADS)

Pradhan, Lagen Kumar; Pandey, Rabichandra; Kumar, Sunil; Supriya, Sweety; Kar, Manoranjan

2018-04-01

Effect of lattice distortion on diffuse phase transition in BNBTO solid solutions near Morphotropic phase boundary (MPB) has been investigated. Solid solutions of (Bi0.5Na0.5)1-xBaxTiO3 (with mole % of x= 0.04, 0.05, 0.06, 0.07 and 0.08) were prepared by the planetary ball mill method in ethanol medium. Rietveld refinement technique with rhombohedral (R3c) and tetragonal (P4bm) crystal symmetry has been employed for structural as well as phase analysis of the solid solutions. Both rhombohedral and tetragonal lattice distortion (c/a) tends toward the pseudo-cubic crystal symmetry with the increase of mole fraction of Ba2+ near MPB (x= 6 mole %). Also, the average crystallite size and grain size decrease with increase of mole fraction of Ba2+ in BNT ceramic are due to larger ionic radius of Ba2+ and grain boundary pinning process in the solid solutions respectively. Additionally, depolarization temperature (Td) and maximum temperature (Tm) reduces due to the lattice distortion of both the phases in BNBTO solid solutions, which is explained extensively. Significant increase of dielectric constant has been observed near MPB composition (x=6%) in BNBTO solid solutions.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

Calibration methods for explosives detectors

NASA Astrophysics Data System (ADS)

MacDonald, Stephen J.; Rounbehler, David P.

1992-05-01

Airport security has become an important concern to cultures in every corner of the world. Presently, efforts to improve airport security have brought additional technological solutions, in the form of advanced instrumentation for the detection of explosives, into use at airport terminals in many countries. This new generation of explosives detectors is often used to augment existing security measures and provide a more encompassing screening capability for airline passengers. This paper describes two calibration procedures used for the Thermedics' EGIS explosives detectors. The systems were designed to screen people, electronic components, luggage, automobiles, and other objects for the presence of concealed explosives. The detectors have the ability to detect a wide range of explosives in both the vapor state or as surface adsorbed solids, therefore, calibrations were designed to challenge the system with explosives in each form.

The growth of metastable peritectic compounds

NASA Technical Reports Server (NTRS)

Larson, D. J., Jr.

1984-01-01

The influence of gravitationally driven convection on the directional solidification of peritectic alloys was evaluated. The Pb-Bi peritectic was studied as a model solidification system. Analyses of directionally solidified Pb-Bi peritectic samples indicate that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. The macrosegregation results in sequantial change of phase and morphology as solidification progresses down the length of the sample. Banding was eliminated when furnace conditions were selected which resulted in a planar solidification interface. The directional solidification that occurs in the vicinity of the Pb-Bi peritectic isothermal was found to be isocompositional and to consist solely of the equilibrium terminal solid solution and peritectic phases on an extremely fine scale. Evidence was found to support the peritectic supercooling mechanism, but not the proposed peritectic superheat mechanism.

Degree of Biomimicry of Artificial Spider Silk Spinning Assessed by NMR Spectroscopy.

PubMed

Otikovs, Martins; Andersson, Marlene; Jia, Qiupin; Nordling, Kerstin; Meng, Qing; Andreas, Loren B; Pintacuda, Guido; Johansson, Jan; Rising, Anna; Jaudzems, Kristaps

2017-10-02

Biomimetic spinning of artificial spider silk requires that the terminal domains of designed minispidroins undergo specific structural changes in concert with the β-sheet conversion of the repetitive region. Herein, we combine solution and solid-state NMR methods to probe domain-specific structural changes in the NT2RepCT minispidroin, which allows us to assess the degree of biomimicry of artificial silk spinning. In addition, we show that the structural effects of post-spinning procedures can be examined. By studying the impact of NT2RepCT fiber drying, we observed a reversible beta-to-alpha conversion. We think that this approach will be useful for guiding the optimization of artificial spider silk fibers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The chemistry and preparation of tantalum complexes with 2,3-dihydroxy benzoic acid: Experimental and theoretical investigation

NASA Astrophysics Data System (ADS)

Hatzipanayioti, Despina; Kontotheodorou, Konstantinos

2011-03-01

The effect of 2,3-dihydroxybenzoic acid (2,3DHBA, pyrocatechuic acid) on the chloro-alkoxo-species [TaCl 5- x(OMe) x], formed by dissolving TaCl 5 in MeOH, has been studied. The coordination of 2,3DHBA-H 2- on Ta (V) replacing MeO-terminal groups was monitored via NMR spectroscopy. The yellow solid 1 was isolated from the mixture of TaCl 5, with neutral 2,3-DHBA, in MeOH. From this solid the elemental (C, H and Ta), the thermogravimetric analyses, the IR, NMR, ESR and electronic spectra support the formula Ta 2(2,3DHBA) 2(O) 2Cl 4(MeO) 4. The ESR spectrum of solid 1, at 4.2 K, shows a half-field signal apart from a multiline signal around g = 2, supporting evidence for semiquinone and Ta (IV) presence. The occurrence of superoxide radical, in the low temperature of ESR spectrum recording, cannot be ruled out. By heating the solid 1 at 500 °C, an oxide phase showing porous character (SEM) and retaining CO 2 (IR), is evident. Solid 1 heated at 900 °C, leads to the formation of β-Ta 2O 5 orthorhombic phase, as the XRD pattern indicates. The hydrolytic process of solid 1, in aqueous solutions, has been studied; the presence of paramagnetic species generated in situ upon addition of base and the consequent degradative process of 2,3-DHBA, under aerobic conditions is obvious. In order to gain information for the structure of solid 1, DFT calculations have been performed for some theoretical models, based on the empirical formula of solid 1. The calculated structural and spectroscopic parameters have been correlated to experimental results. The energy optimized structures may give an idea about the way of MeCl and MeOMe formation as well some possible intermediates of the hydrolytic mechanism.

Real-time and label-free ring-resonator monitoring of solid-phase recombinase polymerase amplification.

PubMed

Sabaté Del Río, Jonathan; Steylaerts, Tim; Henry, Olivier Y F; Bienstman, Peter; Stakenborg, Tim; Van Roy, Wim; O'Sullivan, Ciara K

2015-11-15

In this work we present the use of a silicon-on-insulator (SOI) chip featuring an array of 64 optical ring resonators used as refractive index sensors for real-time and label-free DNA detection. Single ring functionalisation was achieved using a click reaction after precise nanolitre spotting of specific hexynyl-terminated DNA capture probes to link to an azido-silanised chip surface. To demonstrate detectability using the ring resonators and to optimise conditions for solid-phase amplification, hybridisation between short 25-mer single stranded DNA (ssDNA) fragments and a complementary capture probe immobilised on the surface of the ring resonators was carried out and detected through the shift in the resonant wavelength. Using the optimised conditions demonstrated via the solid-phase hybridisation, a 144-bp double stranded DNA (dsDNA) was then detected directly using recombinase and polymerase proteins through on-chip target amplification and solid-phase elongation of immobilised forward primers on specific rings, at a constant temperature of 37°C and in less than 60min, achieving a limit of detection of 7.8·10(-13)M (6·10(5) copies in 50µL). The use of an automatic liquid handler injection instrument connected to an integrated resealable chip interface (RCI) allowed programmable multiple injection protocols. Air plugs between different solutions were introduced to prevent intermixing and a proportional-integral-derivative (PID) temperature controller minimised temperature based drifts. Published by Elsevier B.V.

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

Rai, R.N., E-mail: rn_rai@yahoo.co.in; Kant, Shiva; Reddi, R.S.B.

Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB andmore » UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solution • Solid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.« less

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

Precipitation in Al–Mg solid solution prepared by solidification under high pressure

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

Jie, J.C., E-mail: jiejc@dlut.edu.cn; School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001; Wang, H.W.

2014-01-15

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al{sub 12}Mg{sub 17} phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solutionmore » appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β.« less

Enhanced photocatalytic degradation of 2-propanol over macroporous GaN/ZnO solid solution prepared by a novel sol-gel method

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

Wang, Lizhong; Ouyang, Shuxin; Ren, Bofan

2015-10-01

Macroporous GaN/ZnO solid solution photocatalyst is synthesized through a novel sol-gel method under mild conditions. The performance of as-synthesized solid solution photocatalyst is evaluated for decomposition of gaseous 2-propanol (IPA). It is found that due to enhancement in both the adsorption to gaseous IPA and the absorbance to visible light, the porous GaN/ZnO solid solution exhibits a good photocatalytic performance for IPA decomposition. Moreover, the mechanism for photocatalytic degradation IPA over porous GaN/ZnO solid solution is also investigated in comparison with those for the two end materials ZnO and GaN. The trapping effects with different scavengers prove that both themore » photoexcited electrons and holes affect the IPA photodegradation process, simultaneously.« less

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

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

Menon, Sumithra Sivadas; Anitha, R.; Baskar, K.

2016-05-23

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 °more » C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.« less

Exploring hardness enhancement in superhard tungsten tetraboride-based solid solutions using radial X-ray diffraction

DOE PAGES

Xie, Miao; Mohammadi, Reza; Turner, Christopher L.; ...

2015-07-29

In this paper, we explore the hardening mechanisms in WB4-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under nonhydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB 4 solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

Ion mobility and transport properties of bismuth fluoride-containing solid solutions with tysonite-type structure

NASA Astrophysics Data System (ADS)

Kavun, V. Ya.; Uvarov, N. F.; Slobodyuk, A. B.; Merkulov, E. B.; Polyantsev, M. M.

2018-07-01

The ion mobility and conductivity of solid solutions with tysonite-type structure obtained by doping bismuth trifluoride with lead (II) fluoride, and zirconium and bismuth oxides have been studied using 19F NMR, X-ray diffraction analysis, and impedance spectroscopy. The types of ionic motions in the fluoride sublattice of the synthesized solid solutions in the temperature range 150-450 K have been determined and the energy of their activation has been estimated. Due to high ionic conductivity, above 10-2 S/cm at 570 K, these solid solutions can be considered as superionic conductors.

Solid-solution CrCoCuFeNi high-entropy alloy thin films synthesized by sputter deposition

DOE PAGES

An, Zhinan; Jia, Haoling; Wu, Yueying; ...

2015-05-04

The concept of high configurational entropy requires that the high-entropy alloys (HEAs) yield single-phase solid solutions. However, phase separations are quite common in bulk HEAs. A five-element alloy, CrCoCuFeNi, was deposited via radio frequency magnetron sputtering and confirmed to be a single-phase solid solution through the high-energy synchrotron X-ray diffraction, energy-dispersive spectroscopy, wavelength-dispersive spectroscopy, and transmission electron microscopy. The formation of the solid-solution phase is presumed to be due to the high cooling rate of the sputter-deposition process.

Investigation of solid nitrogen for cryogenic thermal storage in superconducting cable terminations for enhanced resiliency

NASA Astrophysics Data System (ADS)

Suttell, N.; Zhang, Z.; Kweon, J.; Nes, T.; Kim, C. H.; Pamidi, S.; Ordonez, J. C.

2017-12-01

Low heat capacity of helium makes the helium gas cooled high temperature superconducting (HTS) power devices susceptible to large temperature rises during unexpected heat loads such as electrical faults or cryogenic system failures. Cryogenic thermal storage in the form of solid nitrogen designed in the terminations is explored as a means to increase the thermal stability and operational time of HTS power cables in the event of unexpected heat loads. An external tank containing activated charcoal is used as an adsorption buffer tank for nitrogen gas. The use of activated charcoal minimizes the volume of the buffer tank and prevents pressure rises during melting and boiling of the solid nitrogen. Calculations of the cryogenic thermal storage needed and a description of the experimental setup used to understand the design constraints are discussed.

Modelling solid solutions with cluster expansion, special quasirandom structures, and thermodynamic approaches

NASA Astrophysics Data System (ADS)

Saltas, V.; Horlait, D.; Sgourou, E. N.; Vallianatos, F.; Chroneos, A.

2017-12-01

Modelling solid solutions is fundamental in understanding the properties of numerous materials which are important for a range of applications in various fields including nanoelectronics and energy materials such as fuel cells, nuclear materials, and batteries, as the systematic understanding throughout the composition range of solid solutions for a range of conditions can be challenging from an experimental viewpoint. The main motivation of this review is to contribute to the discussion in the community of the applicability of methods that constitute the investigation of solid solutions computationally tractable. This is important as computational modelling is required to calculate numerous defect properties and to act synergistically with experiment to understand these materials. This review will examine in detail two examples: silicon germanium alloys and MAX phase solid solutions. Silicon germanium alloys are technologically important in nanoelectronic devices and are also relevant considering the recent advances in ternary and quaternary groups IV and III-V semiconductor alloys. MAX phase solid solutions display a palette of ceramic and metallic properties and it is anticipated that via their tuning they can have applications ranging from nuclear to aerospace industries as well as being precursors for particular MXenes. In the final part, a brief summary assesses the limitations and possibilities of the methodologies discussed, whereas there is discussion on the future directions and examples of solid solution systems that should prove fruitful to consider.

Quench-age method for the fabrication of niobium-aluminum superconductors

DOEpatents

Pickus, Milton R.; Ciardella, Robert L.

1978-01-01

A flexible Nb.sub.3 Al superconducting wire is fabricated from a niobium-aluminum composite wire by heating to form a solid solution which is retained at room temperature as a metastable solid solution by quenching. The metastable solid solution is then transformed to the stable superconducting A-15 phase by low temperature aging. The transformation induced by aging can be controlled to yield either a multifilamentary or a solid A-15 core surrounded by ductile niobium.

The origin of the post-tetanic hyperpolarization of mammalian motor nerve terminals

PubMed Central

Gage, P. W.; Hubbard, J. I.

1966-01-01

1. Motor nerve terminals in magnesium-poisoned rat hemidiaphragm-phrenic nerve preparations in vitro were stimulated with short depolarizing pulses of approximately threshold strength and the evoked antidromic responses recorded from the phrenic nerve. The percentage of these 1/sec or 0·5/sec stimuli to which there was no antidromic response was used as a quantitative measure of the terminal excitability. After standard tetanic stimulation (1000 impulses at 100/sec) the excitability of the terminals was depressed for an average duration of 60-70 sec, during most of which time no antidromic responses to stimuli of pretetanic intensity were recorded. There was no significant interaction between stimuli to the terminals at rates of 1 or 0·5/sec. 2. Potassium-free solutions at first increased, then decreased, the post-tetanic depression of excitability. Raising [K]o threefold (15 mM) abolished the post-tetanic depression and often converted it to an exaltation of excitability. 3. Polarizing currents were applied to the terminals with a second electrode. Depolarizing currents increased, while hyperpolarizing currents decreased, the post-tetanic depression of excitability. 4. In solutions with 70% of the normal NaCl content replaced by sucrose, the post-tetanic depression of excitability was reversibly prolonged. 5. In the presence of 7·7 × 10-6 M digoxin or 0·42 mM ouabain there was a small reversible reduction of post-tetanic excitability. 6. After exposure to solutions containing no glucose or to solutions containing 3-5 mM sodium azide the excitability of the terminals was not altered by the tetanus. After washing with the control solution, post-tetanic depression of excitability returned. Antimycin-A (1·8 × 10-6 M) had little or no effect upon post-tetanic excitability. 7. It was concluded that the post-tetanic depression of excitability reflected hyperpolarization of the terminals and that this hyperpolarization was caused by a shift of the membrane potential towards the potassium equilibrium potential because of an increase in potassium permeability. ImagesFig. 1 PMID:5921834

Correlation of Solid State and Solution Coordination Numbers with Infrared Spectroscopy in Five-, Six-, and Eight-Coordinate Transition Metal Complexes of DOTAM.

PubMed

Nagata, Maika K C T; Brauchle, Paul S; Wang, Sen; Briggs, Sarah K; Hong, Young Soo; Laorenza, Daniel W; Lee, Andrea G; Westmoreland, T David

2016-08-16

Three new DOTAM (1,4,7,10-tetrakis(acetamido)-1,4,7,10-tetraazacyclododecane) complexes have been synthesized and characterized by X-ray crystallography: [Co(DOTAM)]Cl 2 •3H 2 O, [Ni(DOTAM)]Cl 2 •4H 2 O, and [Cu(DOTAM)](ClO 4 ) 2 •H 2 O. Solid state and solution IR spectroscopic features for a series of [M(DOTAM)] 2+ complexes (M=Mn, Co, Cu, Ni, Ca, Zn) correlate with solid state and solution coordination numbers. [Co(DOTAM)] 2+ , [Ni(DOTAM)] 2+ , and [Zn(DOTAM)] 2+ are demonstrated to be six-coordinate in both the solid state and in solution, while [Mn(DOTAM)] 2+ and [Ca(DOTAM)] 2+ are eight-coordinate in the solid state and remain so in solution. [Cu(DOTAM)] 2+ , which is five-coordinate by X-ray crystallography, is shown to increase its coordination number in solution to six-coordinate.

Solid/liquid interfacial free energies in binary systems

NASA Technical Reports Server (NTRS)

Nason, D.; Tiller, W. A.

1973-01-01

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

pH-resistant titania hybrid organic-inorganic sol-gel coating for solid-phase microextraction of polar compounds.

PubMed

Li, Xiujuan; Gao, Jie; Zeng, Zhaorui

2007-05-02

A novel titania-hydroxy-terminated silicone oil (titania-OH-TSO) sol-gel coating was developed for solid-phase microextraction of polar compounds. In general, titania-based sol-gel reaction is very fast and need to be decelerated by the use of suitable chelating agents. But in the present work, a judiciously designed sol solution ingredients was used to create the titania-OH-TSO coating without the addition of any chelating agent, which simplified the sol-gel procedure. Thanks to the variety of titania's adsorption sites and their acid-base characteristics, aromatic amines, phenols and polycyclic aromatic hydrocarbons were efficiently extracted and preconcentrated from aqueous samples followed by thermal desorption and GC analysis. The newly developed sol-gel hybrid titania coating demonstrated excellent pH stability, and retained its extraction characteristics intact even after continuous rinsing with a 3 M HCl or NaOH solution for 12 h. Furthermore, it could withstand temperatures as high as 320 degrees C. Practical application was demonstrated through the analysis of six aromatic amines in dye process wastewater. A linearity of four orders of magnitude was obtained with correlation coefficient better than 0.9982. The detection limits ranged from 0.22 to 0.84 microg L(-1) and the repeatability of the measurements was <7.0%. The recoveries of these compounds studied in the wastewater were in the ranges 83.6-101.4%, indicating the method accuracy.

Method for joining metal by solid-state bonding

DOEpatents

Burkhart, L. Elkin; Fultz, Chester R.; Maulden, Kerry A.

1979-01-01

The present development is directed to a method for joining metal at relatively low temperatures by solid-state bonding. Planar surfaces of the metal workpieces are placed in a parallel abutting relationship with one another. A load is applied to at least one of the workpieces for forcing the workpieces together while one of the workpieces is relatively slowly oscillated in a rotary motion over a distance of about 1.degree.. After a preselected number of oscillations, the rotary motion is terminated and the bond between the abutting surfaces is effected. An additional load may be applied to facilitate the bond after terminating the rotary motion.

77 FR 16679 - Emergency Planning and Notification; Emergency Planning and List of Extremely Hazardous...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-22

...The U.S. Environmental Protection Agency (EPA or the Agency) is taking final action to revise the manner for applying the threshold planning quantities (TPQs) for those extremely hazardous substances (EHSs) that are non-reactive solid chemicals in solution. This revision allows facilities subject to the Emergency Planning requirements that have a non-reactive solid EHS in solution, to first multiply the amount of the solid chemical in solution on-site by 0.2 before determining if this quantity equals or exceeds the lower published TPQ. This change is based on data that shows less potential for non-reactive solid chemicals in solution to remain airborne and dispersed beyond a facility's fence line in the event of an accidental release. Previously, EPA assumed that 100% of non-reactive solid chemicals in solution could become airborne and dispersed beyond the fenceline in the event of an accidental release.

Experimental studies of fundamental issues in electron transfer through nanometer scale devices

NASA Astrophysics Data System (ADS)

Yamamoto, Hiromichi

Electron transfer reactions constitute many of the primary events in materials science, chemistry, physics, and biochemistry, e.g. the electron transport properties and photoexcited processes in solids and molecules, chemical reactions, corrosion, photosynthesis, respiration, and so forth. A self-assembled monolayer (SAM) film provides us with a unique environment not only to understand and manipulate the surface electronic properties of a solid, but also to control electron transfer processes at the interface. The first topic in this thesis describes the structure and electron tunneling characterization of alkanethiol SAMs on InP(100). Angle-resolved X-ray photoelectron spectroscopy was used to characterize the bonding of alkanethiols to n-InP surfaces and to measure the monolayer thickness. The results showed that the sulfur binds to In atoms on the surface, and provided film thicknesses of 6.4 A for C8H17SH, 11.1 A for C12H25SH, and 14.9 A for C16H 33SH, resulting in an average tilt angle of 55°. The analysis indicated that super-exchange coupling between the alkane chains plays an important role in defining electron tunneling barriers, especially for highly tilted chains. The second topic describes studies of cytochrome c bound to pure and mixed SAMs of o-terminated alkanethiol (terminated with pyridine, imidazole or nitrile groups) and alkanethiol on gold. Electrochemical methods are used to determine electron transfer rate constants of cytochrome c, and scanning tunneling microscopy to observe the cytochrome c on the SAM. Detailed analysis revealed direct association of the heme of cytochrome c with the terminal groups of the SAMs and a 'turning-over' of the electron transfer of cytochrome c from adiabatic to non-adiabatic regime. The third topic describes studies of oxidation and reduction of cytochrome c in solution through eleven different self-assembled monolayers (SAMs) on gold electrodes by cyclic voltammetry. Electron transfer rate constants of cytochrome c through the eleven SAMs ranged from ≤10-4 to ˜10-1 cm/sec. A strong correlation between the electron transfer rate constants and the hydrogen bonding ability of the SAM is identified. This correlation is discussed in terms of the dependence of the rate constant on the outer-sphere reorganization energy and the electronic coupling between the cytochrome and the differently terminated monolayer films.

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.

Analytical solution for the transient wave propagation of a buried cylindrical P-wave line source in a semi-infinite elastic medium with a fluid surface layer

NASA Astrophysics Data System (ADS)

Shan, Zhendong; Ling, Daosheng

2018-02-01

This article develops an analytical solution for the transient wave propagation of a cylindrical P-wave line source in a semi-infinite elastic solid with a fluid layer. The analytical solution is presented in a simple closed form in which each term represents a transient physical wave. The Scholte equation is derived, through which the Scholte wave velocity can be determined. The Scholte wave is the wave that propagates along the interface between the fluid and solid. To develop the analytical solution, the wave fields in the fluid and solid are defined, their analytical solutions in the Laplace domain are derived using the boundary and interface conditions, and the solutions are then decomposed into series form according to the power series expansion method. Each item of the series solution has a clear physical meaning and represents a transient wave path. Finally, by applying Cagniard's method and the convolution theorem, the analytical solutions are transformed into the time domain. Numerical examples are provided to illustrate some interesting features in the fluid layer, the interface and the semi-infinite solid. When the P-wave velocity in the fluid is higher than that in the solid, two head waves in the solid, one head wave in the fluid and a Scholte wave at the interface are observed for the cylindrical P-wave line source.

Solid lipid nanoparticles suspension versus commercial solutions for dermal delivery of minoxidil.

PubMed

Padois, Karine; Cantiéni, Céline; Bertholle, Valérie; Bardel, Claire; Pirot, Fabrice; Falson, Françoise

2011-09-15

Solid lipid nanoparticles have been reported as possible carrier for skin drug delivery. Solid lipid nanoparticles are produced from biocompatible and biodegradable lipids. Solid lipid nanoparticles made of semi-synthetic triglycerides stabilized with a mixture of polysorbate and sorbitan oleate were loaded with 5% of minoxidil. The prepared systems were characterized for particle size, pH and drug content. Ex vivo skin penetration studies were performed using Franz-type glass diffusion cells and pig ear skin. Ex vivo skin corrosion studies were realized with a method derived from the Corrositex(®) test. Solid lipid nanoparticles suspensions were compared to commercial solutions in terms of skin penetration and skin corrosion. Solid lipid nanoparticles suspensions have been shown as efficient as commercial solutions for skin penetration; and were non-corrosive while commercial solutions presented a corrosive potential. Solid lipid nanoparticles suspensions would constitute a promising formulation for hair loss treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

The application design of a mobile terminal: key technologies of mobile location-based service system

NASA Astrophysics Data System (ADS)

Tong, Xiaohui; Liu, Jingao; Wang, Zhenghao; Wang, Shuxian

2004-03-01

This paper presents several key technologies in the Mobile Location Based Service (MLBS) system of Shanghai. In the paper, the author presents a solution of handset mobile terminal, PDA+GPS+GSM/GPRS. The paper particularly introduces the hardware of the terminal and the acquirement of GPS information at the terminal. The paper also introduces how the terminal communicates with the special service center.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers

NASA Astrophysics Data System (ADS)

Del Rosso, T.; Rey, N. A.; Rosado, T.; Landi, S.; Larrude, D. G.; Romani, E. C.; Freire Junior, F. L.; Quinteiro, S. M.; Cremona, M.; Aucelio, R. Q.; Margheri, G.; Pandoli, O.

2016-06-01

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Synthesis of oxocarbon-encapsulated gold nanoparticles with blue-shifted localized surface plasmon resonance by pulsed laser ablation in water with CO2 absorbers.

PubMed

Del Rosso, T; Rey, N A; Rosado, T; Landi, S; Larrude, D G; Romani, E C; Junior, F L Freire; Quinteiro, S M; Cremona, M; Aucelio, R Q; Margheri, G; Pandoli, O

2016-06-24

Colloidal suspensions of oxocarbon-encapsulated gold nanoparticles have been synthesized in a one-step procedure by pulsed-laser ablation (PLA) at 532 nm of a solid gold target placed in aqueous solution containing CO2 absorbers, but without any stabilizing agent. Multi-wavelength surface enhanced Raman spectroscopy allows the identification of adsorbed amorphous carbon and graphite, Au-carbonyl, Au coordinated CO2-derived bicarbonates/carbonates and hydroxyl groups around the AuNPs core. Scanning electron microscopy, energy dispersive x-ray analysis and high resolution transmission electron microscopy highlight the organic shell structure around the crystalline metal core. The stability of the colloidal solution of nanocomposites (NCs) seems to be driven by solvation forces and is achieved only in neutral or basic pH using monovalent hydroxide counter-ions (NaOH, KOH). The NCs are characterized by a blue shift of the localized surface plasmon resonance (LSPR) band typical of metal-ligand stabilization by terminal π-back bonding, attributed to a core charging effect caused by Au-carbonyls. Total organic carbon measurements detect the final content of organic carbon in the colloidal solution of NCs that is about six times higher than the value of the water solution used to perform PLA. The colloidal dispersions of NCs are stable for months and are applied as analytical probes in amino glycoside antibiotic LSPR based sensing.

Role of the chemical substitution on the luminescence properties of solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} (0 ≤ x ≤1)

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

Taoufyq, A.; Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir; CEA, DEN, Département d'Etudes des Réacteurs, Service de Physique Expérimentale, Laboratoire Dosimétrie Capteurs Instrumentation, 13108 Saint-Paul-lez-Durance

2015-10-15

Highlights: • Luminescence can be modified by chemical substitution in solid solutions Ca{sub 1−x}Cd{sub x}WO{sub 4}. • The various emission spectra (charge transfer) were obtained under X-ray excitation. • Scheelite or wolframite solid solutions presented two types of emission spectra. • A luminescence component depended on cadmium substitution in each solid solution. • A component was only characteristic of oxyanion symmetry in each solid solution. - Abstract: We have investigated the chemical substitution effects on the luminescence properties under X-ray excitation of the solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} with 0 ≤ x ≤ 1. Two types of wide spectralmore » bands, associated with scheelite-type or wolframite-type solid solutions, have been observed at room temperature. We decomposed each spectral band into several spectral components characterized by energies and intensities varying with composition x. One Gaussian component was characterized by an energy decreasing regularly with the composition x, while the other Gaussian component was only related to the tetrahedral or octahedral configurations of tungstate groups WO{sub 4}{sup 2−} or WO{sub 6}{sup 6−}. The luminescence intensities exhibited minimum values in the composition range x < 0.5 corresponding to scheelite-type structures, then, they regularly increased for cadmium compositions x > 0.5 corresponding to wolframite-type structures.« less

Immobilization methods for the rapid total chemical synthesis of proteins on microtiter plates.

PubMed

Zitterbart, Robert; Krumrey, Michael; Seitz, Oliver

2017-07-01

The chemical synthesis of proteins typically involves the solid-phase peptide synthesis of unprotected peptide fragments that are stitched together in solution by native chemical ligation (NCL). The process is slow, and throughput is limited because of the need for repeated high performance liquid chromatography purification steps after both solid-phase peptide synthesis and NCL. With an aim to provide faster access to functional proteins and to accelerate the functional analysis of synthetic proteins by parallelization, we developed a method for the high performance liquid chromatography-free synthesis of proteins on the surface of microtiter plates. The method relies on solid-phase synthesis of unprotected peptide fragments, immobilization of the C-terminal fragment and on-surface NCL with an unprotected peptide thioester in crude form. Herein, we describe the development of a suitable immobilization chemistry. We compared (i) formation of nickel(II)-oligohistidine complexes, (ii) Cu-based [2 + 3] alkine-azide cycloaddition and (iii) hydrazone ligation. The comparative study identified the hydrazone ligation as most suitable. The sequence of immobilization via hydrazone ligation, on-surface NCL and radical desulfurization furnished the targeted SH3 domains in near quantitative yield. The synthetic proteins were functional as demonstrated by an on-surface fluorescence-based saturation binding analysis. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd.

Eutectics as improved pharmaceutical materials: design, properties and characterization.

PubMed

Cherukuvada, Suryanarayan; Nangia, Ashwini

2014-01-28

Eutectics are a long known class of multi-component solids with important and useful applications in daily life. In comparison to other multi-component crystalline solids, such as salts, solid solutions, molecular complexes and cocrystals, eutectics are less studied in terms of molecular structure organization and bonding interactions. Classically, a eutectic is defined based on its low melting point compared to the individual components. In this article, we attempt to define eutectics not just based on thermal methods but from a structural organization view point, and discuss their microstructures and properties as organic materials vis-a-vis solid solutions and cocrystals. The X-ray crystal structure of a cocrystal is different from that of the individual components whereas the unit cell of a solid solution is similar to that of one of the components. Eutectics are closer to the latter species in that their crystalline arrangement is similar to the parent components but they are different with respect to the structural integrity. A solid solution possesses structural homogeneity throughout the structure (single phase) but a eutectic is a heterogeneous ensemble of individual components whose crystal structures are like discontinuous solid solutions (phase separated). Thus, a eutectic may be better defined as a conglomerate of solid solutions. A structural analysis of cocrystals, solid solutions and eutectics has led to an understanding that materials with strong adhesive (hetero) interactions between the unlike components will lead to cocrystals whereas those having stronger cohesive (homo/self) interactions will more often give rise to solid solutions (for similar structures of components) and eutectics (for different structures of components). We demonstrate that the same crystal engineering principles which have been profitably utilized for cocrystal design in the past decade can now be applied to make eutectics as novel composite materials, illustrated by stable eutectics of the hygroscopic salt of the anti-tuberculosis drug ethambutol as a case study. A current gap in the characterization of eutectic microstructure may be fulfilled through pair distribution function (PDF) analysis of X-ray diffraction data, which could be a rapid signature technique to differentiate eutectics from their components.

Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

PubMed

Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

2014-01-01

We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

NEUTRALIZATIONS OF HIGH ALUMINUM LOW URANIUM USED NUCLEAR FUEL SOLUTIONS CONTAINING GADOLINIUM AS A NEUTRON POISON

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

Taylor-Pashow, K.

2011-06-08

H-Canyon will begin dissolving High Aluminum - Low Uranium (High Al/Low U) Used Nuclear Fuel (UNF) following approval by DOE which is anticipated in CY2011. High Al/Low U is an aluminum/enriched uranium UNF with small quantities of uranium relative to aluminum. The maximum enrichment level expected is 93% {sup 235}U. The High Al/Low U UNF will be dissolved in H-Canyon in a nitric acid/mercury/gadolinium solution. The resulting solution will be neutralized and transferred to Tank 39H in the Tank Farm. To confirm that the solution generated could be poisoned with Gd, neutralized, and discarded to the Savannah River Site (SRS)more » high level waste (HLW) system without undue nuclear safety concerns the caustic precipitation of simulant solutions was examined. Experiments were performed with three simulant solutions representative of the H-Canyon estimated concentrations in the final solutions after dissolution. The maximum U, Gd, and Al concentration were selected for testing from the range of solution compositions provided. Simulants were prepared in three different nitric acid concentrations, ranging from 0.5 to 1.5 M. The simulant solutions were neutralized to four different endpoints: (1) just before a solid phase was formed (pH 3.5-4), (2) the point where a solid phase was obtained, (3) 0.8 M free hydroxide, and (4) 1.2 M free hydroxide, using 50 wt % sodium hydroxide (NaOH). The settling behavior of the neutralized solutions was found to be slower compared to previous studies, with settling continuing over a one week period. Due to the high concentration of Al in these solutions, precipitation of solids was observed immediately upon addition of NaOH. Precipitation continued as additional NaOH was added, reaching a point where the mixture becomes almost completely solid due to the large amount of precipitate. As additional NaOH was added, some of the precipitate began to redissolve, and the solutions neutralized to the final two endpoints mixed easily and had expected densities of typical neutralized waste. Based on particle size and scanning electron microscopy analyses, the neutralized solids were found to be homogeneous and less than 20 microns in size. The majority of solids were less than 4 microns in size. Compared to previous studies, a larger percentage of the Gd was found to precipitate in the partially neutralized solutions (at pH 3.5-4). In addition the Gd:U mass ratio was found to be at least 1.0 in all of the solids obtained after partial or full neutralization. The hydrogen to U (H:U) molar ratios for two accident scenarios were also determined. The first was for transient neutralization and agitator failure. Experimentally this scenario was determined by measuring the H:U ratio of the settled solids. The minimum H:U molar ratio for solids from fully neutralized solutions was 388:1. The second accident scenario is for the solids drying out in an unagitiated pump box. Experimentally, this scenario was determined by measuring the H:U molar ratio in centrifuged solids. The minimum H:U atom ratios for centrifuged precipitated solids was 250:1. It was determined previously that a 30:1 H:Pu atom ratio was sufficient for a 1:1 Gd:Pu mass ratio. Assuming a 1:1 equivalence with {sup 239}Pu, the results of these experiments show Gd is a viable poison for neutralizing U/Gd solutions with the tested compositions.« less

Estimated heats of fusion of fluoride salt mixtures suitable for thermal energy storage applications

NASA Technical Reports Server (NTRS)

Misra, A. K.; Whittenberger, J. D.

1986-01-01

The heats of fusion of several fluoride salt mixtures with melting points greater than 973 K were estimated from a coupled analysis of the available thermodynamic data and phase diagrams. Simple binary eutectic systems with and without terminal solid solutions, binary eutectics with congruent melting intermediate phases, and ternary eutectic systems were considered. Several combinations of salts were identified, most notable the eutectics LiF-22CaF2 and NaF-60MgF2 which melt at 1039 and 1273 K respectively which posses relatively high heats of fusion/gm (greater than 0.7 kJ/g). Such systems would seemingly be ideal candidates for the light weight, high energy storage media required by the thermal energy storage unit in advanced solar dynamic power systems envisioned for the future space missions.

General solutions for the oxidation kinetics of polymers

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

Gillen, K.T.; Clough, R.L.; Wise, J.

1996-08-01

The simplest general kinetic schemes applicable to the oxidation of polymers are presented, discussed and analyzed in terms of the underlying kinetic assumptions. For the classic basic autoxidation scheme (BAS), which involves three bimolecular termination steps and is applicable mainly to unstabilized polymers, typical assumptions used singly or in groups include (1) long kinetic chain length, (2) a specific ratio of the termination rate constants and (3) insensitivity to the oxygen concentration (e.g., domination by a single termination step). Steady-state solutions for the rate of oxidation are given in terms of one, two, three, or four parameters, corresponding respectively tomore » three, two, one, or zero kinetic assumptions. The recently derived four-parameter solution predicts conditions yielding unusual dependencies of the oxidation rate on oxygen concentration and on initiation rate, as well as conditions leading to some unusual diffusion-limited oxidation profile shapes. For stabilized polymers, unimolecular termination schemes are typically more appropriate than bimolecular. Kinetics incorporating unimolecular termination reactions are shown to result in very simple oxidation expressions which have been experimentally verified for both radiation-initiated oxidation of an EPDM and thermoxidative degradation of nitrile and chloroprene elastomers.« less

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Pyrolysis process for producing condensed stabilized hydrocarbons utilizing a beneficially reactive gas

DOEpatents

Durai-Swamy, Kandaswamy

1982-01-01

In a process for recovery of values contained in solid carbonaceous material, the solid carbonaceous material is comminuted and then subjected to pyrolysis, in the presence of a carbon containing solid particulate source of heat and a beneficially reactive transport gas in a transport flash pyrolysis reactor, to form a pyrolysis product stream. The pyrolysis product stream contains a gaseous mixture and particulate solids. The solids are separated from the gaseous mixture to form a substantially solids-free gaseous stream which comprises volatilized hydrocarbon free radicals newly formed by pyrolysis. Preferably the solid particulate source of heat is formed by oxidizing part of the separated particulate solids. The beneficially reactive transport gas inhibits the reactivity of the char product and the carbon-containing solid particulate source of heat. Condensed stabilized hydrocarbons are obtained by quenching the gaseous mixture stream with a quench fluid which contains a capping agent for stabilizing and terminating newly formed volatilized hydrocarbon free radicals. The capping agent is partially depleted of hydrogen by the stabilization and termination reaction. Hydrocarbons of four or more carbon atoms in the gaseous mixture stream are condensed. A liquid stream containing the stabilized liquid product is then treated or separated into various fractions. A liquid containing the hydrogen depleted capping agent is hydrogenated to form a regenerated capping agent. At least a portion of the regenerated capping agent is recycled to the quench zone as the quench fluid. In another embodiment capping agent is produced by the process, separated from the liquid product mixture, and recycled.

Artificial Intelligence Techniques for the Berth Allocation and Container Stacking Problems in Container Terminals

NASA Astrophysics Data System (ADS)

Salido, Miguel A.; Rodriguez-Molins, Mario; Barber, Federico

The Container Stacking Problem and the Berth Allocation Problem are two important problems in maritime container terminal's management which are clearly related. Terminal operators normally demand all containers to be loaded into an incoming vessel should be ready and easily accessible in the terminal before vessel's arrival. Similarly, customers (i.e., vessel owners) expect prompt berthing of their vessels upon arrival. In this paper, we present an artificial intelligence based-integrated system to relate these problems. Firstly, we develop a metaheuristic algorithm for berth allocation which generates an optimized order of vessel to be served according to existing berth constraints. Secondly, we develop a domain-oriented heuristic planner for calculating the number of reshuffles needed to allocate containers in the appropriate place for a given berth ordering of vessels. By combining these optimized solutions, terminal operators can be assisted to decide the most appropriated solution in each particular case.

Flight demonstration of flight termination system and solid rocket motor ignition using semiconductor laser initiated ordnance

NASA Astrophysics Data System (ADS)

Schulze, Norman R.; Maxfield, B.; Boucher, C.

1995-01-01

Solid State Laser Initiated Ordnance (LIO) offers new technology having potential for enhanced safety, reduced costs, and improved operational efficiency. Concerns over the absence of programmatic applications of the technology, which has prevented acceptance by flight programs, should be abated since LIO has now been operationally implemented by the Laser Initiated Ordnance Sounding Rocket Demonstration (LOSRD) Program. The first launch of solid state laser diode LIO at the NASA Wallops Flight Facility (WFF) occurred on March 15, 1995 with all mission objectives accomplished. This project, Phase 3 of a series of three NASA Headquarters LIO demonstration initiatives, accomplished its objective by the flight of a dedicated, all-LIO sounding rocket mission using a two-stage Nike-Orion launch vehicle. LIO flight hardware, made by The Ensign-Bickford Company under NASA's first Cooperative Agreement with Profit Making Organizations, safely initiated three demanding pyrotechnic sequence events, namely, solid rocket motor ignition from the ground and in flight, and flight termination, i.e., as a Flight Termination System (FTS). A flight LIO system was designed, built, tested, and flown to support the objectives of quickly and inexpensively putting LIO through ground and flight operational paces. The hardware was fully qualified for this mission, including component testing as well as a full-scale system test. The launch accomplished all mission objectives in less than 11 months from proposal receipt. This paper concentrates on accomplishments of the ordnance aspects of the program and on the program's implementation and results. While this program does not generically qualify LIO for all applications, it demonstrated the safety, technical, and operational feasibility of those two most demanding applications, using an all solid state safe and arm system in critical flight applications.

LEACHING OF TITANIUM FROM MONOSODIUM TITANATE AND MODIFIED MST

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

Taylor-Pashow, K.; Fondeur, F.; Fink, S.

2012-08-01

Analysis of a fouled coalescer and pre-filters from Actinide Removal Process/Modular Caustic Side Solvent Extraction Unit (ARP/MCU) operations showed evidence of Ti containing solids. Based on these results a series of tests were planned to examine the extent of Ti leaching from monosodium titanate (MST) and modified monosodium titanate (mMST) in various solutions. The solutions tested included a series of salt solutions with varying free hydroxide concentrations, two sodium hydroxide concentrations, 9 wt % and 15 wt %, nitric and oxalic acid solutions. Overall, the amount of Ti leached from the MST and mMST was much greater in the acidmore » solutions compared to the sodium hydroxide or salt solutions, which is consistent with the expected trend. The leaching data also showed that increasing hydroxide concentration, whether pure NaOH solution used for filter cleaning in ARP or the waste salt solution, increased the amount of Ti leached from both the MST and mMST. For the respective nominal contact times with the MST solids - for filter cleaning or the normal filter operation, the dissolved Ti concentrations are comparable suggesting either cause may contribute to the increased Ti fouling on the MCU coalescers. Tests showed that Ti containing solids could be precipitated from solution after the addition of scrub acid and a decrease in temperature similar to expected in MCU operations. FTIR analysis of these solids showed some similarity to the solids observed on the fouled coalescer and pre-filters. Although only a cursory study, this information suggests that the practice of increasing free hydroxide in feed solutions to MCU as a mitigation to aluminosilicate formation may be offset by the impact of formation of Ti solids in the overall process. Additional consideration of this finding from MCU and SWPF operation is warranted.« less

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Simple formula for the thermal conductivity of a quaternary solid solution

NASA Astrophysics Data System (ADS)

Nakwaski, W.

1988-11-01

An analysis is made of the thermal conductivity of quaternary solid solutions (alloys) allowing for their disordered structure on the basis of a phenomenological analysis proposed by Abeles. This method is applied to a quaternary solid solution In1 - xGaxAsyP1 - y. A simple analytic expression is derived for the thermal conductivity of this material.

Lattice Parameter Behavior with Different Nd and O Concentrations in (U 1-yNd y)O 2±x Solid Solution

DOE PAGES

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.; ...

2016-02-02

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Crankshaft motion in a highly congested bis(triarylmethyl)peroxide.

PubMed

Khuong, Tinh-Alfredo V; Zepeda, Gerardo; Sanrame, Carlos N; Dang, Hung; Bartberger, Michael D; Houk, K N; Garcia-Garibay, Miguel A

2004-11-17

Crankshaft motion has been proposed in the solid state for molecular fragments consisting of three or more rotors linked by single bonds, whereby the two terminal rotors are static and the internal rotors experience circular motion. Bis-[tri-(3,5-di-tert-butyl)phenylmethyl]-peroxide 2 was tested as a model in search of crankshaft motion at the molecular level. In the case of peroxide 2, the bulky trityl groups may be viewed as the external static rotors, while the two peroxide oxygens can undergo the sought after internal rotation. Evidence for this process in the case of peroxide 2 was obtained from conformational dynamics determined by variable-temperature (13)C and (1)H NMR between 190 and 375 K in toluene-d(8). Detailed spectral assignments for the interpretation of two coalescence processes were based on a correlation between NMR spectra obtained in solution at low temperature, in the solid state by (13)C CPMAS NMR, and by GIAO calculations based on a B3LYP/6-31G structure of 2 obtained from its X-ray coordinates as the input. Evidence supporting crankshaft rotation rather than slippage of the trityl groups was obtained from molecular mechanics calculations.

Hopping Diffusion of Nanoparticles in Polymer Matrices

PubMed Central

2016-01-01

We propose a hopping mechanism for diffusion of large nonsticky nanoparticles subjected to topological constraints in both unentangled and entangled polymer solids (networks and gels) and entangled polymer liquids (melts and solutions). Probe particles with size larger than the mesh size ax of unentangled polymer networks or tube diameter ae of entangled polymer liquids are trapped by the network or entanglement cells. At long time scales, however, these particles can diffuse by overcoming free energy barrier between neighboring confinement cells. The terminal particle diffusion coefficient dominated by this hopping diffusion is appreciable for particles with size moderately larger than the network mesh size ax or tube diameter ae. Much larger particles in polymer solids will be permanently trapped by local network cells, whereas they can still move in polymer liquids by waiting for entanglement cells to rearrange on the relaxation time scales of these liquids. Hopping diffusion in entangled polymer liquids and networks has a weaker dependence on particle size than that in unentangled networks as entanglements can slide along chains under polymer deformation. The proposed novel hopping model enables understanding the motion of large nanoparticles in polymeric nanocomposites and the transport of nano drug carriers in complex biological gels such as mucus. PMID:25691803

Revisiting HgCl 2: A solution- and solid-state 199Hg NMR and ZORA-DFT computational study

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Carver, Colin T.; Larsen, Ross E.; Dmitrenko, Olga; Bai, Shi; Dybowski, C.

2009-07-01

The 199Hg chemical-shift tensor of solid HgCl 2 was determined from spectra of polycrystalline materials, using static and magic-angle spinning (MAS) techniques at multiple spinning frequencies and field strengths. The chemical-shift tensor of solid HgCl 2 is axially symmetric ( η = 0) within experimental error. The 199Hg chemical-shift anisotropy (CSA) of HgCl 2 in a frozen solution in dimethylsulfoxide (DMSO) is significantly smaller than that of the solid, implying that the local electronic structure in the solid is different from that of the material in solution. The experimental chemical-shift results (solution and solid state) are compared with those predicted by density functional theory (DFT) calculations using the zeroth-order regular approximation (ZORA) to account for relativistic effects. 199Hg spin-lattice relaxation of HgCl 2 dissolved in DMSO is dominated by a CSA mechanism, but a second contribution to relaxation arises from ligand exchange. Relaxation in the solid state is independent of temperature, suggesting relaxation by paramagnetic impurities or defects.

Magnetism and Solid Solution Effects in NiAI (40% AI) Alloys

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

Liu, Chain T; Fu, Chong Long; Chisholm, Matthew F

2007-01-01

The solid solution effects of ternary additions of transition elements in intermetallic Ni-40% Al were investigated by both experimental studies and theoretical calculations. Co solute atoms when sitting at Ni sublattice sites do not affect the lattice parameter and hardening behavior of Ni-40Al. On the other hand, Fe, Mn, and Cr solutes, which are mainly on Al sublattice sites, substantially expand the lattice parameter and produce an unusual solid solution softening effect. First-principles calculations predict that these solute atoms with large unfilled d-band electrons develop large magnetic moments and effectively expand the lattice parameter when occupying Al sublattice sites. Themore » theoretical predictions were verified by both electron loss-energy spectroscopy (EELS) analyses and magnetic susceptibility measurements. The observed softening behavior can be explained quantitatively by the replacement of Ni anti-site defects (potent hardeners) by Fe, Mn, and Cr anti-site defects with smaller atom size mismatch between solute and Al atoms. This study has led to the identification of magnetic interaction as an important physical parameter affecting the solid solution hardening in intermetallic alloys containing transition elements.« less

Research on the synergistic doped effects and the catalysis properties of Cu2+ and Zn2+ co-doped CeO2 solid solutions

NASA Astrophysics Data System (ADS)

Zhang, Guofang; Li, Yiming; Hou, Zhonghui; Xv, Jianyi; Wang, Qingchun; Zhang, Yanghuan

2018-08-01

The Cu2+ and Zn2+ co-doped CeO2-based solid solutions were synthesized via hydrothermal method. The microstructure and the spectra features of the solid solutions were characterized systematically. The XRD results showed that the dopants were incorporated into the CeO2 lattice to form Ce1-xCu0.5xZn0.5xO2 solid solutions when x was lower than 0.14. The cell parameters and the crystalline size decreased linearly, and the lattice strain gradually increased with increasing the doping level. The TEM patterns showed that the particle size in the solid solution was lower than 10 nm which is in accordance with the XRD results. The ICP analysis indicated that the real doped content in the solid solution was close to the nominal proportion. XPS proved that the Ce3+ component was increased by doping. The Raman and PL spectra indicated that the lattice distortion and the oxygen vacancies also increased following the same trend. At the same time, the synergistic effects of two ions co-doped solid solutions were studied by comparing them with that of single ions doped samples. The catalysis effects of Cu2+ and Zn2+ co-doped CeO2-based solid solutions on the hydrogen storage electrochemical and kinetic properties of Mg2Ni alloys were detected. The electrochemistry properties of the Mg2Ni-Ni-5 wt% Ce1-xCu0.5xZn0.5xO2 composites indicated that the doped catalysts could provide better optimizations to improve the maximum discharge capacities and the discharge potentials. On the other hand, the charge transfer abilities on the surface and diffusion rate of H atoms in the bulk of alloys also got improved. The DSC measurements showed that the hydrogen desorption activation of the hydrogenated composites with Ce0.88Cu0.06Zn0.06O2 solid solutions decreased to 77.03 kJ mol-1, while that of the composites with pure CeO2 was 97.62 kJ mol-1. The catalysis effect was enhanced by the doped content increase that means that the catalysis mechanism had close links to the oxygen vacancy concentration and the lattice defects in the solid solutions. On the other hand, the doped Cu2+ and Zn2+ ions could also play an important role in the catalytic process.

Generalized gradient algorithm for trajectory optimization

NASA Technical Reports Server (NTRS)

Zhao, Yiyuan; Bryson, A. E.; Slattery, R.

1990-01-01

The generalized gradient algorithm presented and verified as a basis for the solution of trajectory optimization problems improves the performance index while reducing path equality constraints, and terminal equality constraints. The algorithm is conveniently divided into two phases, of which the first, 'feasibility' phase yields a solution satisfying both path and terminal constraints, while the second, 'optimization' phase uses the results of the first phase as initial guesses.

Engagement and Termination in Marital and Familial Therapy: Special Ethical Issues.

ERIC Educational Resources Information Center

Wilcoxon, S. Allen; Gladding, Samuel T.

1985-01-01

Addresses ethical issues in the engagement and termination phases of marital and family therapy. Engagement phase must examine commitment to systemic intervention versus serving motivated clients. Termination phase must examine client's and therapist's ways of managing readiness, prematurity, and follow-up. Proposed solutions are suggested. (ABL)

Mars Ascent Vehicle-Propellant Aging

NASA Technical Reports Server (NTRS)

Dankanich, John; Rousseau, Jeremy; Williams, Jacob

2015-01-01

This project is to develop and test a new propellant formulation specifically for the Mars Ascent Vehicle (MAV) for the robotic Mars Sample Return mission. The project was initiated under the Planetary Sciences Division In-Space Propulsion Technology (ISPT) program and is continuing under the Mars Exploration Program. The two-stage, solid motor-based MAV has been the leading MAV solution for more than a decade. Additional studies show promise for alternative technologies including hybrid and bipropellant options, but the solid motor design has significant propellant density advantages well suited for physical constraints imposed while using the SkyCrane descent stage. The solid motor concept has lower specific impulse (Isp) than alternatives, but if the first stage and payload remain sufficiently small, the two-stage solid MAV represents a potential low risk approach to meet the mission needs. As the need date for the MAV slips, opportunities exist to advance technology with high on-ramp potential. The baseline propellant for the MAV is currently the carboxyl terminated polybutadiene (CTPB) based formulation TP-H-3062 due to its advantageous low temperature mechanical properties and flight heritage. However, the flight heritage is limited and outside the environments, the MAV must endure. The ISPT program competed a propellant formulation project with industry and selected ATK to develop a new propellant formulation specifically for the MAV application. Working with ATK, a large number of propellant formulations were assessed to either increase performance of a CTPB propellant or improve the low temperature mechanical properties of a hydroxyl terminated polybutadiene (HTPB) propellant. Both propellants demonstrated potential to increase performance over heritage options, but an HTPB propellant formulation, TP-H-3544, was selected for production and testing. The test plan includes propellant aging first at high vacuum conditions, representative of the Mars transit, followed by an additional year at simulated Mars surface conditions. The actual Mars surface environment is based on the igloo design, actively maintains the propellant at or above -40 degC, 95% carbon dioxide at Mars surface pressure. The NASA Marshall Space Flight Center (MSFC) Mars environment test facility is shown in figure 1 and located in the East Test area of Redstone Arsenal due to storage of live propellants. The facility consists of a vacuum chamber placed inside a large freezer unit. The facility includes pressure and temperature monitoring equipment in addition to a vacuum quality monitoring system spectrometer to record any outgassing products.

49 CFR 232.205 - Class I brake test-initial terminal inspection.

Code of Federal Regulations, 2010 CFR

2010-10-01

... § 232.205 Class I brake test-initial terminal inspection. (a) Each train and each car in the train shall... tested solid block of cars to the train; (iii) Changing motive power; (iv) Removing or changing the... conduct a brake test pursuant to § 232.209 on those cars added to the train. (B) [Reserved] (b) Except as...

Spatial structure peculiarities of influenza A virus matrix M1 protein in an acidic solution that simulates the internal lysosomal medium.

PubMed

Shishkov, Alexander; Bogacheva, Elena; Fedorova, Natalia; Ksenofontov, Alexander; Badun, Gennadii; Radyukhin, Victor; Lukashina, Elena; Serebryakova, Marina; Dolgov, Alexey; Chulichkov, Alexey; Dobrov, Evgeny; Baratova, Lyudmila

2011-12-01

The structure of the C-terminal domain of the influenza virus A matrix M1 protein, for which X-ray diffraction data were still missing, was studied in acidic solution. Matrix M1 protein was bombarded with thermally-activated tritium atoms, and the resulting intramolecular distribution of the tritium label was analyzed to assess the steric accessibility of the amino acid residues in this protein. This technique revealed that interdomain loops and the C-terminal domain of the protein are the most accessible to labeling with tritium atoms. A model of the spatial arrangement of the C-terminal domain of matrix M1 protein was generated using rosetta software adjusted to the data obtained by tritium planigraphy experiments. This model suggests that the C-terminal domain is an almost flat layer with a three-α-helical structure. To explain the high level of tritium label incorporation into the C-terminal domain of the M1 protein in an acidic solution, we also used independent experimental approaches (CD spectroscopy, limited proteolysis and MALDI-TOF MS analysis of the proteolysis products, dynamic light scattering and analytical ultracentrifugation), as well as multiple computational algorithms, to analyse the intrinsic protein disorder. Taken together, the results obtained in the present study indicate that the C-terminal domain is weakly structured. We hypothesize that the specific 3D structural peculiarities of the M1 protein revealed in acidic pH solution allow the protein greater structural flexibility and enable it to interact effectively with the components of the host cell. © 2011 The Authors Journal compilation © 2011 FEBS.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

Influence of carbonate ion in the crystallization medium on the formation and chemical composition of CaHA-SrHA solid solutions

NASA Astrophysics Data System (ADS)

Nikolaev, Anton; Kuz'mina, Maria; Frank-Kamenetskaya, Olga; Zorina, Maina

2015-06-01

The study of the influence of carbonate ions in a solution to Sr-distribution in system «solution-crystal» and to ion substitutions and the non-stoichiometry of formed CaHA-SrHA solid solutions was carried out. The CaHA-SrHA solid solutions were synthesized by precipitation from aqueous solutions with the atomic C/P ratio equal to 0, 0.05 and 0.1 at T = 90 °C. Resulting precipitates were studied using various methods including X-ray powder diffraction, infrared spectroscopy and different chemical analyses. The results of the study have shown that in the range of values of (Ca + Sr)/P in the water solution from 40% to 85%, the presence of carbonate ions (C/P = 0.05-0.1) promotes the incorporation of strontium in the apatite. Crystalline apatite solid solutions formed from water solutions of such composition are more defective compared to apatites that are mainly calcium or strontium. They are characterized by a smaller size coherence scattering domain length along [0 0 1] direction and a greater number of carbonate ions, water molecules and vacancies at the Ca-sites.

Aeroacoustics of contoured and solid/porous conical plug-nozzle supersonic jet flows

NASA Technical Reports Server (NTRS)

Dosanjh, D. S.; Das, I. S.

1985-01-01

The acoustic far field, the shock-associated noise and characteristics of the repetitive shock structure of supersonic jet flows issuing from a contoured plug-nozzle and uncontoured plug-nozzle having a short conical plug of either a solid or a combination of solid/porous surface with pointed termination operated at a range of supercritical pressure are reported. The contoured and the uncontoured plug-nozzles had the same throat area and the same annular-radius ratio.

Effects of ruthenium ions on the sensory terminal discharges of the frog muscle spindle.

PubMed

Ito, F; Fujitsuka, N; Komatsu, Y

1983-10-16

The presence of a mixed Na+-Ca2+ spike along the sensory terminal of the frog muscle spindle was verified. When the terminal was perfused with Ringer's solution containing 0.1-0.5 mM ruthenium red (RuR), the amplitude and duration of the spike were increased, occurring as a prolonged or a long-lasting depolarization of up to 20-30 s duration following individual afferent spikes evoked spontaneously or antidromically by electrical stimulation. In an isotonic TEA solution, the amplitude and duration of the afferent spikes were increased; however, no prolonged depolarization occurred. Adding 0.2 mM RuR to the TEA solution produced the prolonged and long-lasting depolarization. All responses disappeared in the presence of 3 microM TTX or Na+-free Ringer's solution. An impedance decrease along the terminal was observed during the prolonged or long-lasting depolarization. The prolonged depolarization was blocked by the addition of Ca2+-blockers; the afferent spikes remained. In preparations preincubated with 0.1 mM RuR, increasing CaCl2 in Ringer's solution from 0.2 mM, resulted in shortening of the duration of individual spikes with prolonged depolarization and in increase in the maximum rate of rise (MRR) of the spikes. Preincubation with higher concentrations of RuR produced higher sensitivities in the modifications of the duration and MRR to the change in [Ca2+]O. The responses were retained by adding RuR or RuCl3 to Ca2+-free Ringer's solution containing 0.1-5 mM EGTA, although all responses disappeared in Ca2+-free EGTA Ringer's solution. It is concluded that the RuR-induced prolonged response is produced by an influx of Na+.

Terminal velocity and drag reduction measurements on superhydrophobic spheres

NASA Astrophysics Data System (ADS)

McHale, G.; Shirtcliffe, N. J.; Evans, C. R.; Newton, M. I.

2009-02-01

Super water-repellent surfaces occur naturally on plants and aquatic insects and are created in the laboratory by combining micro- or nanoscale surface topographic features with hydrophobic surface chemistry. When such types of water-repellent surfaces are submerged they can retain a film of air (a plastron). In this work, we report measurements of the terminal velocity of solid acrylic spheres with various surface treatments settling under the action of gravity in water. We observed increases in terminal velocity corresponding to drag reduction of between 5% and 15% for superhydrophobic surfaces that carry plastrons.

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Calculation of open and closed system elastic coefficients for multicomponent solids

NASA Astrophysics Data System (ADS)

Mishin, Y.

2015-06-01

Thermodynamic equilibrium in multicomponent solids subject to mechanical stresses is a complex nonlinear problem whose exact solution requires extensive computations. A few decades ago, Larché and Cahn proposed a linearized solution of the mechanochemical equilibrium problem by introducing the concept of open system elastic coefficients [Acta Metall. 21, 1051 (1973), 10.1016/0001-6160(73)90021-7]. Using the Ni-Al solid solution as a model system, we demonstrate that open system elastic coefficients can be readily computed by semigrand canonical Monte Carlo simulations in conjunction with the shape fluctuation approach. Such coefficients can be derived from a single simulation run, together with other thermodynamic properties needed for prediction of compositional fields in solid solutions containing defects. The proposed calculation approach enables streamlined solutions of mechanochemical equilibrium problems in complex alloys. Second order corrections to the linear theory are extended to multicomponent systems.

Local Structure and Short-Range Order in a NiCoCr Solid Solution Alloy

DOE PAGES

Zhang, F. X.; Zhao, Shijun; Jin, Ke; ...

2017-05-19

Multi-element solid solution alloys are intrinsically disordered on the atomic scale, and many of their advanced properties originate from the unique local structural characteristics. We measured the local structure of a NiCoCr solid solution alloy with X-ray/neutron total scattering and extended X-ray absorption fine structure (EXAFS) techniques. The atomic pair distribution function analysis (PDF) did not exhibit distinct structural distortion. But, EXAFS analysis suggested that the Cr atoms are favorably bonded with Ni and Co in the solid solution alloys. This short-range order (SRO) plays a role in the distinct low values of electrical and thermal conductivities in Ni-based solidmore » solution alloys when Cr is incorporated. Both the long-range and local structures of the NiCoCr alloy upon Ni ion irradiation were studied and an irradiation-induced enhancement of SRO was found.« less

Investigation of Termination in Free Radical Polymerization by Use of >Diffusion-Limited Interactions in Polymer Solutions

NASA Astrophysics Data System (ADS)

Wisnudel, Marc; Torkelson, John

1997-03-01

Termination between radicals has been simulated by use of phosphorescence quenching interactions, showing that segmental diffusion plays a strong role in the origin of autoacceleration or the gel effect. Quenching rate constants (k_q) were measured between benzil-labeled polymer as a function of anthracene-labeled polymer in polystyrene or polymethylmethacrylate solutions. Values of kq were obtained for interactions involving end- or center-labeled chains as a function of polymer MW and concentration. A large effect of label location was observed as interactions between center-labeled chains resulted in values of kq that were more MW-dependent and smaller in magnitude than those for interactions between end-labeled chains. For interactions between end-labeled chains at concentrations between 0 and 600 g/L, data show only very weak dependencies of kq on MW and concentration dependencies similar to that of segmental mobility. In addition, comparisons of kq data for interactions in PMMA-toluene solutions with termination rate constant (k_t) data for MMA polymerizations, showing weaker concentration dependencies for both kq and kt than translational diffusion coefficients in similar solutions, also indicate that segmental diffusion is important in termination.

Modeling of the Temperature Field Recovery in the Oil Pool

NASA Astrophysics Data System (ADS)

Khabibullin, I. L.; Davtetbaev, A. Ya.; Mar'in, D. F.; Khisamov, A. A.

2018-05-01

This paper considers the problem on mathematical modeling of the temperature field recovery in the oil pool upon termination of injection of water into the pool. The problem is broken down into two stages: injection of water and temperature and pressure recovery upon termination of injection. A review of the existing mathematical models is presented, analytical solutions for a number of cases have been constructed, and a comparison of the analytical solutions of different models has been made. In the general form, the expression has been obtained that permits determining the temperature change in the oil pool upon termination of injection of water (recovery of the temperature field).

Surface Defects Enhanced Visible Light Photocatalytic H2 Production for Zn-Cd-S Solid Solution.

PubMed

Zhang, Xiaoyan; Zhao, Zhao; Zhang, Wanwan; Zhang, Guoqiang; Qu, Dan; Miao, Xiang; Sun, Shaorui; Sun, Zaicheng

2016-02-10

In order to investigate the defect effect on photocatalytic performance of the visible light photocatalyst, Zn-Cd-S solid solution with surface defects is prepared in the hydrazine hydrate. X-ray photoelectron spectra and photoluminescence results confirm the existence of defects, such as sulfur vacancies, interstitial metal, and Zn and Cd in the low valence state on the top surface of solid solutions. The surface defects can be effectively removed by treating with sulfur vapor. The solid solution with surface defect exhibits a narrower band gap, wider light absorption range, and better photocatalytic perfomance. The optimized solid solution with defects exhibits 571 μmol h(-1) for 50 mg photocatalyst without loading Pt as cocatalyst under visible light irradiation, which is fourfold better than that of sulfur vapor treated samples. The wavelength dependence of photocatalytic activity discloses that the enhancement happens at each wavelength within the whole absorption range. The theoretical calculation shows that the surface defects induce the conduction band minimum and valence band maximum shift downward and upward, respectively. This constructs a type I junction between bulk and surface of solid solution, which promotes the migration of photogenerated charges toward the surface of nanostructure and leads to enhanced photocatalytic activity. Thus a new method to construct highly efficient visible light photocatalysts is opened. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilized antiferroelectricity in xBiScO3-(1-x)NaNbO3 lead-free ceramics with established double hysteresis loops

NASA Astrophysics Data System (ADS)

Gao, Lisheng; Guo, Hanzheng; Zhang, Shujun; Randall, Clive A.

2018-02-01

We previously reported various solid solution systems that demonstrated the stabilized antiferroelectric (P) phases in NaNbO3 through lowering the tolerance factor. However, all those reported modifications were achieved by adding A2+B4+O3 type solid solutions. A lead-free antiferroelectric (AFE) solid solution xBiScO3-(1-x)NaNbO3 was rationalized by adopting the tolerance factor design rule. Specifically, adding BiScO3 was found to effectively stabilize the AFE phase without changing the crystal symmetry of NaNbO3. Microstructure and electron zone axis diffraction patterns from transmission electron microscopy revealed the stabilized AFE (P) phase in this solid solution. Besides, the electric-field-induced polarization with a double-hysteresis loop was observed. The present results pointed out that the strategy could also be applied while adding A3+B3+O3 type solid solutions. In addition, it expanded the compositional design that can be applied to antiferroelectric materials.

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Materials research for passive solar systems: Solid-state phase-change materials

NASA Astrophysics Data System (ADS)

Benson, D. K.; Webb, J. D.; Burrows, R. W.; McFadden, J. D. O.; Christensen, C.

1985-03-01

A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C5H12O4), pentaglycerinve (C5H12O3), and neopentyl glycol (C5H12O2). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature between 25 C and 188 C, and have latent heats of transformation etween 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier.

A new pH-responsive peptide tag for protein purification.

PubMed

Nonaka, Takahiro; Tsurui, Noriko; Mannen, Teruhisa; Kikuchi, Yoshimi; Shiraki, Kentaro

2018-06-01

This paper describes a new pH-responsive peptide tag that adds a protein reversible precipitation and redissolution character. This peptide tag is a part of a cell surface protein B (CspB) derived from Corynebacterium glutamicum. Proinsulin that genetically fused with a peptide of N-terminal 6, 17, 50, or 250 amino acid residues of CspB showed that the reversible precipitation and redissolution depended on the pH. The transition occurred within a physiological and narrow pH range. A CspB50 tag comprising 50 amino acid residues of N-terminal CspB was further evaluated as a representative using other pharmaceutical proteins. Below pH 6.8, almost all CspB50-Teriparatide fusion formed an aggregated state. Subsequent addition of alkali turned the cloudy protein solution transparent above pH 7.3, in which almost all the CspB50-Teriparatide fusion redissolved. The CspB50-Bivalirudin fusion showed a similar behavior with slightly different pH range. This tag is offering a new protein purification method based on liquid-solid separation which does not require an affinity ligand. This sharp response around neutral pH is useful as a pH-responsive tag for the purification of unstable proteins at a non-physiological pH. Copyright © 2018 Elsevier Inc. All rights reserved.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

Design principles for radiation-resistant solid solutions

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Trinkle, Dallas R.; Bellon, Pascal; Averback, Robert

2017-05-01

We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

N-(L-2-aminopentanoyl)-L-phenylalanine dihydrate, a hydrophobic dipeptide with a nonproteinogenic residue.

PubMed

Görbitz, Carl Henrik; Yadav, Vitthal N

2013-09-01

The title dipeptide, better known as L-norvalyl-L-phenylalanine {systematic name: (S)-2-[(S)-2-aminopentanamido]-3-phenylpropanoic acid dihydrate}, C14H20N2O3·2H2O, has a nonproteinogenic N-terminal residue. In the solid state, it takes on a molecular conformation typical for one of the three classes of nanoporous dipeptides, but like two related compounds with a hydrophobic N-terminal residue and a C-terminal L-phenylalanine, it fails to form channels or pores. Instead, the crystal structure is divided into distinct hydrophobic and hydrophilic layers, the latter encompassing cocrystallized water molecules connecting the charged N- and C-terminal groups.

Structure determination of a peptide model of the repeated helical domain in Samia cynthia ricini silk fibroin before spinning by a combination of advanced solid-state NMR methods.

PubMed

Nakazawa, Yasumoto; Asakura, Tetsuo

2003-06-18

Fibrous proteins unlike globular proteins, contain repetitive amino acid sequences, giving rise to very regular secondary protein structures. Silk fibroin from a wild silkworm, Samia cynthia ricini, consists of about 100 repeats of alternating polyalanine (poly-Ala) regions of 12-13 residues in length and Gly-rich regions. In this paper, the precise structure of the model peptide, GGAGGGYGGDGG(A)(12)GGAGDGYGAG, which is a typical repeated sequence of the silk fibroin, was determined using a combination of three kinds of solid-state NMR studies; a quantitative use of (13)C CP/MAS NMR chemical shift with conformation-dependent (13)C chemical shift contour plots, 2D spin diffusion (13)C solid-state NMR under off magic angle spinning and rotational echo double resonance. The structure of the model peptide corresponding to the silk fibroin structure before spinning was determined. The torsion angles of the central Ala residue, Ala(19), in the poly-Ala region were determined to be (phi, psi) = (-59 degrees, -48 degrees ) which are values typically associated with alpha-helical structures. However, the torsion angles of the Gly(25) residue adjacent to the C-terminal side of the poly-Ala chain were determined to be (phi, psi) = (-66 degrees, -22 degrees ) and those of Gly(12) and Ala(13) residues at the N-terminal of the poly-Ala chain to be (phi, psi) = (-70 degrees, -30 degrees ). In addition, REDOR experiments indicate that the torsion angles of the two C-terminal Ala residues, Ala(23) and Ala(24), are (phi, psi) = (-66 degrees, -22 degrees ) and those of N-terminal two Ala residues, Ala(13) and Ala(14) are (phi, psi) = (-70 degrees, -30 degrees ). Thus, the local structure of N-terminal and C-terminal residues, and also the neighboring residues of alpha-helical poly-Ala chain in the model peptide is a more strongly wound structure than found in typical alpha-helix structures.

Lipid immiscibility and biophysical properties: Molecular order within and among unit cell volumes

USDA-ARS?s Scientific Manuscript database

Saturated and unsaturated fatty acids clearly have a discrete chemical structure in the solid state. In a saturated solution, the solid state and solution state are in chemical equilibrium. The lipid stearic acid packs in unit cell volumes in the liquid state as well as in the solid state. Normal...

Multiferroic properties in NdFeO3-PbTiO3 solid solutions

NASA Astrophysics Data System (ADS)

Kumar, Sunil; Pal, Jaswinder; Kaur, Shubhpreet; Agrawal, P.; Singh, Mandeep; Singh, Anupinder

2018-05-01

The x(NdFeO3) - 1-x(PbTiO3) where x = 0.2 solid solution was prepared using solid state reaction route. The X-ray diffraction (XRD) data reveals the single phase formation. The microstructure shows grain growth with lesser porosity. The energy dispersive analysis confirms the presence of elements in stochiometric proportion. The polarization vs. Electric field loop estabilished a ferroelectric type behavior but lossy in nature. This lossy nature may be due to the presence of large leakage current in solid solution. The Magnetization vs. Magnetic field plot exhibits a unsaturated hysteriss loop indicates that the sample is not purely ferromagnetic.

Study of low-temperature active rare-earth oxide catalysts for automotive exhaust clean-up.

DOT National Transportation Integrated Search

2014-02-01

We report a facile onepot synthesis of CexZr1-xO2 (0x1) solid solution nanocrystals using hydrothermal reactions. A direct formation of oxide solid solutions in aqueous solution under pressure at low temperatures was clearly revealed by X-ra...

Closeup view of the Solid Rocket Booster (SRB) Forward Skirt ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Close-up view of the Solid Rocket Booster (SRB) Forward Skirt sitting on ground support equipment in the Solid Rocket Booster Assembly and Refurbishment Facility at Kennedy Space Center while being prepared for mating with the Frustum-Nose Cap Assembly and the Forward Rocket Motor Segment. The prominent feature in this view is the electrical, data, telemetry and safety systems terminal which connects to the Aft Skirt Assembly systems via the Systems Tunnel that runs the length of the Rocket Motor. - Space Transportation System, Solid Rocket Boosters, Lyndon B. Johnson Space Center, 2101 NASA Parkway, Houston, Harris County, TX

Band positions of Rutile surfaces and the possibility of water splitting

NASA Astrophysics Data System (ADS)

Esch, Tobit R.; Bredow, Thomas

2017-11-01

It is well known that both the band gap and the band edge positions of oxide semiconductors are important for the photocatalytic water splitting. In this study, we show that different surface terminations of the same crystalline solid lead to considerable variations of the band gaps and band edges. As an example, we investigate the low-index surfaces of rutile TiO2. A series of hybrid methods based on the PBE exchange-correlation functional, PBE0, HSE06 and HISS, are employed to study the effect of long-range exchange on the electronic properties. In aqueous solution, the oxide particles employed in photocatalysis are fully covered with water molecules. We therefore study the influence of molecularly and dissociatively adsorbed water on the band positions. It is found that water adsorption leads to significant shifts of the band edge positions due to changes of the electrostatic potential at the surface atom positions.

Metastable phase equilibria in co-deposited Ni(1-x)Zr(x) thin films

NASA Astrophysics Data System (ADS)

Rubin, J. B.; Schwarz, R. B.

We determine the glass forming range (GFR) of co-deposited Ni(1-x)Zr(x) (0 less than x less than 1) thin films by measuring their electrical resistance during in situ constant-heating-rate anneals. The measured GFR is continuous for 0.10 less than x less than 0.87. We calculate the GFR of Ni-Zr melts as a function of composition and cooling rate using homogeneous nucleation theory and a published CALPHAD-type thermodynamic modeling of the equilibrium phase diagram. Assuming that the main competition to the retention of the amorphous structure during the cooling of the liquid comes from the partitionless crystallization of the terminal solid solutions, we calculate that for dT/dt = 10(exp 12) K/s, the GFR extends to x = 0.05 and x = 0.96. Better agreement with the measured values is obtained assuming a lower effective cooling rate during the condensation of the films.

A New Acceptor (N-type) Polyphenylenevinylene Building Block: SF-PPV-I

NASA Technical Reports Server (NTRS)

Wang, Yiqing; Fan, Zhen; Taft, Charles; Sun, Sam-Shajing

2002-01-01

A new sulfone derivatized acceptor (n-type) polyphenylenevinylene "SF-PPV" with nano meter sizes and functional terminals has been synthesized and characterized. The SF-PPV-I that contains hydrocarbon alkyl-sulfone moieties has a strong photoluminescence in both solution and in solid thin film states. In dichloromethane, the 5-10 nm sized SF-PPV has a maximum emission at about 530 nm with excitation maximum at about 490 nm. UV-VIS shows a absorption peak onsite at about 500 nm. Optical spectroscopy and electrochemical studies revealed that the SF-PPV-I has an LUMO level at about -3.6 eV (relative to vacuum), and an HOMO level at about -6.1 eV. The average size (length) of SF-PPV-I can be controlled on the nano meter scale via synthetic means. The SF-PPV has the potential in developing polymer based supramolecular opto-electronic semiconductor devices.

Development of new solid-phase microextraction fibers by sol-gel technology for the determination of organophosphorus pesticide multiresidues in food.

PubMed

Yu, Jianxin; Wu, Caiying; Xing, Jun

2004-05-21

Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples.

Sequence-controlled methacrylic multiblock copolymers via sulfur-free RAFT emulsion polymerization

NASA Astrophysics Data System (ADS)

Engelis, Nikolaos G.; Anastasaki, Athina; Nurumbetov, Gabit; Truong, Nghia P.; Nikolaou, Vasiliki; Shegiwal, Ataulla; Whittaker, Michael R.; Davis, Thomas P.; Haddleton, David M.

2017-02-01

Translating the precise monomer sequence control achieved in nature over macromolecular structure (for example, DNA) to whole synthetic systems has been limited due to the lack of efficient synthetic methodologies. So far, chemists have only been able to synthesize monomer sequence-controlled macromolecules by means of complex, time-consuming and iterative chemical strategies such as solid-state Merrifield-type approaches or molecularly dissolved solution-phase systems. Here, we report a rapid and quantitative synthesis of sequence-controlled multiblock polymers in discrete stable nanoscale compartments via an emulsion polymerization approach in which a vinyl-terminated macromolecule is used as an efficient chain-transfer agent. This approach is environmentally friendly, fully translatable to industry and thus represents a significant advance in the development of complex macromolecule synthesis, where a high level of molecular precision or monomer sequence control confers potential for molecular targeting, recognition and biocatalysis, as well as molecular information storage.

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

Xie, Miao; Mohammadi, Reza; Turner, Christopher L.

In this paper, we explore the hardening mechanisms in WB4-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under nonhydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB 4 solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

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

Xie, Miao; Turner, Christopher L.; Mohammadi, Reza

In this work, we explore the hardening mechanisms in WB{sub 4}-based solid solutions upon addition of Ta, Mn, and Cr using in situ radial X-ray diffraction techniques under non-hydrostatic pressure. By examining the lattice-supported differential strain, we provide insights into the mechanism for hardness increase in binary solid solutions at low dopant concentrations. Speculations on the combined effects of electronic structure and atomic size in ternary WB{sub 4} solid solutions containing Ta with Mn or Cr are also included to understand the extremely high hardness of these materials.

Solid-solution thermodynamics in Al-Li alloys

NASA Astrophysics Data System (ADS)

Alekseev, A. A.; Lukina, E. A.

2016-05-01

The relative equilibrium concentrations of lithium atoms distributed over different electron-structural states has been estimated. The possibility of the existence of various nonequilibrium electron-structural states of Li atoms in the solid solution in Al has been substantiated thermodynamically. Upon the decomposition of the supersaturated solid solution, the supersaturation on three electron-structural states of Li atoms that arises upon the quenching of the alloy can lead to the formation of lithium-containing phases in which the lithium atoms enter in one electron-structural state.

Concentration Dependent Physical Properties of Ge1-xSnx Solid Solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Jani, A. R.

2011-12-01

Our own proposed potential is used to investigate few physical properties like total energy, bulk modulus, pressure derivative of bulk modulus, elastic constants, pressure derivative of elastic constants, Poisson's ratio and Young's modulus of Ge1-xSnx solid solution with x is atomic concentration of α-Sn. The potential combines linear plus quadratic types of electron-ion interaction. First time screening function proposed by Sarkar et al is used to investigate the properties of the Ge-Sn solid solution system.

New anatase-type Til-2xNbxAlxO2 solid solution nanoparticles: direct formation, phase stability, and photocatalytic performance.

PubMed

Hirano, Masanori; Ito, Takaharu

2006-12-01

New anatase-type titania solid solutions co-doped with niobium and aluminum (Til-2xNbxAIlxO2 (X = 0 -0.20)) were synthesized as nanoparticles from precursor solutions of TiOSO4, NbCl5, and Al(NO3)3 under mild hydrothermal conditions at 180 degrees C for 5 h using the hydrolysis of urea. The lattice parameters a0 and c0 of anatase slightly and gradually increased, when the content of niobium and aluminum increased from X = 0 to 0.20. The crystallite size of anatase increased from 12 to 28 nm with increasing the value of X from 0 to 0.20. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The adsorptivity of TiO2 was improved by the formation of anatase-type Til-2xNbxAlxO2 solid solutions. The photocatalytic activity of anatase-type Til-2xNbxAlxO2 solid solutions was superior to that of commercially available anatase-type pure TiO2 (ST-01) and anatase-type pure TiO2 hydrothermally prepared. The new anatase phase of Til-2xNbxAlxO2 (X = 0-0.20) solid solutions existed stably up to 850 0C during heat treatment in air. In comparison with hydrothermal pure TiO2, the starting temperature of anatase-to-rutile phase transformation was delayed by the formation of Ti1-2xNbxAlxO, (X = 0-0.20) solid solutions, although its completing temperature was accelerated.

Experimental millimeter-wave personal satellite communications system

NASA Technical Reports Server (NTRS)

Suzuki, Yoshiaki; Kimura, Shigeru; Shimada, Masaaki; Tanaka, Masato; Takahashi, Yasuhiro

1991-01-01

Communications Research Laboratory (CRL) has investigated an advanced millimeter (mm)-wave satellite communications system for personal use. Experiments in mm-wave personal satellite communication are to be conducted for 3 years using Japan's Engineering Test Satellite VI (ETS-VI). This paper describes an experimental mm-wave (43/38 GHz) personal satellite communication system, including an onboard transponder and an earth terminal. The on-board transponder is almost completed, and the ground experiment system is still in the design stage. The transponder employs advanced mm-wave solid state technology. It uses 38 GHz high power solid state amplifiers to accelerate the development of mm-wave solid state devices which are indispensable to personal earth terminals. The transponder consists of a 43 GHz receiver with a built-in low noise amplifier, an IF filter section with very narrow bandwidth to improve the carrier-to-noise power ratio of the weak personal communication signal, and two high power amplifiers using newly developed high power Gallium Arsenide (GaAs) metal-semiconductor field effect transistors (MESFETs).

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

Optimizing Integrated Terminal Airspace Operations Under Uncertainty

NASA Technical Reports Server (NTRS)

Bosson, Christabelle; Xue, Min; Zelinski, Shannon

2014-01-01

In the terminal airspace, integrated departures and arrivals have the potential to increase operations efficiency. Recent research has developed geneticalgorithm- based schedulers for integrated arrival and departure operations under uncertainty. This paper presents an alternate method using a machine jobshop scheduling formulation to model the integrated airspace operations. A multistage stochastic programming approach is chosen to formulate the problem and candidate solutions are obtained by solving sample average approximation problems with finite sample size. Because approximate solutions are computed, the proposed algorithm incorporates the computation of statistical bounds to estimate the optimality of the candidate solutions. A proof-ofconcept study is conducted on a baseline implementation of a simple problem considering a fleet mix of 14 aircraft evolving in a model of the Los Angeles terminal airspace. A more thorough statistical analysis is also performed to evaluate the impact of the number of scenarios considered in the sampled problem. To handle extensive sampling computations, a multithreading technique is introduced.

Termination of String Rewriting Rules that have One Pair of Overlaps

NASA Technical Reports Server (NTRS)

Geser, Alfons; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

This paper presents a partial solution to the long standing open problem of termination of one-rule string rewriting. Overlaps between the two sides of the rule play a central role in existing termination criteria. We characterize termination of all one-rule string rewriting systems that have one such overlap at either end. This both completes a result of Kurth and generalizes a result of Shikishima-Tsuji et al.

Effect of varying Ga content in ZnO:GaN solid solution synthesized by solution combustion technique for photocatalytic applications

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Janani, R.; Baskar, K.; Gupta, Bhavana; Singh, Shubra

2017-05-01

ZnO:GaN (oxy)nitride solid solution has been established as the most efficient non-oxide photocatalyst for water splitting under visible irradiation with one step photoexcitation and also boasts a band gap tunability from 2.8 eV to 2.5 eV[1]. The solid solution of GaN in ZnO is formed by the intersubstitution of few of Zn/O ions by Ga/N ions, and this results in the introduction of new defect levels above the valence band which narrows the effective band gap enabling activity under visible region of spectra. In this work, we report the synthesis of ZnO:GaN solid solution by a solution combustion technique where metal nitrates and urea are used as precursors. The Zn/Ga ratio was varied from 16 to 1 in the precursors. The as synthesized samples were characterized as phase pure by X-ray diffraction, where the wurtzite structure was retained up to Zn/Ga ratio of 5. The Diffuse reflectance spectroscopy studies revealed that as the Ga content in the solid solution increases there is a reduction in band gap, from 2.9 eV to 2.4 eV. The reduced band gap of the samples facilitates its photocatalytic activity under visible region of the spectra as evaluated by photoelectrochemical measurements.

Method of fabricating lipid bilayer membranes on solid supports

NASA Technical Reports Server (NTRS)

Cho, Nam-Joon (Inventor); Frank, Curtis W. (Inventor); Glenn, Jeffrey S. (Inventor); Cheong, Kwang Ho (Inventor)

2012-01-01

The present invention provides a method of producing a planar lipid bilayer on a solid support. With this method, a solution of lipid vesicles is first deposited on the solid support. Next, the lipid vesicles are destabilized by adding an amphipathic peptide solution to the lipid vesicle solution. This destabilization leads to production of a planar lipid bilayer on the solid support. The present invention also provides a supported planar lipid bilayer, where the planar lipid bilayer is made of naturally occurring lipids and the solid support is made of unmodified gold or titanium oxide. Preferably, the supported planar lipid bilayer is continuous. The planar lipid bilayer may be made of any naturally occurring lipid or mixture of lipids, including, but not limited to phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinsitol, cardiolipin, cholesterol, and sphingomyelin.

77 FR 13145 - Notice of Realty Action: Direct Sale of Public Land in Esmeralda County, Nevada

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-05

... which solids or hazardous substances or wastes, as defined by Federal and State environmental laws are..., publication in the Federal Register of a termination of the segregation, or on March 5, 2014, unless extended..., or damages of any kind incurred by the United States; (4) Releases or threatened releases of solid or...

Thermochemical Stability and Friction Properties of Soft Organosilica Networks for Solid Lubrication.

PubMed

Gonzalez Rodriguez, Pablo; Dral, A Petra; van den Nieuwenhuijzen, Karin J H; Lette, Walter; Schipper, Dik J; Ten Elshof, Johan E

2018-01-24

In view of their possible application as high temperature solid lubricants, the tribological and thermochemical properties of several organosilica networks were investigated over a range of temperatures between 25 and 580 °C. Organosilica networks, obtained from monomers with terminal and bridging organic groups, were synthesized by a sol-gel process. The influence of carbon content, crosslink density, rotational freedom of incorporated hydrocarbon groups, and network connectivity on the high temperature friction properties of the polymer was studied for condensed materials from silicon alkoxide precursors with terminating organic groups, i.e., methyltrimethoxysilane, propyltrimethoxysilane, diisopropyldimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and 4-biphenylyltriethoxysilane networks, as well as precursors with organic bridging groups between Si centers, i.e., 1,4-bis(triethoxysilyl)benzene and 4,4'-bis(triethoxysilyl)-1,1'-biphenyl. Pin-on-disc measurements were performed using all selected solid lubricants. It was found that materials obtained from phenyltrimethoxysilane and cyclohexyltrimethoxysilane precursors showed softening above 120 °C and performed best in terms of friction reduction, reaching friction coefficients as low as 0.01. This value is lower than that of graphite films (0.050 ± 0.005), a common bench mark for solid lubricants.

Thermochemical Stability and Friction Properties of Soft Organosilica Networks for Solid Lubrication

PubMed Central

Gonzalez Rodriguez, Pablo; van den Nieuwenhuijzen, Karin J. H.; Lette, Walter; Schipper, Dik J.

2018-01-01

In view of their possible application as high temperature solid lubricants, the tribological and thermochemical properties of several organosilica networks were investigated over a range of temperatures between 25 and 580 °C. Organosilica networks, obtained from monomers with terminal and bridging organic groups, were synthesized by a sol-gel process. The influence of carbon content, crosslink density, rotational freedom of incorporated hydrocarbon groups, and network connectivity on the high temperature friction properties of the polymer was studied for condensed materials from silicon alkoxide precursors with terminating organic groups, i.e., methyltrimethoxysilane, propyltrimethoxysilane, diisopropyldimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and 4-biphenylyltriethoxysilane networks, as well as precursors with organic bridging groups between Si centers, i.e., 1,4-bis(triethoxysilyl)benzene and 4,4′-bis(triethoxysilyl)-1,1′-biphenyl. Pin-on-disc measurements were performed using all selected solid lubricants. It was found that materials obtained from phenyltrimethoxysilane and cyclohexyltrimethoxysilane precursors showed softening above 120 °C and performed best in terms of friction reduction, reaching friction coefficients as low as 0.01. This value is lower than that of graphite films (0.050 ± 0.005), a common bench mark for solid lubricants. PMID:29364164

Planet Patrol. An Educational Unit on Solid Waste Solutions for Grades 4-6.

ERIC Educational Resources Information Center

Shively, Patti J.; And Others

This educational unit on solid waste solutions is intended to convey to students an understanding of the four methods of solid waste handling, in priority order, as recommended by the Environmental Protection Agency: (1) reduction in the volume of waste produced; (2) recycling and composting; (3) waste combustion, i.e., incineration of waste; and…

Vanadium(IV/V) complexes of Triapine and related thiosemicarbazones: Synthesis, solution equilibrium and bioactivity.

PubMed

Kowol, Christian R; Nagy, Nóra V; Jakusch, Tamás; Roller, Alexander; Heffeter, Petra; Keppler, Bernhard K; Enyedy, Éva A

2015-11-01

The stoichiometry and thermodynamic stability of vanadium(IV/V) complexes of Triapine and two related α(N)-heterocyclic thiosemicarbazones (TSCs) with potential antitumor activity have been determined by pH-potentiometry, EPR and (51)V NMR spectroscopy in 30% (w/w) dimethyl sulfoxide/water solvent mixtures. In all cases, mono-ligand complexes in different protonation states were identified. Dimethylation of the terminal amino group resulted in the formation of vanadium(IV/V) complexes with considerably higher stability. Three of the most stable complexes were also synthesized in solid state and comprehensively characterized. The biological evaluation of the synthesized vanadium complexes in comparison to the metal-free ligands in different human cancer cell lines revealed only minimal influence of the metal ion. Thus, in addition the coordination ability of salicylaldehyde thiosemicarbazone (STSC) to vanadium(IV/V) ions was investigated. The exchange of the pyridine nitrogen of the α(N)-heterocyclic TSCs to a phenolate oxygen in STSC significantly increased the stability of the complexes in solution. Finally, this also resulted in increased cytotoxicity activity of a vanadium(V) complex of STSC compared to the metal-free ligand. Copyright © 2015 Elsevier Inc. All rights reserved.

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

Michaels, K.F.; Lange, W.F. III; Bradley, J.R.

The Kaufman approach to phase equilibria involving primarily the fcc, bcc, and hcp phases was examined outside the Group Nos. 4 to 10 range where it is customarily employed. The stability parameters ($delta$H and $delta$S of transformation) for most elements in the Group Nos. 1 to 3 region were found to fit satisfactorily the correlation curves of stability parameter vs group no.; some of the parameters for Al, Be, Mg, and Ti, however, did not. The rare earth parameters fit well in the Group No. 3.5 position they were expected to occupy. A sample phase diagram calculated between two Groupmore » 1 elements was in good agreement with experiment. Phase boundaries of fcc + bcc regions adjacent to terminal solid solutions in several Group 1/Group 2 and Group 1/Group 3 systems, on the other hand, were quite unsatisfactory. This difficulty was traced to the high, positive regular solution constants calculated for both phases. Such constants were shown to result from the downward concavity of a plot of enthalpy of vaporization vs Group No. in the Nos. 1 to 3 region; in the Nos. 4 to 10 range this plot is concave upward. (auth)« less

Thickness effect of nickel oxide thin films on associated solution-processed write-once-read-many-times memory devices

NASA Astrophysics Data System (ADS)

Wang, Xiao Lin; Liu, Zhen; Wen, Chao; Liu, Yang; Wang, Hong Zhe; Chen, T. P.; Zhang, Hai Yan

2018-06-01

With self-prepared nickel acetate based solution, NiO thin films with different thicknesses have been fabricated by spin coating followed by thermal annealing. By forming a two-terminal Ag/NiO/ITO structure on glass, write-once-read-many-times (WORM) memory devices are realized. The WORM memory behavior is based on a permanent switching from an initial high-resistance state (HRS) to an irreversible low-resistance state (LRS) under the application of a writing voltage, due to the formation of a solid bridge across Ag and ITO electrodes by conductive filaments (CFs). The memory performance is investigated as a function of the NiO film thickness, which is determined by the number of spin-coated NiO layers. For devices with 4 and 6 NiO layers, data retention up to 104 s and endurance of 103 reading operations in the measurement range have been obtained with memory window maintained above four orders for both HRS and LRS. Before and after writing, the devices show the hopping and ohmic conduction behaviors, respectively, confirming that the CF formation could be the mechanism responsible for writing in the WORM memory devices.

Polarization-sensitive nanowire photodetectors based on solution-synthesized CdSe quantum-wire solids.

PubMed

Singh, Amol; Li, Xiangyang; Protasenko, Vladimir; Galantai, Gabor; Kuno, Masaru; Xing, Huili Grace; Jena, Debdeep

2007-10-01

Polarization-sensitive photodetectors are demonstrated using solution-synthesized CdSe nanowire (NW) solids. Photocurrent action spectra taken with a tunable white light source match the solution linear absorption spectra of the NWs, showing that the NW network is responsible for the device photoconductivity. Temperature-dependent transport measurements reveal that carriers responsible for the dark current through the nanowire solids are thermally excited across CdSe band gap. The NWs are aligned using dielectrophoresis between prepatterned electrodes using conventional optical photolithography. The photocurrent through the NW solid is found to be polarization-sensitive, consistent with complementary absorption (emission) measurements of both single wires and their ensembles. The range of solution-processed semiconducting NW materials, their facile synthesis, ease of device fabrication, and compatibility with a variety of substrates make them attractive for potential nanoscale polarization-sensitive photodetectors.

The solid-solution region for the langasite-type Ca3TaGa3Si2O14 crystal as determined by a lever rule

NASA Astrophysics Data System (ADS)

Zhao, Hengyu; Uda, Satoshi; Maeda, Kensaku; Nozawa, Jun; Koizumi, Haruhiko; Fujiwara, Kozo

2015-04-01

A lever rule was applied to data concerning the compositions and proportions of secondary phases coexisting with a Ca3TaGa3Si2O14 (CTGS) matrix to determine the boundary compositions of the solid-solution region for CTGS at 1320 °C, as a means of ascertaining the solid-solution for the langasite-type phase in the quaternary CaO-Ta2O5-Ga2O3-SiO2 system. The compositions and proportions of secondary phases were assessed by electron probe micro-analysis as well as through back-scattered electron images. The experimental results showed that the narrow solid-solution region for CTGS is located in a Ta-poor, Ga-poor and Si-rich region relative to its stoichiometric composition.

Dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT formation and decay after picosecond pulsed X-ray excitation and femtosecond UV excitation.

PubMed

Zhao, Liyan; Odaka, Hideho; Ono, Hiroshi; Kajimoto, Shinji; Hatanaka, Koji; Hobley, Jonathan; Fukumura, Hiroshi

2005-01-01

The dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT state formation and decay were determined after femtosecond UV laser excitation and picosecond pulsed X-ray excitation, in an N,N-dimethylformamide (DMF) solution as well as in its solid form. At room temperature, after UV excitation, this MLCT excited state emits both in DMF solution and in the solid form. Transient absorption spectra were measured in solution at various delay times following excitation by a 160 fs, 390 nm laser pulse. There was a prompt absorption increase at around 460 nm occurring within the pump probe convolution (<1 ps), which was assigned to the formation of the 3MLCT state. This transient absorbance was constant over 100 ps. In contrast to the solution state, in the solid state, the emission maximum slightly red-shifts with increasing time after laser excitation. In both solid and solution the emission rises within the system response time. The solid sample exhibited a 1.4 ns emission decay that was not observed for the solution sample. The emission rise from a solid sample after 20 ps pulsed X-ray excitation was significantly slower than the system's time resolution. It is proposed that kinetically energetic electrons are ejected following X-ray induced ionisation, creating ionised tracks in which energetic cations and electrons take time to recombine yielding delayed 3MLCT states that emit.

Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

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

Li, Yan; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen; Kowalski, Piotr M., E-mail: p.kowalski@fz-juelich.de

2014-12-15

We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computedmore » for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

DOE PAGES

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun; ...

2017-04-27

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

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

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

Solid-water detoxifying reagents for chemical and biological agents

DOEpatents

Hoffman, Dennis M [Livermore, CA; Chiu, Ing Lap [Castro Valley, CA

2006-04-18

Formation of solid-water detoxifying reagents for chemical and biological agents. Solutions of detoxifying reagent for chemical and biological agents are coated using small quantities of hydrophobic nanoparticles by vigorous agitation or by aerosolization of the solution in the presence of the hydrophobic nanoparticles to form a solid powder. For example, when hydrophobic fumed silica particles are shaken in the presence of IN oxone solution in approximately a 95:5-weight ratio, a dry powder results. The hydrophobic silica forms a porous coating of insoluble fine particles around the solution. Since the chemical or biological agent tends to be hydrophobic on contact with the weakly encapsulated detoxifying solution, the porous coating breaks down and the detoxifying reagent is delivered directly to the chemical or biological agent for maximum concentration at the point of need. The solid-water (coated) detoxifying solutions can be blown into contaminated ventilation ducting or other difficult to reach sites for detoxification of pools of chemical or biological agent. Once the agent has been detoxified, it can be removed by flushing the area with air or other techniques.

Native Chemical Ligation Strategy to Overcome Side Reactions during Fmoc-Based Synthesis of C-Terminal Cysteine-Containing Peptides.

PubMed

Lelièvre, Dominique; Terrier, Victor P; Delmas, Agnès F; Aucagne, Vincent

2016-03-04

The Fmoc-based solid phase synthesis of C-terminal cysteine-containing peptides is problematic, due to side reactions provoked by the pronounced acidity of the Cα proton of cysteine esters. We herein describe a general strategy consisting of the postsynthetic introduction of the C-terminal Cys through a key chemoselective native chemical ligation reaction with N-Hnb-Cys peptide crypto-thioesters. This method was successfully applied to the demanding peptide sequences of two natural products of biological interest, giving remarkably high overall yields compared to that of a state of the art strategy.

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Nonvolatile Ionic Two-Terminal Memory Device

NASA Technical Reports Server (NTRS)

Williams, Roger M.

1990-01-01

Conceptual solid-state memory device nonvolatile and erasable and has only two terminals. Proposed device based on two effects: thermal phase transition and reversible intercalation of ions. Transfer of sodium ions between source of ions and electrical switching element increases or decreases electrical conductance of element, turning switch "on" or "off". Used in digital computers and neural-network computers. In neural networks, many small, densely packed switches function as erasable, nonvolatile synaptic elements.

Hydrodynamic Coating of a Fiber

NASA Astrophysics Data System (ADS)

Quéré, D.; de Ryck, A.

We discuss how a solid (especially a fiber) is coated when drawn out of a bath of liquid. 1. For slow withdrawals out of pure viscous liquids, the data are found to be fitted by the famous Landau law: then, the coating results from a balance between viscosity and capillarity. For quicker withdrawals, the thickness of the entrained film suddenly diverges, at a velocity on order 1 m/s. Inertia is shown to be responsible for this effect. At still higher velocities, the thickness decreases with the velocity because the solid can only entrain the viscous boundary layer. 2. For complex fluids, surface effects are found in the low velocity regime: out of a surfactant solution, films are thicker than predicted by Landau, by a factor of order 2. The thickening factor is shown to be fixed by the Marangoni flow due to the presence of surfactants; out of an emulsion, the film can be enriched with oil , which can be understood by a simple model of capture; out of a polymer solution, a strong swelling of the film is observed if normal stresses are present. Hence, the problem has two families of solution: (i) at low velocity, the thickness of the layer is fixed by a balance between viscous and surface forces and thus is sensitive to the presence of surfactants, or other heterogeneities; (ii) at high velocity, inertia must be considered and the film thickness is fixed by the bulk properties of the liquid (density and viscosity). In these regimes, it is not affected by the presence of surfactants in the bath. Nous décrivons le dépôt de liquide sur un solide (le plus souvent une fibre) qui advient quand on tire ce solide d'un bain. 1. Si le retrait se fait lentement hors d'un liquide pur et visqueux, les données expérimentales suivent la loi de Landau : le dépôt résulte d'un compromis entre forces visqueuses et forces capillaires. Pour des retraits plus rapides, on observe que l'épaisseur du dépôt diverge, pour une vitesse de l'ordre du mètre par seconde. Nous montrons comment l'inertie du fluide engendre un tel effet. Plus vite encore, l'épaisseur décroît lentement avec la vitesse, le solide ne parvenant à entraîner avec lui que la couche limite visqueuse qu'il a mis en mouvement. 2. Pour des liquides complexes, des effets de surface sont observés dans le régime basse vitesse : hors d'une solution de tensioactifs, les films sont plus épais que ce que prévoit la loi de Landau, d'un facteur 2 environ. Nous montrons que l'épaississement est déterminé par l'écoulement Marangoni dû à la présence des tensioactifs ; hors d'une émulsion, le film peut être enrichi en huile, ce que l'on peut interpréter à l'aide d'un modèle de capture ; hors d'une solution de polymère, on observe un fort gonflement du film dès que la solution est semi-diluée, à cause de l'effet des contraintes normales (effet Weissenberg). Le problème étudié a donc deux familles de solution : (i) à basse vitesse, le dépôt résulte d'un compromis entre viscosité et capillarité, si bien qu'il est sensible à la présence dans le bain d'hétérogénéités (tensioactifs, gouttes d'huile) ; (ii) à plus grande vitesse, l'inertie doit être prise en compte et l'épaisseur du film est alors liée aux propriétés de volume du liquide (densité et viscosité).

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluidized bed gasification of extracted coal

DOEpatents

Aquino, Dolores C.; DaPrato, Philip L.; Gouker, Toby R.; Knoer, Peter

1986-01-01

Coal or similar carbonaceous solids are extracted by contacting the solids in an extraction zone (12) with an aqueous solution having a pH above 12.0 at a temperature between 65.degree. C. and 110.degree. C. for a period of time sufficient to remove bitumens from the coal into said aqueous solution and the extracted solids are then gasified at an elevated pressure and temperature in a fluidized bed gasification zone (60) wherein the density of the fluidized bed is maintained at a value above 160 kg/m.sup.3. In a preferred embodiment of the invention, water is removed from the aqueous solution in order to redeposit the extracted bitumens onto the solids prior to the gasification step.

76 FR 21299 - Emergency Planning and Notification; Emergency Planning and List of Extremely Hazardous...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-15

...EPA is proposing to revise the manner by which the regulated community would apply the threshold planning quantities (TPQs) for those extremely hazardous substances (EHSs) that are non-reactive solid chemicals in solution form. Specifically, facilities with a solid EHS in solution would be subject to the Emergency Planning requirements if the amount of the solid chemical on-site, when multiplied by 0.2, equaled or exceeded the lower published TPQ, based on data that shows less potential for the solid chemical in solution to remain airborne in the event of an accidental release. Previously, EPA assumed that 100% of the chemical could become airborne in the event of an accidental release.

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

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Solution structure of the N-terminal domain of a replication restart primosome factor, PriC, in Escherichia coli

PubMed Central

Aramaki, Takahiko; Abe, Yoshito; Katayama, Tsutomu; Ueda, Tadashi

2013-01-01

In eubacterial organisms, the oriC-independent primosome plays an essential role in replication restart after the dissociation of the replication DNA-protein complex by DNA damage. PriC is a key protein component in the replication restart primosome. Our recent study suggested that PriC is divided into two domains: an N-terminal and a C-terminal domain. In the present study, we determined the solution structure of the N-terminal domain, whose structure and function have remained unknown until now. The revealed structure was composed of three helices and one extended loop. We also observed chemical shift changes in the heteronuclear NMR spectrum and oligomerization in the presence of ssDNA. These abilities may contribute to the PriC-ssDNA complex, which is important for the replication restart primosome. PMID:23868391

Computer simulation of concentrated solid solution strengthening

NASA Technical Reports Server (NTRS)

Kuo, C. T. K.; Arsenault, R. J.

1976-01-01

The interaction forces between a straight edge dislocation moving through a three-dimensional block containing a random array of solute atoms were determined. The yield stress at 0 K was obtained by determining the average maximum solute-dislocation interaction force that is encountered by edge dislocation, and an expression relating the yield stress to the length of the dislocation and the solute concentration is provided. The magnitude of the solid solution strengthening due to solute atoms can be determined directly from the numerical results, provided the dislocation line length that moves as a unit is specified.

Supercritical fluid molecular spray film deposition and powder formation

DOEpatents

Smith, Richard D.

1986-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.

Group A Streptococcal vaccine candidate: contribution of epitope to size, antigen presenting cell interaction and immunogenicity.

PubMed

Zaman, Mehfuz; Chandrudu, Saranya; Giddam, Ashwini K; Reiman, Jennifer; Skwarczynski, Mariusz; McPhun, Virginia; Moyle, Peter M; Batzloff, Michael R; Good, Michael F; Toth, Istvan

2014-12-01

Utilize lipopeptide vaccine delivery system to develop a vaccine candidate against Group A Streptococcus. Lipopeptides synthesized by solid-phase peptide synthesis-bearing carboxyl (C)-terminal and amino (N)-terminal Group A Streptococcus peptide epitopes. Nanoparticles formed were evaluated in vivo. Immune responses were induced in mice without additional adjuvant. We demonstrated for the first time that incorporation of the C-terminal epitope significantly enhanced the N-terminal epitope-specific antibody response and correlated with forming smaller nanoparticles. Antigen-presenting cells had increased uptake and maturation by smaller, more immunogenic nanoparticles. Antibodies raised by vaccination recognized isolates. Demonstrated the lipopeptidic nanoparticles to induce an immune response which can be influenced by the combined effect of epitope choice and size.

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

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

Bette, Sebastian; Dinnebier, Robert E.; Röder, Christian

2015-08-15

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these twomore » metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.« less

SOLIDS PRECIPITATION EVENT IN MCU CAUSAL ANALYSIS AND RECOMMENDATIONS FROM SOLIDS RECOVERY TEAM

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

Garrison, A.; Aponte, C.

A process upset occurred in the Modular Caustic-Side Solvent Extraction Unit (MCU) facility on April 6th, 2014. During recovery efforts, a significant amount of solids were found in the Salt Solution Feed Tank (SSFT), Salt Solution Receipt Tanks (SSRTs), two extraction contactors, and scrub contactors. The solids were identified by Savannah River National Laboratory (SRNL) as primarily sodium oxalate and sodium alumina silicate (NAS) with the presence of some aluminum hydroxide. NAS solids have been present in the SSFT since simulant runs during cold chemical startup of MCU in 2007, and have not hindered operations since that time. During themore » process upset in April 2014, the oxalate solids partially blocked the aqueous outlet of the extraction contactors, causing salt solution to exit through the contactor organic outlet to the scrub contactors with the organic phase. This salt solution overwhelmed the scrub contactors and passed with the organic phase to the strip section of MCU. The partially reversed flow of salt solution resulted in a Strip Effluent (SE) stream that was high in Isopar™ L, pH and sodium. The primary cause of the excessive solids accumulation in the SSRTs and SSFT at MCU is attributed to an increase in the frequency of oxalic acid cleaning of the 512-S primary filter. Agitation in the SSRTs at MCU in response to cold weather likely provided the primary mechanism to transfer the solids to the contactors. Sources of the sodium oxalate solids are attributed to the oxalic acid cleaning solution used to clean the primary filter at the Actinide Removal Process (ARP) filtration at 512-S, as well as precipitation from the salt batch feed, which is at or near oxalate saturation. The Solids Recovery Team was formed to determine the cause of the solids formation and develop recommendations to prevent or mitigate this event in the future. A total of 53 recommendations were generated. These recommendations were organized into 4 focus areas: • Improve understanding of oxalate equilibrium and kinetics in salt solutions • Reduction/elimination of oxalic acid cleaning in 512-S • Flowsheet optimization • Improving diagnostic capability The recommendations implemented prior to resumption of MCU operations provide a risk mitigation or detection function through additional sampling and observation. The longer term recommendations provide a framework to increase the basic process knowledge of both oxalate chemistry and filtration behavior and then facilitate decisions that improve the salt flowsheet as a system.« less

Finite element analysis of the effect of a non-planar solid-liquid interface on the lateral solute segregation during unidirectional solidification

NASA Technical Reports Server (NTRS)

Carlson, F. M.; Chin, L.-Y.; Fripp, A. L.; Crouch, R. K.

1982-01-01

The effect of solid-liquid interface shape on lateral solute segregation during steady-state unidirectional solidification of a binary mixture is calculated under the assumption of no convection in the liquid. A finite element technique is employed to compute the concentration field in the liquid and the lateral segregation in the solid with a curved boundary between the liquid and solid phases. The computational model is constructed assuming knowledge of the solid-liquid interface shape; no attempt is made to relate this shape to the thermal field. The influence of interface curvature on the lateral compositional variation is investigated over a range of system parameters including diffusivity, growth speed, distribution coefficient, and geometric factors of the system. In the limiting case of a slightly nonplanar interface, numerical results from the finite element technique are in good agreement with the analytical solutions of Coriell and Sekerka obtained by using linear theory. For the general case of highly non-planar interface shapes, the linear theory fails and the concentration field in the liquid as well as the lateral solute segregation in the solid can be calculated by using the finite element method.

Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN)1-x(ZnO)x solid solution.

PubMed

Wu, Aimin; Li, Jing; Liu, Baodan; Yang, Wenjin; Jiang, Yanan; Liu, Lusheng; Zhang, Xinglai; Xiong, Changmin; Jiang, Xin

2017-02-21

(GaN) 1-x (ZnO) x solid solution has attracted extensive attention due to its feasible band-gap tunability and excellent photocatalytic performance in overall water splitting. However, its potential application in the photodegradation of organic pollutants and environmental processing has rarely been reported. In this study, we developed a rapid synthesis process to fabricate porous (GaN) 1-x (ZnO) x solid solution with a tunable band gap in the range of 2.38-2.76 eV for phenol photodegradation. Under visible-light irradiation, (GaN) 0.75 (ZnO) 0.25 solid solution achieved the highest photocatalytic performance compared to other (GaN) 1-x (ZnO) x solid solutions with x = 0.45, 0.65 and 0.85 due to its higher redox capability and lower lattice deformation. Slight Ag decoration with a content of 1 wt% on the surface of the (GaN) 0.75 (ZnO) 0.25 solid solution leads to a significant enhancement in phenol degradation, with a reaction rate eight times faster than that of pristine (GaN) 0.75 (ZnO) 0.25 . Interestingly, phenol in aqueous solution (10 mg L -1 ) can also be completely degraded within 60 min, even under the direct exposure of sunlight irradiation. The photocurrent response indicates that the enhanced photocatalytic activity of (GaN) 0.75 (ZnO) 0.25 /Ag is directly induced by the improved transfer efficiency of the photogenerated electrons at the interface. The excellent phenol degradation performance of (GaN) 1-x (ZnO) x /Ag further broadens their promising photocatalytic utilization in environmental processing, besides in overall water splitting for hydrogen production.

Fabrication of Heterogeneous-Phase Solid-Solution Promoting Band Structure and Charge Separation for Enhancing Photocatalytic CO2 Reduction: A Case of ZnXCa1-XIn2S4.

PubMed

Zeng, Chao; Huang, Hongwei; Zhang, Tierui; Dong, Fan; Zhang, Yihe; Hu, Yingmo

2017-08-23

Photocatalytic CO 2 reduction into solar fuels illustrates huge charm for simultaneously settling energy and environmental issues. The photoreduction ability of a semiconductor is closely correlated to its conduction band (CB) position. A homogeneous-phase solid-solution with the same crystal system always has a monotonously changed CB position, and the high CB level has to be sacrificed to achieve a benign photoabsorption. Herein, we report the fabrication of heterogeneous-phase solid-solution Zn X Ca 1-X In 2 S 4 between trigonal ZnIn 2 S 4 and cubic CaIn 2 S 4 . The Zn X Ca 1-X In 2 S 4 solid solutions with orderly tuned photoresponsive range from 540 to 640 nm present a more negative CB level and highly enhanced charge-separation efficiency. Profiting from these merits, all of these Zn X Ca 1-X In 2 S 4 solid solutions exhibit remarkably strengthened photocatalytic CO 2 reduction performance under visible light (λ > 420 nm) irradiation. Zn 0.4 Ca 0.6 In 2 S 4 , bearing the most negative CB position and highest charge-separation efficiency, casts the optimal photocatalytic CH 4 and CO evolution rates, which reach 16.7 and 6.8 times higher than that of ZnIn 2 S 4 and 7.2 and 3.9 times higher than that of CaIn 2 S 4 , respectively. To verify the crucial role of the heterogeneous-phase solid solution in promoting the band structure and photocatalytic performance, another heterogeneous-phase solid-solution Zn X Cd 1-X In 2 S 4 has been synthesized. It also displays an upshifted CB level and promoted charge separation. This work may provide a new perspective into the development of an efficient visible-light driven photocatalyst for CO 2 reduction and other photoreduction reactions.

The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Zhuk, N.A.; Korolev, D.A.

2016-01-15

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.

Isotope Labeling for Solution and Solid-State NMR Spectroscopy of Membrane Proteins

PubMed Central

Verardi, Raffaello; Traaseth, Nathaniel J.; Masterson, Larry R.; Vostrikov, Vitaly V.; Veglia, Gianluigi

2013-01-01

In this chapter, we summarize the isotopic labeling strategies used to obtain high-quality solution and solid-state NMR spectra of biological samples, with emphasis on integral membrane proteins (IMPs). While solution NMR is used to study IMPs under fast tumbling conditions, such as in the presence of detergent micelles or isotropic bicelles, solid-state NMR is used to study the structure and orientation of IMPs in lipid vesicles and bilayers. In spite of the tremendous progress in biomolecular NMR spectroscopy, the homogeneity and overall quality of the sample is still a substantial obstacle to overcome. Isotopic labeling is a major avenue to simplify overlapped spectra by either diluting the NMR active nuclei or allowing the resonances to be separated in multiple dimensions. In the following we will discuss isotopic labeling approaches that have been successfully used in the study of IMPs by solution and solid-state NMR spectroscopy. PMID:23076578

Efficacy of pectin solution for preventing gastro-esophageal reflux events in patients with percutaneous endoscopic gastrostomy.

PubMed

Adachi, Kyoichi; Furuta, Kenji; Aimi, Masahito; Fukazawa, Kousuke; Shimura, Shino; Ohara, Shunji; Nakata, Shuji; Inoue, Yukiko; Ryuko, Kanji; Ishine, Junichi; Katoh, Kyoko; Hirata, Toshiaki; Ohhata, Shuzo; Katoh, Setsushi; Moriyama, Mika; Sumikawa, Masuko; Sanpei, Mari; Kinoshita, Yoshikazu

2012-05-01

The aim of this study was to determine the efficacy of pectin solution, which increases the viscosity of liquid nutrient, for prevention of gastro-esophageal reflux in comparison with half-solid nutrient. The subjects were 10 elderly patients undergoing percutaneous endoscopic gastrostomy feeding. Twenty-four-hour esophageal multichannel intraluminal impedance and pH testing was performed during intake of half-solid nutrient and a combination of pectin solution and liquid nutrient. During 4 h after delivery, there was no significant difference in the total number of gastro-esophageal reflux events between the feeding of the half-solid nutrient and the combination of pectin solution and liquid nutrient (5.7 ± 1.2 vs 5.3 ± 1.0/4 h). Acidic reflux after delivery of the half-solid nutrient was significantly more frequent than that after delivery of the combination of pectin solution and liquid nutrient (80.7% vs 60.4%, p = 0.018). The incidence of gastro-esophageal reflux reaching the upper portion of the esophagus tended to be higher during delivery of the half-solid nutrient than during delivery of the combination of pectin solution and liquid nutrient (47.4% vs 34.0%, p = 0.153). In conclusion, the usage of pectin solution combined with liquid nutrient is effective for preventing acidic gastro-esophageal reflux and gastro-esophageal reflux reaching the upper portion of the esophagus.

Driving CARs on the Highway to Solid Cancer: Some Considerations on the Adoptive Therapy with CAR T Cells.

PubMed

Abken, Hinrich

2017-11-01

Adoptive therapy with chimeric antigen receptor (CAR) redirected T cells achieved lasting remissions in hematologic malignancies, even in terminal stages of the disease. Exploring CAR T cell therapy in the treatment of solid tumors has just begun, balancing efficacy versus toxicity in early phase trials. In contrast to leukemia/lymphoma, solid tumors display a tremendously variable biology demanding different strategies to make a T cell attack successful in the long term. This article summarizes current developments, discusses the hurdles, and considers some modifications to improve the CAR T cell therapy in the treatment of solid tumors.

Hopping Diffusion of Nanoparticles Subjected to Topological Constraints

NASA Astrophysics Data System (ADS)

Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael

2013-03-01

We describe a novel hopping mechanism for diffusion of large non-sticky nanoparticles subjected to topological constraints in polymer solids (networks and gels) and entangled polymer liquids (melts and solutions). Probe particles with size larger than the mesh size of unentangled polymer networks (tube diameter of entangled polymer liquids) are trapped by the network (entanglement) cages at time scales longer than the relaxation time of the network (entanglement) strand. At long time scales, however, these particles can move further by hopping between neighboring confinement cages. This hopping is controlled by fluctuations of surrounding confinement cages, which could be large enough to allow particles to slip through. The terminal particle diffusion coefficient dominated by this hopping diffusion is appreciable for particles with size slightly larger than the network mesh size (tube diameter). Very large particles in polymer solids will be permanently trapped by local network cages, whereas they can still move in polymer liquids by waiting for entanglement cages to rearrange on the relaxation time scale of the liquids. We would like to acknowledge the financial support of NSF CHE-0911588, DMR-0907515, DMR-1121107, DMR-1122483, and CBET-0609087, NIH R01HL077546 and P50HL107168, and Cystic Fibrosis Foundation under grant RUBIN09XX0.

Chemically durable polymer electrolytes for solid-state alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Park, Eun Joo; Capuano, Christopher B.; Ayers, Katherine E.; Bae, Chulsung

2018-01-01

Generation of high purity hydrogen using electrochemical splitting of water is one of the most promising methods for sustainable fuel production. The materials to be used as solid-state electrolytes for alkaline water electrolyzer require high thermochemical stability against hydroxide ion attack in alkaline environment during the operation of electrolysis. In this study, two quaternary ammonium-tethered aromatic polymers were synthesized and investigated for anion exchange membrane (AEM)-based alkaline water electrolyzer. The membranes properties including ion exchange capacity (IEC), water uptake, swelling degree, and anion conductivity were studied. The membranes composed of all C-C bond polymer backbones and flexible side chain terminated by cation head groups exhibited remarkably good chemical stability by maintaining structural integrity in 1 M NaOH solution at 95 °C for 60 days. Initial electrochemical performance and steady-state operation performance were evaluated, and both membranes showed a good stabilization of the cell voltage during the steady-state operation at the constant current density at 200 mA/cm2. Although both membranes in current form require improvement in mechanical stability to afford better durability in electrolysis operation, the next generation AEMs based on this report could lead to potentially viable AEM candidates which can provide high electrolysis performance under alkaline operating condition.

The effect of solute additions on the steady-state creep behavior of dispersion-strengthened aluminum.

NASA Technical Reports Server (NTRS)

Reynolds, G. H.; Lenel, F. V.; Ansell, G. S.

1971-01-01

The effect of solute additions on the steady-state creep behavior of coarse-grained dispersion-strengthened aluminum alloys was studied. Recrystallized dispersion-strengthened solid solutions were found to have stress and temperature sensitivities quite unlike those observed in single-phase solid solutions having the same composition and grain size. The addition of magnesium or copper to the matrix of a recrystallized dispersion-strengthened aluminum causes a decrease in the steady-state creep rate which is much smaller than that caused by similar amounts of solute in single-phase solid solutions. All alloys exhibited essentially a 4.0 power stress exponent in agreement with the model of Ansell and Weertman. The activation energy for steady-state creep in dispersion-strengthened Al-Mg alloys, as well as the stress dependence, was in agreement with the physical model of dislocation climb over the dispersed particles.

Hybrid rockets - Combining the best of liquids and solids

NASA Technical Reports Server (NTRS)

Cook, Jerry R.; Goldberg, Ben E.; Estey, Paul N.; Wiley, Dan R.

1992-01-01

Hybrid rockets employing liquid oxidizer and solid fuel grain answers to cost, safety, reliability, and environmental impact concerns that have become as prominent as performance in recent years. The oxidizer-free grain has limited sensitivity to grain anomalies, such as bond-line separations, which can cause catastrophic failures in solid rocket motors. An account is presently given of the development effort associated with the AMROC commercial hybrid booster and component testing efforts at NASA-Marshall. These hybrid rockets can be fired, terminated, inspected, evaluated, and restarted for additional testing.

Solution Structure of the cGMP Binding GAF Domain from Phosphodiesterase 5: Insights into Nucleotide Specificity, Dimerization, and cGMP-Dependent Conformational Change

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

Heikaus, Clemens C.; Stout, Joseph R.; Sekharan, Monica R.

2008-08-15

Phosphodiesterase 5 (PDE5) controls intracellular levels of cGMP through its regulation of cGMP hydrolysis. Hydrolytic activity of the C-terminal catalytic domain is increased by cGMP binding to the N-terminal GAF A domain. We present the NMR solution structure of the cGMP-bound PDE5A GAF A domain. The cGMP orientation in the buried binding pocket was defined through 37 intermolecular NOEs.

Fluidized bed gasification of extracted coal

DOEpatents

Aquino, D.C.; DaPrato, P.L.; Gouker, T.R.; Knoer, P.

1984-07-06

Coal or similar carbonaceous solids are extracted by contacting the solids in an extraction zone with an aqueous solution having a pH above 12.0 at a temperature between 65/sup 0/C and 110/sup 0/C for a period of time sufficient to remove bitumens from the coal into said aqueous solution, and the extracted solids are then gasified at an elevated pressure and temperature in a fluidized bed gasification zone (60) wherein the density of the fluidized bed is maintained at a value above 160 kg/m/sup 3/. In a preferred embodiment of the invention, water is removed from the aqueous solution in order to redeposit the extracted bitumens onto the solids prior to the gasification step. 2 figs., 1 tab.

Suppression of vacancy cluster growth in concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; ...

2016-12-13

Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solutionmore » alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.« less

TM surface wave diffraction by a truncated dielectric slab recessed in a perfectly conducting surface. [considering flush mounted space shuttle antenna

NASA Technical Reports Server (NTRS)

Pathak, P. H.; Kouyoumjian, R. G.

1974-01-01

The diffraction of a TM sub o surface wave by a terminated dielectric slab which is flush mounted in a perfectly conducting surface is studied. The incident surface wave gives rise to waves reflected and diffracted by the termination; these reflected and diffracted fields may be expressed in terms of the geometrical theory of diffraction by introducing surface wave reflection and diffraction coefficients which are associated with the termination. In this investigation, the surface wave reflection and diffraction coefficients have been deduced from a formally exact solution to this canonical problem. The solution is obtained by a combination of the generalized scattering matrix technique and function theoretic methods.

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Scattering of focused ultrasonic beams by cavities in a solid half-space.

PubMed

Rahni, Ehsan Kabiri; Hajzargarbashi, Talieh; Kundu, Tribikram

2012-08-01

The ultrasonic field generated by a point focused acoustic lens placed in a fluid medium adjacent to a solid half-space, containing one or more spherical cavities, is modeled. The semi-analytical distributed point source method (DPSM) is followed for the modeling. This technique properly takes into account the interaction effect between the cavities placed in the focused ultrasonic field, fluid-solid interface and the lens surface. The approximate analytical solution that is available in the literature for the single cavity geometry is very restrictive and cannot handle multiple cavity problems. Finite element solutions for such problems are also prohibitively time consuming at high frequencies. Solution of this problem is necessary to predict when two cavities placed in close proximity inside a solid can be distinguished by an acoustic lens placed outside the solid medium and when such distinction is not possible.

Abrupt climate changes during Termination III in Southern Europe

PubMed Central

Pérez-Mejías, Carlos; Moreno, Ana; Sancho, Carlos; Bartolomé, Miguel; Stoll, Heather; Cacho, Isabel; Cheng, Hai; Edwards, R. Lawrence

2017-01-01

The Late Quaternary glacial–interglacial transitions represent the highest amplitude climate changes over the last million years. Unraveling the sequence of events and feedbacks at Termination III (T-III), including potential abrupt climate reversals similar to those of the last Termination, has been particularly challenging due to the scarcity of well-dated records worldwide. Here, we present speleothem data from southern Europe covering the interval from 262.7 to 217.9 kyBP, including the transition from marine isotope stage (MIS) 8 to MIS 7e. High-resolution δ13C, δ18O, and Mg/Ca profiles reveal major millennial-scale changes in aridity manifested in changing water availability and vegetation productivity. uranium–thorium dates provide a solid chronology for two millennial-scale events (S8.1 and S8.2) which, compared with the last two terminations, has some common features with Heinrich 1 and Heinrich 2 in Termination I (T-I). PMID:28874530

Abrupt climate changes during Termination III in Southern Europe.

PubMed

Pérez-Mejías, Carlos; Moreno, Ana; Sancho, Carlos; Bartolomé, Miguel; Stoll, Heather; Cacho, Isabel; Cheng, Hai; Edwards, R Lawrence

2017-09-19

The Late Quaternary glacial-interglacial transitions represent the highest amplitude climate changes over the last million years. Unraveling the sequence of events and feedbacks at Termination III (T-III), including potential abrupt climate reversals similar to those of the last Termination, has been particularly challenging due to the scarcity of well-dated records worldwide. Here, we present speleothem data from southern Europe covering the interval from 262.7 to 217.9 kyBP, including the transition from marine isotope stage (MIS) 8 to MIS 7e. High-resolution δ 13 C, δ 18 O, and Mg/Ca profiles reveal major millennial-scale changes in aridity manifested in changing water availability and vegetation productivity. uranium-thorium dates provide a solid chronology for two millennial-scale events (S8.1 and S8.2) which, compared with the last two terminations, has some common features with Heinrich 1 and Heinrich 2 in Termination I (T-I).

Abrupt climate changes during Termination III in Southern Europe

NASA Astrophysics Data System (ADS)

Pérez-Mejías, Carlos; Moreno, Ana; Sancho, Carlos; Bartolomé, Miguel; Stoll, Heather; Cacho, Isabel; Cheng, Hai; Edwards, R. Lawrence

2017-09-01

The Late Quaternary glacial-interglacial transitions represent the highest amplitude climate changes over the last million years. Unraveling the sequence of events and feedbacks at Termination III (T-III), including potential abrupt climate reversals similar to those of the last Termination, has been particularly challenging due to the scarcity of well-dated records worldwide. Here, we present speleothem data from southern Europe covering the interval from 262.7 to 217.9 kyBP, including the transition from marine isotope stage (MIS) 8 to MIS 7e. High-resolution δ13C, δ18O, and Mg/Ca profiles reveal major millennial-scale changes in aridity manifested in changing water availability and vegetation productivity. uranium-thorium dates provide a solid chronology for two millennial-scale events (S8.1 and S8.2) which, compared with the last two terminations, has some common features with Heinrich 1 and Heinrich 2 in Termination I (T-I).

Garnet: featured mineral group at the 1993 Tucson Show

USGS Publications Warehouse

Modreski, P.J.

1993-01-01

The garnets are a common but complex group of minerals. They are perhaps the mineral kingdom's best example of solid solution: a relationship in which minerals have chemical compositions that are intermediate between two or more ideal end-member species. In garnet, we deal with a complex group of solid-solution series between as many as 14 end-member minerals. The varying intergradations of solid solution between these different end-members help to explain the garnet group's variety of color, environment of occurrence, gem use, and variation in such physical properties as specific gravity, refractive index, and hardness. -from Author

Atomic-level simulation of ferroelectricity in perovskite solid solutions

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

Sepliarsky, M.; Instituto de Fisica Rosario, CONICET-UNR, Rosario,; Phillpot, S. R.

2000-06-26

Building on the insights gained from electronic-structure calculations and from experience obtained with an earlier atomic-level method, we developed an atomic-level simulation approach based on the traditional Buckingham potential with shell model which correctly reproduces the ferroelectric phase behavior and dielectric and piezoelectric properties of KNbO{sub 3}. This approach now enables the simulation of solid solutions and defected systems; we illustrate this capability by elucidating the ferroelectric properties of a KTa{sub 0.5}Nb{sub 0.5}O{sub 3} random solid solution. (c) 2000 American Institute of Physics.

[Experimental investigation of the straw pre-treatment to enhance its high solid anaerobic digestion].

PubMed

Jiang, Jian-Guo; Zhao, Zhen-Zhen; Du, Xue-Juan; Sui, Ji-Chao; Wu, Shi-Yao

2007-04-01

The straw contains a high content of lignin, which cannot be well utilized by anaerobic bacteria in high solid anaerobic digestion process. This paper presents the experimental investigation of the straw pre-treatment, which aims to destroy the complex structure of the lignin to enhance its high solid anaerobic digestion. The straw is pre-treated in different solutions including NaOH, ammonia, H2SO4, and carbamide. The pre-treating effects are expressed by COD concentration dissolved in the solutions and the 14-day biogas generation in the enhanced aerogenic experiment. Different affecting factors, such as the concentration of the chemical solution, the species of the straw, the pre-treatment reaction time, the reaction temperature and the size of the straw, are investigated. The results show that NaOH solution is the most effective pre-treatment chemical among the four different solutions. The experimental results still indicate that the accumulative biogas production can be 1 500 mL (10 g straw) in 14 days after pre-treatment in 4 mg/L NaOH solution and the dissolved COD in the solution reaches 39 000 mg/L after 24 hours. In addition, the experiment shows that the lignin content in the straw is reduced from 28% to 19% after pre-treatment in 1.5% (in weight) NaOH solution, and it can improve the straw treatment efficiency using high solid anaerobic digestion process.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

PubMed Central

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-01

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge. PMID:26755070

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation.

PubMed

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-12

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Contribution of Lattice Distortion to Solid Solution Strengthening in a Series of Refractory High Entropy Alloys

NASA Astrophysics Data System (ADS)

Chen, H.; Kauffmann, A.; Laube, S.; Choi, I.-C.; Schwaiger, R.; Huang, Y.; Lichtenberg, K.; Müller, F.; Gorr, B.; Christ, H.-J.; Heilmaier, M.

2018-03-01

We present an experimental approach for revealing the impact of lattice distortion on solid solution strengthening in a series of body-centered-cubic (bcc) Al-containing, refractory high entropy alloys (HEAs) from the Nb-Mo-Cr-Ti-Al system. By systematically varying the Nb and Cr content, a wide range of atomic size difference as a common measure for the lattice distortion was obtained. Single-phase, bcc solid solutions were achieved by arc melting and homogenization as well as verified by means of scanning electron microscopy and X-ray diffraction. The atomic radii of the alloying elements for determination of atomic size difference were recalculated on the basis of the mean atomic radii in and the chemical compositions of the solid solutions. Microhardness (μH) at room temperature correlates well with the deduced atomic size difference. Nevertheless, the mechanisms of microscopic slip lead to pronounced temperature dependence of mechanical strength. In order to account for this particular feature, we present a combined approach, using μH, nanoindentation, and compression tests. The athermal proportion to the yield stress of the investigated equimolar alloys is revealed. These parameters support the universality of this aforementioned correlation. Hence, the pertinence of lattice distortion for solid solution strengthening in bcc HEAs is proven.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

NASA Astrophysics Data System (ADS)

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-01

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Superhard Rhenium/Tungsten Diboride Solid Solutions.

PubMed

Lech, Andrew T; Turner, Christopher L; Lei, Jialin; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

2016-11-02

Rhenium diboride (ReB 2 ), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB 2 ), which takes a structural hybrid between that of ReB 2 and AlB 2 , where half of the boron layers are planar (as in AlB 2 ) and half are corrugated (as in ReB 2 ), has been shown not to be superhard. Here, we demonstrate that the ReB 2 -type structure can be maintained for solid solutions of tungsten in ReB 2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB 2 . These results further indicate that ReB 2 -structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

System issues and considerations associated with design of ground mobile strategic satellite communication terminals

NASA Astrophysics Data System (ADS)

Poliakon, J. A.

The current national defense doctrine calls for increased use of ground mobile strategic satellite communication earth terminals. This paper discusses some of the key communication terminal system issues and considerations associated with the design of nuclear hardened strategic ground mobile earth terminals. It considers system requirements such as nuclear hardness, rapid mobility, low profile, signal interference resistance, high availability, and long term independent operation. It also discusses impacts and implications associated with these requirements when imposed on a satellite earth terminal. It gives special focus to the ramifications of imposing mobility on earth terminals and its relationship to the system design approach used to arrive at an optimal system solution.

Aeroacoustics of supersonic jet flows from contoured and solid/porous conical plug-nozzles

NASA Technical Reports Server (NTRS)

Dosanjh, Darshan S.; Das, Indu S.

1987-01-01

The results of an experimental study of the acoustic far-field, the shock associated noise, and the nature of the repetitive shock structure of supersonic jet flows issuing from plug-nozzles having externally-expanded plugs with pointed termination operated at a range of supercritical pressure ratios Xi approaching 2 to 4.5 are reported. The plug of one of these plug-nozzles was contoured. The other plug-nozzles had short conical plugs with either a solid surface or a combination of solid/porous surface of different porosities. The contoured and the uncontoured plug-nozzles had the same throat area and the same annulus-radius ratio K = R sub p/R sub N = 0.43. As the result of modifications of the shock structure, the acoustic performance of improperly expanded jet flows of an externally-expanded short uncontoured plug of an appropriate geometry with suitably perforated plug and a pointed termination, is shown to approach the acoustic performance of a shock-free supersonic jet issuing from an equivalent externally-expanded contoured plug-nozzle.

NMR solution structure of the N-terminal domain of hERG and its interaction with the S4-S5 linker

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

Li, Qingxin; Gayen, Shovanlal; Chen, Angela Shuyi

Research highlights: {yields} The N-terminal domain (NTD, eag domain) containing 135 residues of hERG was expressed and purified from E. coli cells. {yields} Solution structure of NTD was determined with NMR spectroscopy. {yields} The alpha-helical region (residues 13-23) was demonstrated to possess the characteristics of an amphipathic helix. {yields} NMR titration confirmed the interaction between NTD and the peptide from the S4-S5 linker. -- Abstract: The human Ether-a-go-go Related Gene (hERG) potassium channel mediates the rapid delayed rectifier current (IKr) in the cardiac action potential. Mutations in the 135 amino acid residue N-terminal domain (NTD) cause channel dysfunction or mis-translocation.more » To study the structure of NTD, it was overexpressed and purified from Escherichia coli cells using affinity purification and gel filtration chromatography. The purified protein behaved as a monomer under purification conditions. Far- and near-UV, circular dichroism (CD) and solution nuclear magnetic resonance (NMR) studies showed that the purified protein was well-folded. The solution structure of NTD was obtained and the N-terminal residues 13-23 forming an amphipathic helix which may be important for the protein-protein or protein-membrane interactions. NMR titration experiment also demonstrated that residues from 88 to 94 in NTD are important for the molecular interaction with the peptide derived from the S4-S5 linker.« less

Method of making supercritical fluid molecular spray films, powder and fibers

DOEpatents

Smith, Richard D.

1988-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a heated nozzle having a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.

Using solid 13C NMR coupled with solution 31P NMR spectroscopy to investigate molecular species and lability of organic carbon and phosphorus from aquatic plants in Tai Lake, China

USDA-ARS?s Scientific Manuscript database

Aquatic plants are involved in the storage and release capacity for organic matter and nutrients. In this study, solid 13C and solution 31P nuclear magnetic resonance (NMR) spectroscopy were used to characterize the biomass samples of six aquatic plants. Solid 13C NMR spectroscopy revealed the domin...

A phase I dose escalation study of TTI-237 in patients with advanced malignant solid tumors.

PubMed

Wang-Gillam, Andrea; Arnold, Susanne M; Bukowski, Ronald M; Rothenberg, Mace L; Cooper, Wendy; Wang, Kenneth K; Gauthier, Eric; Lockhart, A Craig

2012-02-01

This study was to determine the maximum tolerated dose, dose-limiting toxicities, and pharmacokinetic profile of TTI-237, a novel anti-tubulin drug, administered weekly in patients with refractory solid tumors. Using an accelerated dose escalation design, patients with refractory solid tumors were enrolled in this study and treated with TTI-237 intravenously on days 1, 8 and 15 of a 28-day cycle. The starting dose was 4.5 mg/m(2). Pharmacokinetic studies were performed in patients at all dose levels. Twenty-eight patients were enrolled and treated with TTI-237 at dose of 4.5, 9, 15, 22.5 and 31.5 mg/m(2). One dose-limiting toxicity neutropenia fever was observed at 31.5 mg/m(2), and all seven patients developed grade 3 or 4 neutropenia at that dose level. TTI-237 dosage was de-escalated to 22.5 and 18 mg/m(2). Six patients were treated at the 18 mg/m(2) dose level without dose-limiting toxicity prior to trial termination. The mean terminal-phase elimination half-life (t(1/2)) for TTI-237 was 25-29 h, and the mean area under the concentration time curve at 31.5 mg/m(2) was 2,768 ng•h/mL. A protocol defined maximum tolerated dose was not determined because of early termination of the TTI-237 trial by the sponsor. 18 mg/m(2) may be a tolerable dose of TTI-237.

Simulation of radial solute segregation in vertical Bridgman growth of pyridine-doped benzene, a surrogate for binary organic nonlinear optical materials

NASA Astrophysics Data System (ADS)

Lee, Hanjie; Pearlstein, Arne J.

2000-09-01

We present steady axisymmetric computations of solute distributions and radial segregation for vertical Bridgman growth of pyridine-doped benzene, a binary aromatic system with anisotropic solid-phase thermal conductivity, that serves as a model of solute transport in crystal growth of organic nonlinear optical materials. The radial variation of solid-phase mass fraction ( Cs) of pyridine, which is rejected at the growing interface, depends strongly on growth conditions. High growth velocities tend to increase Cs near the centerline, the ampoule wall, or both, and low growth velocities give more nearly uniform radial distributions. The maximum ampoule-wall temperature gradient also affects radial segregation, with convex-to-the-liquid interfaces at small temperature gradients being associated with radially monotonic Cs distributions, and ridged interfaces at higher gradients being associated with nonmonotonic distributions having maxima at the centerline and ampoule wall. Nonuniformity is strongly determined by both interface shape and the nature of the flow near the interface. Solute is transported down to the interface by a large toroidal vortex, and swept radially inward to the centerline by a second, flattened toroidal cell. When the interface is depressed at its junction with the ampoule wall, rejected solute accumulates in the overlying liquid, where convection is relatively weak, resulting in local solute enrichment of the solid. Computations at normal and zero gravity show that for two very similar interface shapes, a maximum in the radial solid-phase solute distribution at the ampoule wall is associated with the interface shape, while the maximum on the centerline is associated with sweeping of solute to the centerline by a vortical flow on the interface. We also show that radial solute segregation depends significantly on whether account is taken of the anisotropy of the solid-phase thermal conductivity. Finally, the computations provide guidance as to the minimum ampoule length required to produce an axially uniform solute distribution over at least part of the length of a boule.

The interface character distribution of cold-rolled and annealed duplex stainless steel

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

Fang, Xiaoying, E-mail: fxy@sdut.edu.cn

The interface character distributions (ICDs) of cold-rolled and annealed duplex stainless steel specimens, previously solid-solution-heated (SHT) at 1573 K and 1323 K, are investigated using electron backscatter diffraction (EBSD) and five-parameter analysis (FPA). For the δ-ferrite phase, high concentrations of low angle grain boundaries (LAGBs) are developed, and the boundary planes are predominantly oriented on (111). High angle grain boundaries (HAGBs) with misorientations ranging from 50{sup o} to 60° are mostly pure tilt boundaries, and the boundary planes are primarily located on (112). For the austenite phase, very high density of coherent twin boundaries are introduced, implying that the boundarymore » planes are exactly oriented on (111). The phase boundary character distribution (PBPD) appears to be connected with the K-S and N-W orientation relationships (ORs) terminating on (110) {sub F}‖(111) {sub A} and (110){sub F}‖(hkl){sub A}, respectively. - Highlights: •Five-parameter analysis was used to determine interface character distribution. •ICD results of statistical meaning were achieved. •Initial microstructure has a significant effect on ICD. •Low and high angle GBs in δ phase prefer in (111) and (112) planes, respectively. •K-S phase boundaries terminate on (110){sub F}‖(111){sub A} while N-W ones on (110){sub F}‖(hkl){sub A}.« less

Maintenance of the secondary structure of horse cytochrome c during the conversion process of monomers to oligomers by addition of ethanol.

PubMed

Hirota, Shun; Ueda, Mariko; Hayashi, Yugo; Nagao, Satoshi; Kamikubo, Hironari; Kataoka, Mikio

2012-12-01

We have previously shown that polymerization of cytochrome c (cyt c) occurs by successively domain swapping its C-terminal α-helix in the presence of ethanol. However, the factors that govern the conversion process of monomers to domain-swapped oligomers remain unknown. We found that oligomeric cyt c is produced in the presence of ethanol and the oligomers precipitate due to low solubility. The optical absorption spectra revealed that in the presence of 30-40% ethanol, the Met-heme coordination in cyt c is dissociated. However, according to circular dichroism and small-angle X-ray scattering measurements, the α-helical structure of cyt c is maintained in solution with a little perturbation and the radius of gyration increases slightly but without dissociation of the C-terminal α-helix from the rest of the protein by the addition of ethanol. Solid-state nuclear magnetic resonance spectra showed that oligomeric cyt c in the precipitate also retains most of its α-helical structure. In the transmission electron microscopic image of the precipitate obtained by the addition of ethanol to cyt c, spherical particles with diameters of about 3 nm were detected. These results indicate that oligomeric cyt c forms through a state with the Met80 region locally unfolded, while maintaining the secondary structure, possibly an open monomer.

Microwave spectroscopic observation of distinct electron solid phases in wide quantum wells

NASA Astrophysics Data System (ADS)

Hatke, A. T.; Liu, Yang; Magill, B. A.; Moon, B. H.; Engel, L. W.; Shayegan, M.; Pfeiffer, L. N.; West, K. W.; Baldwin, K. W.

2014-06-01

In high magnetic fields, two-dimensional electron systems can form a number of phases in which interelectron repulsion plays the central role, since the kinetic energy is frozen out by Landau quantization. These phases include the well-known liquids of the fractional quantum Hall effect, as well as solid phases with broken spatial symmetry and crystalline order. Solids can occur at the low Landau-filling termination of the fractional quantum Hall effect series but also within integer quantum Hall effects. Here we present microwave spectroscopy studies of wide quantum wells that clearly reveal two distinct solid phases, hidden within what in d.c. transport would be the zero diagonal conductivity of an integer quantum-Hall-effect state. Explanation of these solids is not possible with the simple picture of a Wigner solid of ordinary (quasi) electrons or holes.

Free energies of formation of WC and WzC and the thermodynamic properties of carbon in solid tungsten

NASA Technical Reports Server (NTRS)

Gupta, D. K.; Seigle, L. L.

1974-01-01

The activity of carbon in the two-phase regions - W + WC and W + W2C was obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W2C were calculated. The temperature of the invariant reaction W2C = W + WC was fixed at 1570 + or - 5K. Using available solubility data for C in solid W, the partial molar free energy of C in the dilute solid solution was also calculated. The heat of solution of C in W, and the excess entropy for the interstitial solid solution, were computed, assuming that the carbon atoms reside in the octahedral interstices of bcc W.

New interpretation of data of the Earth's solid core

NASA Astrophysics Data System (ADS)

Guliyev, H. H.

2017-06-01

The commonly accepted scientific opinions on the inner core as the deformable solid globe are based on the solution of the problem on the distribution of elastic parameters in the inner structures of the Earth. The given solution is obtained within the necessary integral conditions on its self-weight, moment of inertia concerning the axes of rotation and periods of free oscillations of the Earth. It is shown that this solution does not satisfy the mechanics of the deformable solid body with sufficient local conditions following from basic principles concerning the strength, stability and actuality of velocities of propagation of elastic waves. The violation of local conditions shows that the inner core cannot exist in the form of the deformable solid body within the commonly accepted elastic parameters.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe.

PubMed

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-09-28

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La 3+ -Mn 4+ and Eu 3+ -Fe 3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La 3+ -Mn 4+ and Eu 3+ -Fe 3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe

PubMed Central

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-01-01

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La3+–Mn4+ and Eu3+–Fe3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La3+–Mn4+ and Eu3+–Fe3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications. PMID:28773925

Trace element abundances in single presolar silicon carbide grains by synchrotron X-ray fluorescence

NASA Astrophysics Data System (ADS)

Kashiv, Yoav

2004-12-01

Synchrotron x-ray fluorescence (SXRF) was applied to the study of presolar grains for the first time in this study. 41 single SiC grains of the KJF size fraction (mass-weighted median size of 1.86 μm) from the Murchison (CM2) Meteorite were analyzed. The absolute abundances of the following elements were determined (not every element in every grain): S, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Sr, Y, Zr, Nb, Mo, Ru, Os, Ir and Pt (underlined elements were detected here for the first time in single grains). There is good agreement between the heavier trace element abundances in the grains and s-process nucleosynthesis calculations. It suggests that smaller 13C pocket sizes are needed in the parent stars, a free parameter in the stellar models, than is deduced from isotopic analyses of s-, and s-mainly, elements, such as Zr and Mo. In addition, the data confirms the radiogenic nature of the Nb in the grains, due to the in situ decay of 93Zr (t 1/2 = 1.5 × 106 year). The data suggest that the trace elements condensed into the host SiC grains by a combination of condensation in solid solution and incorporation of subgrains. It seems that many of the trace elements reside mainly in subgrains of two solid solution: (1)a TiC based solid solution, and (2)a Mo-Ru carbide based solid solution. The presence of subgrains of an Fe-Ni alloy solid solution is suggested as well. Subgrains of all 3 solid solutions were observed previously in presolar graphite grains.* *This dissertation is a compound document (contains both a paper copy and a CD as part of the dissertation). The CD requires the following system requirements: Adobe Acrobat.

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Korolev, D.A.; Zhuk, N.A.

On the basis of the results of magnetic susceptibility and ESR studies of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions iron atoms in the solid solutions of cubic modification of bismuth niobate were found to exist as Fe(III) monomers and exchange bound Fe(III)-O-Fe(III) dimers with antiferro- and ferromagnetic type of superexchange. The exchange parameters and the distribution of monomers and dimers in the solid solutions were calculated as a function of paramagnetic atom content. - Graphical abstract: The study of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions showed that the introduction of iron atoms into the structure ofmore » Bi{sub 3}NbO{sub 7} stabilizes the cubic structure of bismuth niobate making the phase transition tetragonal ↔ cubic structure irreversible. In the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions we observe the formation of dimers with antiferro- and ferromagnetic exchange. Such clusters are partially retained even at the infinite dilution of the solid solution, which testifies for their rigidity. A sufficiently high parameter of ferromagnetic exchange in a dimer (+53 cm{sup −1}) seems to result from iron atoms being located in the vicinity of oxygen vacancy. - Highlights: • The reversible transition cubic – tetragonal modifications in Bi{sub 3}NbO{sub 7} becomes irreversible. • Only cubic modification of Bi{sub 3}Nb{sub 1-x}Fe{sub x}O{sub 7-δ} is stable due to clusters of Fe atoms. • These clusters are sufficiently strong and retained even at the infinite dilution. • The calculations of magnetic susceptibility give the distribution of the clusters and single atoms.« less

Roles of Segmental and Oligomeric Diffusion on the Gel Effect in Free Radical Polymerization

NASA Astrophysics Data System (ADS)

Wisnudel, M. B.; Torkelson, J. M.

1996-03-01

Termination between radicals has been simulated by phosphorescence quenching, showing strong roles for segmental and oligomeric radical self-diffusion in the origin of the gel effect. Quenching rate constants (k_q) were measured between benzil-terminated polymer as a function of anthracene-terminated polymer in polymer solutions. In dilute solution, interactions between 10k or 73k MW benzil-terminated polystyrene (PS- B) and anthracence-terminated polystyrene (PS-A) of varying MW, the MW effect is weaker than the Smoluchowski eq. prediction (kq MW^- 0.5). At higher concentration, interactions of PS-B and PS-A of like MW show only weak dependence of kq on MW and a concentration dependence similar to that of segmental mobility, indicating that segmental diffusion is important in termination. Finally, with interactions between 73k MW PS-B and PS-A of varying MW at 35 wt% PS, kq decreases by a factor of 10 in going from MW's of 100 to 1000 g/mol; beyond 1000 g/mol, kq is MW independent. Such effects cannot be explained by polymer-radical self-diffusion. However, they support the notion that the gel effect onset is associated with the concentration dependence of oligomeric radical self-diffusion and polymer radical chain-end segmental mobility.

Using colloidal silica as isolator, diverter and blocking agent for subsurface geological applications

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

Bourcier, William L.; Roberts, Sarah K.; Roberts, Jeffery J.

A system for blocking fast flow paths in geological formations includes preparing a solution of colloidal silica having a nonviscous phase and a solid gel phase. The solution of colloidal silica is injected into the geological formations while the solution of colloidal silica is in the nonviscous phase. The solution of colloidal silica is directed into the fast flow paths and reaches the solid gel phase in the fast flow paths thereby blocking flow of fluid in the fast paths.

Containerless synthesis of amorphous and nanophase organic materials

DOEpatents

Benmore, Chris J.; Weber, Johann R.

2016-05-03

The invention provides a method for producing a mixture of amorphous compounds, the method comprising supplying a solution containing the compounds; and allowing at least a portion of the solvent of the solution to evaporate while preventing the solute of the solution from contacting a nucleation point. Also provided is a method for transforming solids to amorphous material, the method comprising heating the solids in an environment to form a melt, wherein the environment contains no nucleation points; and cooling the melt in the environment.

Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.

First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

DOE PAGES

Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; ...

2011-12-15

Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn 1/3Nb 2/3)O₃ and Pb(Mg 1/3Nb 2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies canmore » have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.« less

Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

NASA Astrophysics Data System (ADS)

Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

2013-03-01

A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

Design of high-strength refractory complex solid-solution alloys

DOE PAGES

Singh, Prashant; Sharma, Aayush; Smirnov, A. V.; ...

2018-03-28

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K)more » over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.« less

Atomistic simulation of mineral-melt trace-element partitioning

NASA Astrophysics Data System (ADS)

Allan, Neil L.; Du, Zhimei; Lavrentiev, Mikhail Yu.; Blundy, Jon D.; Purton, John A.; van Westrenen, Wim

2003-09-01

We discuss recent advances in computational approaches to trace-element incorporation in minerals and melts. It is crucial to take explicit account of the local structural environment of each ion in the solid and the change in this environment following the introduction of a foreign atom or atoms. Particular attention is paid to models using relaxation (strain) energies and solution energies, and the use of these different models for isovalent and heterovalent substitution in diopside and forsterite. Solution energies are also evaluated for pyrope and grossular garnets, and pyrope-grossular solid solutions. Unfavourable interactions between dodecahedral sites containing ions of the same size and connected by an intervening tetrahedron lead to larger solubilities of trace elements in the garnet solid solution than in either end member compound and to the failure of Goldschmidt's first rule. Our final two examples are the partitioning behaviour of noble gases, which behave as 'ions of zero charge' and the direct calculation of high-temperature partition coefficients between CaO solid and melt via Monte Carlo simulations.

Design of high-strength refractory complex solid-solution alloys

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

Singh, Prashant; Sharma, Aayush; Smirnov, A. V.

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K)more » over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.« less

Hydrothermal synthesis of pollucite, analcime and their solid solutions and analysis of their properties

NASA Astrophysics Data System (ADS)

Jing, Zhenzi; Cai, Kunchuan; Li, Yan; Fan, Junjie; Zhang, Yi; Miao, Jiajun; Chen, Yuqian; Jin, Fangming

2017-05-01

Pollucite, as a perfect long-term potential host for radioactive Cs immobilization, barely exists in pure form naturally but in an isomorphism form between pollucite and analcime due to coexistence of Cs and Na. Pollucite could be hydrothermally synthesized with Cs-polluted soil or clay minerals which contain Cs and Na, and it is necessary to study the properties of the synthesis if Cs and Na contained. Pure pollucite, analcime and their solid solutions were hydrothermally synthesized with chemicals, and it was found that the most formed pollucite analcime solid solutions with Cs/(Cs + Na) ratios of 2/6-5/6 had very similar properties in mineral composition, morphology and size, structural water (Cs cations) and coordination environment to pollucite. This also suggests that even coexistence of Cs and Na in nature, pollucite favors to form due to site preference for Cs over Na, which leads to the property and the structure of the most solid solutions similar to that of pollucite.

Elastic constants and pressure derivative of elastic constants of Si1-xGex solid solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Baria, J. K.; Vyas, P. S.; Jani, A. R.

2013-02-01

Elastic properties of Si1-xGex solid solution with arbitrary (atomic) concentration (x) are studied using the pseudo-alloy atom model based on the pseudopotential theory and on the higher-order perturbation scheme with the application of our own proposed model potential. We have used local-field correction function proposed by Sarkar et al to study Si-Ge system. The Elastic constants and pressure derivatives of elastic constants of the solid solution is investigated with different concentration x of Ge. It is found in the present study that the calculated numerical values of the aforesaid physical properties of Si-Ge system are function of x. The elastic constants (C11, C12 and C44) decrease linearly with increase in concentration x and pressure derivative of elastic constants (C11, C12 and C44) increase with the concentration x of Ge. This study provides better set of theoretical results for such solid solution for further comparison either with theoretical or experimental results.

Peptidoglycan-associated outer membrane protein Mep45 of rumen anaerobe Selenomonas ruminantium forms a non-specific diffusion pore via its C-terminal transmembrane domain.

PubMed

Kojima, Seiji; Hayashi, Kanako; Tochigi, Saeko; Kusano, Tomonobu; Kaneko, Jun; Kamio, Yoshiyuki

2016-10-01

The major outer membrane protein Mep45 of Selenomonas ruminantium, an anaerobic Gram-negative bacterium, comprises two distinct domains: the N-terminal S-layer homologous (SLH) domain that protrudes into the periplasm and binds to peptidoglycan, and the remaining C-terminal transmembrane domain, whose function has been unknown. Here, we solubilized and purified Mep45 and characterized its function using proteoliposomes reconstituted with Mep45. We found that Mep45 forms a nonspecific diffusion channel via its C-terminal region. The channel was permeable to solutes smaller than a molecular weight of roughly 600, and the estimated pore radius was 0.58 nm. Truncation of the SLH domain did not affect the channel property. On the basis of the fact that Mep45 is the most abundant outer membrane protein in S. ruminantium, we conclude that Mep45 serves as a main pathway through which small solutes diffuse across the outer membrane of this bacterium.

Both solubility and chemical stability of curcumin are enhanced by solid dispersion in cellulose derivative matrices.

PubMed

Li, Bin; Konecke, Stephanie; Wegiel, Lindsay A; Taylor, Lynne S; Edgar, Kevin J

2013-10-15

Amorphous solid dispersions (ASD) of curcumin (Cur) in cellulose derivative matrices, hydroxypropylmethylcellulose acetate succinate (HPMCAS), carboxymethylcellulose acetate butyrate (CMCAB), and cellulose acetate adipate propionate (CAAdP) were prepared in order to investigate the structure-property relationship and identify polymer properties necessary to effectively increase Cur aqueous solution concentration. XRD results indicated that all investigated solid dispersions were amorphous, even at a 9:1 Cur:polymer ratio. Both stability against crystallization and Cur solution concentration from these ASDs were significantly higher than those from physical mixtures and crystalline Cur. Remarkably, curcumin was also stabilized against chemical degradation in solution. Chemical stabilization was polymer-dependent, with stabilization in CAAdP>CMCAB>HPMCAS>PVP, while matrices enhanced solution concentration as PVP>HPMCAS>CMCAB≈CAAdP. HPMCAS/Cur dispersions have useful combinations of pH-triggered release profile, chemical stabilization, and strong enhancement of Cur solution concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

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

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE PAGES

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

2016-10-11

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

A Simple Procedure for Constructing 5'-Amino-Terminated Oligodeoxynucleotides in Aqueous Solution

NASA Technical Reports Server (NTRS)

Bruick, Richard K.; Koppitz, Marcus; Joyce, Gerald F.; Orgel, Leslie E.

1997-01-01

A rapid method for the synthesis of oligodeoxynucleotides (ODNs) terminated by 5'-amino-5'-deoxythymidine is described. A 3'-phosphorylated ODN (the donor) is incubated in aqueous solution with 5'-amino- 5'-deoxythymidine in the presence of N-(3-dimethylaminopropyl)-)N'-ethylcarbodiimide hydrochloride (EDC), extending the donor by one residue via a phosphoramidate bond. Template- directed ligation of the extended donor and an acceptor ODN, followed by acid hydrolysis, yields the acceptor ODN extended by a single 5'-amino-5'-deoxythymidine residue at its 5'terminus.

A facile synthesis of Zn(x)Cd(1-x)S/CNTs nanocomposite photocatalyst for H2 production.

PubMed

Wang, Lei; Yao, Zhongping; Jia, Fangzhou; Chen, Bin; Jiang, Zhaohua

2013-07-21

The sulfide solid solution has become a promising and important visible-light-responsive photocatalyst for hydrogen production nowadays. Zn(x)Cd(1-x)S/CNT nanocomposites were synthesized to improve the dispersion, adjust the energy band gap, and enhance the separation of the photogenerated electrons and holes. The as-prepared photocatalysts were characterized by scanning electron-microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra (UV-visible), respectively. And the effects of CNTs on structure, composition and optical absorption property of the sulfide solid solutions were investigated along with their inherent relationships. For Zn0.83Cd0.17S/CNTs, sulfide solid solution is assembled along the CNTs orderly, with a diameter of 100 nm or so. XPS analysis shows that there is bonding effect between the solid solutions and the CNTs due to the strong adsorption of Zn(2+) and Cd(2+) on the surface of CNTs. There are two obvious absorption edges for Zn0.83Cd0.17S/CNTs, corresponding to two kinds of sulfide solid solutions with different molar ratios of Zn/Cd. The hybridization of solid solutions with CNTs makes the absorption spectrum red shift. The photocatalytic property was evaluated by splitting Na2S + Na2SO3 solution into H2, and the highest rate of H2 evolution of 6.03 mmol h(-1) g(-1) was achieved over Zn0.83Cd0.17S/CNTs. The high activity of photocatalytic H2 production is attributed to the following factors: (1) the optimum band gap and a moderate position of the conduction band (which needs to match the irradiation spectrum of the Xe lamp best), (2) the efficient separation of photogenerated electrons and holes by hybridization, and (3) the improvement of the dispersion of nanocomposites by assembling along the CNTs as well.

Synthesis, structural and semiconducting properties of Ba(Cu1/3 Sb2/3)O3-PbTiO3 solid solutions

NASA Astrophysics Data System (ADS)

Singh, Chandra Bhal; Kumar, Dinesh; Prashant, Verma, Narendra Kumar; Singh, Akhilesh Kumar

2018-05-01

We report the synthesis and properties of a new solid solution 0.05Ba(Cu1/3Sb2/3)O3-0.95PbTiO3 (BCS-PT) which shows the semiconducting properties. In this study, we have designed new perovskite-type (ABO3) solid solution of BCS-PT that have tunable optical band gap. BCS-PT compounds were prepared by conventional solid-state reaction method and their structural, micro-structural and optical properties were analyzed. The calcination temperature for BCS-PT solid solutions has been optimized to obtain a phase pure system. The Reitveld analysis of X-ray data show that all samples crystallize in tetragonal crystal structure with space group P4mm. X-ray investigation revealed that increase in calcination temperature led to increase of lattice parameter `a' while `c' parameter value lowered. The band gap of PbTiO3 is reduced from 3.2 eV to 2.8 eV with BCS doping and with increasing calcination temperature it further reduces to 2.56 eV. The reduced band gap indicated that the compounds are semiconducting and can be used for photovoltaic device applications.

Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

PubMed

Wang, Fudong; Buhro, William E

2017-12-26

Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

High temperature resistant cermet and ceramic compositions

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

Cermet compositions having high temperature oxidation resistance, high hardness and high abrasion and wear resistance, and particularly adapted for production of high temperature resistant cermet insulator bodies are presented. The compositions are comprised of a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Also disclosed are novel ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride.

Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

DOEpatents

Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

1994-01-01

A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Electrical resistivity of the UAs 1- xSex solid solutions

NASA Astrophysics Data System (ADS)

Breandon, C.; Bartholin, H.; Tchapoutian, R.; Therond, P. G.; Schoenes, J.; Vogt, O.

1987-01-01

The electrical resistivity ϱ of UAs 1- xSex solid solutions has been measured between 13 K and room temperature. The magnetic phase diagram has been deduced. Effects of uniaxial stress on ϱ allow to understand some results and to reveal anisotropy of ϱ.

TANK 26F SUPERNATANT AND 2F EVAPORATOR EDUCTOR PUMP SAMPLE CHARACTERIZATION RESULTS

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

King, W.; Hay, M.; Coleman, C.

2011-08-23

In an effort to understand the reasons for system plugging problems in the SRS 2F evaporator, supernatant samples were retrieved from the evaporator feed tank (Tank 26F) and solids were collected from the evaporator eductor feed pump for characterization. The variable depth supernatant samples were retrieved from Tank 26F in early December of 2010 and samples were provided to SRNL and the F/H Area laboratories for analysis. Inspection and analysis of the samples at SRNL was initiated in early March of 2011. During the interim period, samples were frequently exposed to temperatures as low as 12 C with daily temperaturemore » fluctuations as high as 10 C. The temperature at the time of sample collection from the waste tank was 51 C. Upon opening the supernatant bottles at SRNL, many brown solids were observed in both of the Tank 26F supernatant samples. In contrast, no solids were observed in the supernatant samples sent to the F/H Area laboratories, where the analysis was completed within a few days after receipt. Based on these results, it is believed that the original Tank 26F supernatant samples did not contain solids, but solids formed during the interim period while samples were stored at ambient temperature in the SRNL shielded cells without direct climate control. Many insoluble solids (>11 wt. % for one sample) were observed in the Tank 26F supernatant samples after three months of storage at SRNL which would not dissolve in the supernatant solution in two days at 51 C. Characterization of these solids along with the eductor pump solids revealed the presence of sodium oxalate and clarkeite (uranyl oxyhydroxide) as major crystalline phases. Sodium nitrate was the dominant crystalline phase present in the unwashed Eductor Pump solids. Crystalline sodium nitrate may have formed during the drying of the solids after filtration or may have been formed in the Tank 26F supernatant during storage since the solution was found to be very concentrated (9-12 M Na{sup +}). Concentrated mineral acids and elevated temperature were required to dissolve all of these solids. The refractory nature of some of the solids is consistent with the presence of metal oxides such as aluminosilicates (observed as a minor phase by XRD). Characterization of the water wash solutions and the digested solids confirmed the presence of oxalate salts in both solid samples. Sulfate enrichment was also observed in the Tank 26F solids wash solution, indicating the presence of sulfate precipitates such as burkeite. OLI modeling of the Tank 26F filtered supernatant composition revealed that sodium oxalate has a very low solubility in this solution. The model predicts that the sodium oxalate solubility in the Tank 26F supernatant is only 0.0011 M at 50 C. The results indicate that the highly concentrated nature of the evaporator feed solution and the addition of oxalate anion to the waste stream each contribute to the formation of insoluble solids in the 2F evaporator system.« less

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

NASA Astrophysics Data System (ADS)

Xiang-Hong, He; Zhao-Lian, Ye; Ming-Yun, Guan; Ning, Lian; Jian-Hua, Sun

2016-02-01

Pr3+-activated barium tungsto-molybdate solid solution phosphor Ba(Mo1-zWz)O4:Pr3+ is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr3+-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO4] for [MoO4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo1-zWz)O4:Pr3+ owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity, well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white light-emitting diodes (LEDs). Project supported by the Construction Fund for Science and Technology Innovation Group from Jiangsu University of Technology, China, the Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, China (Grant No. KHK1409), the Priority Academic Program Development of Jiangsu Higher Education Institutions, China, and the National Natural Science Foundation of China (Grant No. 21373103).

Incorporation of Cadmium and Nickel into Ferrite Spinel Solid Solution: X-ray Diffraction and X-ray Absorption Fine Structure Analyses.

PubMed

Su, Minhua; Liao, Changzhong; Chan, Tingshan; Shih, Kaimin; Xiao, Tangfu; Chen, Diyun; Kong, Lingjun; Song, Gang

2018-01-16

The feasibility of incorporating Cd and Ni in hematite was studied by investigating the interaction mechanism for the formation of Cd x Ni 1-x Fe 2 O 4 solid solutions (CNFs) from CdO, NiO, and α-Fe 2 O 3 . X-ray diffraction results showed that the CNFs crystallized into spinel structures with increasing lattice parameters as the Cd content in the precursors was increased. Cd 2+ ions were found to occupy the tetrahedral sites, as evidenced by Rietveld refinement and extended X-ray absorption fine structure analyses. The incorporation of Cd and Ni into ferrite spinel solid solution strongly relied on the processing parameters. The incorporation of Cd and Ni into the CNFs was greater at high x values (0.7 < x ≤ 1.0) than at low x values (0.0 ≤ x ≤ 0.7). A feasible treatment technique based on the investigated mechanism of CNF formation was developed, involving thermal treatment of waste sludge containing Cd and Ni. Both of these metals in the waste sludge were successfully incorporated into a ferrite spinel solid solution, and the concentrations of leached Cd and Ni from this solid solution were substantially reduced, stabilizing at low levels. This research offers a highly promising approach for treating the Cd and Ni content frequently encountered in electronic waste and its treatment residues.

A Transportable VLF/LF Repeater Terminal - A Design Study,

DTIC Science & Technology

1986-07-01

Corporation and marketed commercially as the ROLM 1602B, is expected to be used on the Airborne Command Post (ABNCP) fleet for MMPM processing. The basic...A suitable keyboard/printer for this application is a solid state teletype, the AN/ UGC -120. This device can also function as an AFSATCOM terminal...and as the VLF output device in the event of CPU failure. The AN/ UGC -120 is an Air Force inventory item. 20 INTERSITE COW4UNICATIONS SUBSYSTEM A single

Computer program development and user's manual for program PARACH. [to investigate parachute spent solid rocket booster during terminal descent

NASA Technical Reports Server (NTRS)

Murphree, H. I.

1979-01-01

A user's manual is provided for program PARACH, a FORTRAN digital computer program operational on the Univac 1108. A description of the program and operating instructions for it are included. Program PARACH is used to study the interaction dynamics of a parachute and its payload during terminal descent. Operating instructions, required input data, program options and limitations, and output data are described. Subroutines used in this program are also listed and explained.

Physical Models of Cognition

NASA Technical Reports Server (NTRS)

Zak, Michail

1994-01-01

This paper presents and discusses physical models for simulating some aspects of neural intelligence, and, in particular, the process of cognition. The main departure from the classical approach here is in utilization of a terminal version of classical dynamics introduced by the author earlier. Based upon violations of the Lipschitz condition at equilibrium points, terminal dynamics attains two new fundamental properties: it is spontaneous and nondeterministic. Special attention is focused on terminal neurodynamics as a particular architecture of terminal dynamics which is suitable for modeling of information flows. Terminal neurodynamics possesses a well-organized probabilistic structure which can be analytically predicted, prescribed, and controlled, and therefore which presents a powerful tool for modeling real-life uncertainties. Two basic phenomena associated with random behavior of neurodynamic solutions are exploited. The first one is a stochastic attractor ; a stable stationary stochastic process to which random solutions of a closed system converge. As a model of the cognition process, a stochastic attractor can be viewed as a universal tool for generalization and formation of classes of patterns. The concept of stochastic attractor is applied to model a collective brain paradigm explaining coordination between simple units of intelligence which perform a collective task without direct exchange of information. The second fundamental phenomenon discussed is terminal chaos which occurs in open systems. Applications of terminal chaos to information fusion as well as to explanation and modeling of coordination among neurons in biological systems are discussed. It should be emphasized that all the models of terminal neurodynamics are implementable in analog devices, which means that all the cognition processes discussed in the paper are reducible to the laws of Newtonian mechanics.

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

Du Hongliang; Zhou Wancheng; Luo Fa

The (1-x)(K{sub 0.5}Na{sub 0.5})NbO{sub 3}-x(Ba{sub 0.5}Sr{sub 0.5})TiO{sub 3} (KNN-BST) solid solution has been synthesized by conventional solid-state sintering in order to search for the new lead-free relaxor ferroelectrics for high temperature applications. The phase structure, dielectric properties, and relaxor behavior of the (1-x)KNN-xBST solid solution are systematically investigated. The phase structure of the (1-x)KNN-xBST solid solution gradually changes from pure perovskite phase with an orthorhombic symmetry to the tetragonal symmetry, then to the pseudocubic phase, and to the cubic phase with increasing addition of BST. The 0.90KNN-0.10BST solid solution shows a broad dielectric peak with permittivity maximum near 2500 andmore » low dielectric loss (<4%) in the temperature range of 100-250 deg. C. The result indicates that this material may have great potential for a variety of high temperature applications. The diffuse phase transition and the temperature of the maximum dielectric permittivity shifting toward higher temperature with increasing frequency, which are two typical characteristics for relaxor ferroelectrics, are observed in the (1-x)KNN-xBST solid solution. The dielectric relaxor behavior obeys a modified Curie-Weiss law and a Vogel-Fulcher relationship. The relaxor nature is attributed to the appearance of polar nanoregions owing to the formation of randon fields including local electric fields and elastic fields. These results confirm that the KNN-based relaxor ferroelectrics can be regarded as an alternative direction for the development of high temperature lead-free relaxor ferroelectrics.« less

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition

PubMed Central

Nakayama, Hirokazu; Hayashi, Aki

2014-01-01

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids. PMID:25080007

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition.

PubMed

Nakayama, Hirokazu; Hayashi, Aki

2014-07-30

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids.

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE PAGES

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; ...

2017-11-30

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

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

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

The mechanical problems on additive manufacturing of viscoelastic solids with integral conditions on a surface increasing in the growth process

NASA Astrophysics Data System (ADS)

Parshin, D. A.; Manzhirov, A. V.

2018-04-01

Quasistatic mechanical problems on additive manufacturing aging viscoelastic solids are investigated. The processes of piecewise-continuous accretion of such solids are considered. The consideration is carried out in the framework of linear mechanics of growing solids. A theorem about commutativity of the integration over an arbitrary surface increasing in the solid growing process and the time-derived integral operator of viscoelasticity with a limit depending on the solid point is proved. This theorem provides an efficient way to construct on the basis of Saint-Venant principle solutions of nonclassical boundary-value problems for describing the mechanical behaviour of additively formed solids with integral satisfaction of boundary conditions on the surfaces expanding due to the additional material influx to the formed solid. The constructed solutions will retrace the evolution of the stress-strain state of the solids under consideration during and after the processes of their additive formation. An example of applying the proved theorem is given.

Characterization, dissolution and solubility of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 °C and pH 2-9.

PubMed

Zhu, Yinian; Huang, Bin; Zhu, Zongqiang; Liu, Huili; Huang, Yanhua; Zhao, Xin; Liang, Meina

2016-01-01

The interaction between Ca-HAP and Pb(2+) solution can result in the formation of a hydroxyapatite-hydroxypyromorphite solid solution [(PbxCa1-x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it's necessary to know the physicochemical properties of (PbxCa1-x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported. Dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb(2+) concentrations increased rapidly with time and reached a peak value after 240-720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00-0.80), the aqueous Pb(2+) concentrations increased quickly with time and reached a peak value after 1-12 h dissolution, and then decreased gradually and attained a stable state after 720-2160 h dissolution. The dissolution process of the solids with high XPb (0.89-1.00) was different from that of the solids with low XPb (0.00-0.80). The average K sp values were estimated to be 10(-80.77±0.20) (10(-80.57)-10(-80.96)) for hydroxypyromorphite [Pb5(PO4)3OH] and 10(-58.38±0.07) (10(-58.31)-10(-58.46)) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f (o) ) were determined to be -3796.71 and -6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1‒x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1-x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1-x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution. Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 ˚C and an initial pH of 2.00.

Evidence for phase separation of ethanol-water mixtures at the hydrogen terminated nanocrystalline diamond surface.

PubMed

Janssens, Stoffel D; Drijkoningen, Sien; Saitner, Marc; Boyen, Hans-Gerd; Wagner, Patrick; Larsson, Karin; Haenen, Ken

2012-07-28

Interactions between ethanol-water mixtures and a hydrophobic hydrogen terminated nanocrystalline diamond surface, are investigated by sessile drop contact angle measurements. The surface free energy of the hydrophobic surface, obtained with pure liquids, differs strongly from values obtained by ethanol-water mixtures. Here, a model which explains this difference is presented. The model suggests that, due to a higher affinity of ethanol for the hydrophobic surface, when compared to water, a phase separation occurs when a mixture of both liquids is in contact with the H-terminated diamond surface. These results are supported by a computational study giving insight in the affinity and related interaction at the liquid-solid interface.

In vitro dermal absorption of di(2-ethylhexyl) adipate (DEHA) in a roll-on deodorant using human skin.

PubMed

Zhou, Simon Ningsun; Moody, Richard P; Aikawa, Bio; Yip, Anna; Wang, Bing; Zhu, Jiping

2013-01-01

In vitro dermal absorption experiments were conducted using a roll-on deodorant that contains 1.56% di(2-ethylhexyl) adipate (DEHA), a plasticizer widely used in consumer products. Human skin specimens were fitted in Bronaugh flow-through Teflon diffusion cells. The diffusion cells were maintained at 32 °C to reflect the skin temperature. Two amounts (low dose: 5 mg of the product; high dose: 100 mg) were applied, in triplicate, each on four different human skins. DEHA was determined in the receiver solution at 6-h intervals, using headspace solid-phase microextraction gas chromatography-mass spectrometry (GC-MS). After 24 h, the experiment was terminated and masses of DEHA in the skin depot, skin wash, and upper and lower chambers of the diffusion cell were determined. A significant portion of applied DEHA, 28% in the low amount application and 34% in the high one, was found in the skin depot. In comparison, only 0.04% and 0.002% of applied DEHA were found in the receiver solutions for the low and high doses, respectively. Under our experimental conditions, an apparent steady-state flux of low DEHA mass penetrating from skin into the receiver solution was observed with a penetration rate of 2.2 ng/cm(2)/h for both the low and high doses. The average mass recovery was 81% for the low dose application and 56% for the high dose.

Unexpected Hydrolytic Instability of N-Acylated Amino Acid Amides and Peptides

PubMed Central

2015-01-01

Remote amide bonds in simple N-acyl amino acid amide or peptide derivatives 1 can be surprisingly unstable hydrolytically, affording, in solution, variable amounts of 3 under mild acidic conditions, such as trifluoroacetic acid/water mixtures at room temperature. This observation has important implications for the synthesis of this class of compounds, which includes N-terminal-acylated peptides. We describe the factors contributing to this instability and how to predict and control it. The instability is a function of the remote acyl group, R2CO, four bonds away from the site of hydrolysis. Electron-rich acyl R2 groups accelerate this reaction. In the case of acyl groups derived from substituted aromatic carboxylic acids, the acceleration is predictable from the substituent’s Hammett σ value. N-Acyl dipeptides are also hydrolyzed under typical cleavage conditions. This suggests that unwanted peptide truncation may occur during synthesis or prolonged standing in solution when dipeptides or longer peptides are acylated on the N-terminus with electron-rich aromatic groups. When amide hydrolysis is an undesired secondary reaction, as can be the case in the trifluoroacetic acid-catalyzed cleavage of amino acid amide or peptide derivatives 1 from solid-phase resins, conditions are provided to minimize that hydrolysis. PMID:24617596

Kinetic precipitation of solution-phase polyoxomolybdate followed by transmission electron microscopy: a window to solution-phase nanostructure.

PubMed

Zhu, Yan; Cammers-Goodwin, Arthur; Zhao, Bin; Dozier, Alan; Dickey, Elizabeth C

2004-05-17

This study aimed to elucidate the structural nature of the polydisperse, nanoscopic components in the solution and the solid states of partially reduced polyoxomolybdate derived from the [Mo132] keplerate, [(Mo)Mo5]12-[Mo2 acetate]30. Designer tripodal hexamine-tris-crown ethers and nanoscopic molybdate coprecipitated from aqueous solution. These microcrystalline solids distributed particle radii between 2-30 nm as assayed by transmission electron microscopy (TEM). The solid materials and their particle size distributions were snap shots of the solution phase. The mother liquor of the preparation of the [Mo132] keplerate after three days revealed large species (r=20-30 nm) in the coprecipitate, whereas [Mo132] keplerate redissolved in water revealed small species (3-7 nm) in the coprecipitate. Nanoparticles of coprecipitate were more stable than solids derived solely from partially reduced molybdate. The TEM features of all material analyzed lacked facets on the nanometer length scale; however, the structures diffracted electrons and appeared to be defect-free as evidenced by Moiré patterns in the TEM images. Moiré patterns and size-invariant optical densities of the features in the micrographs suggested that the molybdate nanoparticles were vesicular.

Solute redistribution in dendritic solidification with diffusion in the solid

NASA Technical Reports Server (NTRS)

Ganesan, S.; Poirier, D. R.

1989-01-01

An investigation of solute redistribution during dendritic solidification with diffusion in the solid has been performed using numerical techniques. The extent of diffusion is characterized by the instantaneous and average diffusion parameters. These parameters are functions of the diffusion Fourier number, the partition ratio and the fraction solid. Numerical results are presented as an approximate model, which is used to predict the average diffusion parameter and calculate the composition of the interdendritic liquid during solidification.

Calibration-free quantification of interior properties of porous media with x-ray computed tomography.

PubMed

Hussein, Esam M A; Agbogun, H M D; Al, Tom A

2015-03-01

A method is presented for interpreting the values of x-ray attenuation coefficients reconstructed in computed tomography of porous media, while overcoming the ambiguity caused by the multichromatic nature of x-rays, dilution by void, and material heterogeneity. The method enables determination of porosity without relying on calibration or image segmentation or thresholding to discriminate pores from solid material. It distinguishes between solution-accessible and inaccessible pores, and provides the spatial and frequency distributions of solid-matrix material in a heterogeneous medium. This is accomplished by matching an image of a sample saturated with a contrast solution with that saturated with a transparent solution. Voxels occupied with solid-material and inaccessible pores are identified by the fact that they maintain the same location and image attributes in both images, with voxels containing inaccessible pores appearing empty in both images. Fully porous and accessible voxels exhibit the maximum contrast, while the rest are porous voxels containing mixtures of pore solutions and solid. This matching process is performed with an image registration computer code, and image processing software that requires only simple subtraction and multiplication (scaling) processes. The process is demonstrated in dolomite (non-uniform void distribution, homogeneous solid matrix) and sandstone (nearly uniform void distribution, heterogeneous solid matrix) samples, and its overall performance is shown to compare favorably with a method based on calibration and thresholding. Copyright © 2014 Elsevier Ltd. All rights reserved.

Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

EPA Science Inventory

Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.

1987-01-01

Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

PubMed

Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

2004-07-21

The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

Mechanism of chromium poisoning the conventional cathode material for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Xiaoqiang; Yu, Guangsen; Zeng, Shumao; Parbey, Joseph; Xiao, Shuhao; Li, Baihai; Li, Tingshuai; Andersson, Martin

2018-03-01

Chromium poisoning the La0.875Sr0.125MnO3 (LSM) cathode for solid oxide fuel cells is a critical issue that can strongly affect the stability. In this study, we evaluate the temperature distribution in a SOFC based on a 3D model and then combine conductivity test and material computation to reveal the effects of chromium in SUS430 stainless steels on LSM conductivities. The starch concentration in LSM pellets and the applied pressure on the contact with interconnect materials show close relationships with the chromium poisoning behavior. The density functional theory (DFT) computing results indicate that chromium atoms preferably adsorb on the MnO2-terminated and La (Sr)-O-terminated (001) surfaces. The resulting conclusions are expected to deeply understand mechanism of chromium deactivating conventional cathodes at some typical operational conditions, and offer crucial information to optimize the structure to avoid the poisoning effect.

High-Solids Polyimide Precursor Solutions

NASA Technical Reports Server (NTRS)

Chuang, Chun-Hua (Inventor)

2004-01-01

The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

PROCESS OF MAKING A NEUTRONIC REACTOR FUEL ELEMENT COMPOSITION

DOEpatents

Alter, H.W.; Davidson, J.K.; Miller, R.S.; Mewherter, J.L.

1959-01-13

A process is presented for making a ceramic-like material suitable for use as a nuclear fuel. The material consists of a solid solution of plutonium dioxide in uranium dioxide and is produced from a uranyl nitrate -plutonium nitrate solution containing uraniunm and plutonium in the desired ratio. The uranium and plutonium are first precipitated from the solution by addition of NH/ sub 4/OH and the dried precipitate is then calcined at 600 C in a hydrogen atmosphere to yield the desired solid solution of PuO/sub 2/ in UO/sub 2/.

Smart truck driver assistant : a cost effective solution for real time management of container delivery to trucks.

DOT National Transportation Integrated Search

2015-12-01

The twin ports of Los Angeles and Long Beach are two of the busiest ports in the country. The marine terminals at these ports are under tremendous pressure to enhance their performance levels. One major issue in the terminals' productivity and perfor...

Luminescent substituted fluoranthenes - synthesis, structure, electrochemical and optical properties.

PubMed

Slodek, Aneta; Maroń, Anna; Pająk, Michał; Matussek, Marek; Grudzka-Flak, Iwona; Małecki, Jan Grzegorz; Świtlicka, Anna; Krompiec, Stanisław; Danikiewicz, Witold; Grela, Małgorzata; Gryca, Izabela; Penkala, Mateusz

2018-04-16

Six novel fluoranthene derivatives, three terminally substituted and three bis(fluoranthenes) with fluorene, bithiophene and carbazole spacers were obtained via [2+2+2] cycloaddition and thoroughly characterized. Based on the conducted studies, the obtained derivatives can be classified as D-A (donor-acceptor) and A-D-A (acceptor-donor-acceptor) systems, where fluoranthene unit acts as an electron-withdrawing unit. The optical results revealed that novel fluoranthene derivatives absorb light in the range of 236-417 nm originating from ππ* transition within the conjugated system. The compounds exhibit fluorescence ranging from deep blue to green originating mainly from intramolecular charge transfer (ICT) states. The high Stoke shifts, high quantum yield in solution (φ= 0.22-0.57) and in the solid state (φ= 0.18-0.44) have been observed for fluoranthene derivatives. All derivatives possess multi-step oxidations at low potentials. The electronic structure of presented compounds is additionally supported by TD-DFT computations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic Modeling of the Ge-Nd Binary System

NASA Astrophysics Data System (ADS)

Liu, Miao; Li, Changrong; Du, Zhenmin; Guo, Cuiping; Niu, Chunju

The Ge-Nd has been critically assessed by means of the CALculation of PHAse Diagram (CALPHAD) technique. For the liquid phase, the associate model was used with the constituent species Ge, Nd, Ge3Nd5 and Ge1.6Nd in the Ge-Nd system. The terminal solid solution diamond-(Ge), dhcp-(Nd) and bcc_A2-(Nd) in the Ge-Nd system were described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, α(Ge1.6Nd), β(Ge1.6Nd), (GeNd), (Ge4Nd5) and (Ge3Nd5) were modeled using two sublattices as α(Ge,Nd)1.6Nd, β(Ge,Nd)1.6Nd, (Ge,Nd)Nd, (Ge,Nd)4Nd5 and (Ge,Nd)3Nd5, respectively. A set of self-consistent thermodynamic parameters for each of the Ge-Nd binary systems was obtained. The calculation results agree well with the available experimental data from literatures.

Biological and surface-active properties of double-chain cationic amino acid-based surfactants.

PubMed

Greber, Katarzyna E; Dawgul, Małgorzata; Kamysz, Wojciech; Sawicki, Wiesław; Łukasiak, Jerzy

2014-08-01

Cationic amino acid-based surfactants were synthesized via solid phase peptide synthesis and terminal acylation of their α and ε positions with saturated fatty acids. Five new lipopeptides, N-α-acyl-N-ε-acyl lysine analogues, were obtained. Minimum inhibitory concentration and minimum bactericidal (fungicidal) concentration were determined on reference strains of bacteria and fungi to evaluate the antimicrobial activity of the lipopeptides. Toxicity to eukaryotic cells was examined via determination of the haemolytic activities. The surface-active properties of these compounds were evaluated by measuring the surface tension and formation of micelles as a function of concentration in aqueous solution. The cationic surfactants demonstrated diverse antibacterial activities dependent on the length of the fatty acid chain. Gram-negative bacteria and fungi showed a higher resistance than Gram-positive bacterial strains. It was found that the haemolytic activities were also chain length-dependent values. The surface-active properties showed a linear correlation between the alkyl chain length and the critical micelle concentration.

Emergency deployable core catcher

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

Rosewell, M.P.

An emergency melt down core catcher apparatus for a nuclear reactor having a retrofitable eutectic solute holding vessel connected to a core containment vessel with particle transferring fluid and particles or granules of solid eutectic solute materials contained therein and transferable by automatically operated valve means to transport and position the solid eutectic solute material in a position below the core to catch and react with any partial or complete melt down of the fuel core.

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

Reason, J.

Transmission terminations available today are very reliable, but they need to be. In the field, they are continually exposed to pollution and extremes of ambient temperature. In many cases, they are in the rifle sights of vandals. In contrast, cable joints - often cited as the weakest links from an electrical viewpoint - are generally protected from physical damage underground and many of the short cable systems being installed in the US today can be built without joints. All cable systems need terminations - mostly to air-insulated equipment. At 69 through 138 kV, there is intense competition among manufacturers tomore » supply terminations for solid-dielectric cable that are low in cost, reliable, and require a minimum of skill to install. Some utilities are looking also for terminations that fit a range of cable sizes; terminations that do not contain liquid that can leak out; and terminations that are shatter-proof. All of these improvements are available in the US up to 69 kV. For higher voltages, they are on the horizon, if not already in use, overseas. 16 figs.« less

Effects of drug-carrier interactions on drug dissolution from binary and ternary matrices

NASA Astrophysics Data System (ADS)

Iqbal, Zafar

For nearly five decades, pharmaceutical researchers have studied solid solutions of drugs in polymers as a potential means to enhance the dissolution of drugs with poor aqueous solubility. This has become of greater importance in recent years because most new potential drug compounds (new chemical entities) exhibit poor water solubility and present great challenges to scientists who must design dosage forms from which the drugs are bioavailable. During the formulation of a solid solution, the drug undergoes physical but not chemical alterations that increase its chemical potential in the formulation relative to that of the pure drug in its stable form. This increased chemical potential is responsible for enhanced dissolution as well as physical instabilities, such as amorphous to crystalline conversions and precipitation within the solid state. The chemical potential is derived from the Gibbs free energy, so it is reasonable to explain the behavior of solid solution systems in terms of thermodynamics. Solid solutions and dispersions have been extensively studied by pharmaceutical scientists, both with regard to manufacturing aspects and the proposal of various models in attempts to explain the physical bases for how these systems work. Recently, Dave and Bellantone proposed a model based on the thermodynamic changes resulting from the formulation of binary solid solutions of a drug in the polymer PVP. Their model introduced a modification of the F-H theory, which was used to quantify the drug-polymer interaction energies and calculate the entropy of mixing of the drug and polymer. In this work, the model of Dave and Bellantone was extended to include three-component systems, consisting of one drug mixed in a carrier matrix consisting of mixture of two polymers or a polymer and a surfactant. For this research, solid solutions were formed using various drug weight fractions in the formulations. The study focused on the following points: (1) Prepare solid solution formulations and perform appropriate physical characterizations. (2) Characterize the increase in drug dissolution rates resulting from solid solution formulations. (3) Relate the initial dissolution rates to the drug solubility. (4) Explain the solubility enhancement from solid solution dosage in terms of the drug polymer interactions using the extended thermodynamic model. Two poorly water soluble drugs, levonorgestrel (LEVO) and ethinyl estradiol (EE) were formulated in seven solid solution preparations comprised of four carrier systems. Materials used as carriers included various combinations of the polymers PVP K-30, Copovidone (COP), Poloxamer 182, and the surfactant TweenRTM 20. Additionally, ibuprofen (IBU) was used in three formulations consisting of various combinations of PVP K-30, Copovidone and TweenRTM 20. Formulations with various drug weight fractions (0.5%--30%) were prepared using the solvent evaporation technique. Each formulation was tested for dissolution using intrinsic dissolution apparatus (USP). The solid solutions were compressed into tablets into the sample die that maintained a constant surface area during the dissolution process. DSC, XRD and NIRS scans identified that the crystalline peaks of the drug disappeared with the addition of the polymer for all ratios of EE, indicating the formation of solid solutions (to within the limits of detection of the equipment). This was also observed for the LEVO dispersions up to 10% drug loading. At higher drug loading, solutions were formed but some small degree crystallinity was also present. For each experiment, the initial dissolution rates were obtained from the slope of the mass dissolved vs. time plots taken at early times, and volume normalized initial dissolution rates RV were calculated by dividing the initial dissolution rate by the volume fraction of the drug in the formulation. Comparison of the RV values for the various formulations with a reference RV (typically that of the pure drug or of the formulation with the highest polymer content) allowed calculation of relative volume normalized dissolution rates (RNV). The various RNV were used in the thermodynamic model for data analyses and to determine the interactions between the drug and carrier molecules. It was generally seen that RNV increased with decreased drug fraction, and was adequately modeled by the equations derived from the extended thermodynamic model. It was concluded that the model proposed for the binary and ternary systems successfully represented the mechanism of drug-polymer interaction and the energy changes taken place within the dispersion systems. The dissolution data analysis and subsequent understanding of physical modifications in the dispersion systems characterized by XRD, NIRS and DSC further substantiated the findings. The understanding of the fundamental physical might help scientists to predict the effects of mixing various drugs and polymers, and the effects of varying ratios.

Solution structure of the His12 --> Cys mutant of the N-terminal zinc binding domain of HIV-1 integrase complexed to cadmium.

PubMed Central

Cai, M.; Huang, Y.; Caffrey, M.; Zheng, R.; Craigie, R.; Clore, G. M.; Gronenborn, A. M.

1998-01-01

The solution structure of His12 --> Cys mutant of the N-terminal zinc binding domain (residues 1-55; IN(1-55)) of HIV-1 integrase complexed to cadmium has been solved by multidimensional heteronuclear NMR spectroscopy. The overall structure is very similar to that of the wild-type N-terminal domain complexed to zinc. In contrast to the wild-type domain, however, which exists in two interconverting conformational states arising from different modes of coordination of the two histidine side chains to the metal, the cadmium complex of the His12 --> Cys mutant exists in only a single form at low pH. The conformation of the polypeptide chain encompassing residues 10-18 is intermediate between the two forms of the wild-type complex. PMID:9865962

Closed-form analytical solutions incorporating pumping and tidal effects in various coastal aquifer systems

NASA Astrophysics Data System (ADS)

Wang, Chaoyue; Li, Hailong; Wan, Li; Wang, Xusheng; Jiang, Xiaowei

2014-07-01

Pumping wells are common in coastal aquifers affected by tides. Here we present analytical solutions of groundwater table or head variations during a constant rate pumping from a single, fully-penetrating well in coastal aquifer systems comprising an unconfined aquifer, a confined aquifer and semi-permeable layer between them. The unconfined aquifer terminates at the coastline (or river bank) and the other two layers extend under tidal water (sea or tidal river) for a certain distance L. Analytical solutions are derived for 11 reasonable combinations of different situations of the L-value (zero, finite, and infinite), of the middle layer's permeability (semi-permeable and impermeable), of the boundary condition at the aquifer's submarine terminal (Dirichlet describing direct connection with seawater and no-flow describing the existence of an impermeable capping), and of the tidal water body (sea and tidal river). Solutions are discussed with application examples in fitting field observations and parameter estimations.

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

NASA Astrophysics Data System (ADS)

Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

2016-05-01

A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

Structural Assessment of Solid Propellant Grains (l’Evaluation structurale des blocs de poudre a’ propergol solide)

DTIC Science & Technology

1997-12-01

bonds) This technique is based on the observation of the reflection and attenuation of an ultrasonic wave traversing an object, and is used to check...Nearly all present day composite propellants for tactical rocket motors use hydroxy-terminated polybutadiene ( HTPB ) as a binder as this offers the...polyurethane as a binder. The inferior mechanical properties of these propellants compared to HTPB limited their use. In large space booster and

High temperature resistant cermet and ceramic compositions. [for thermal resistant insulators and refractory coatings

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

High temperature oxidation resistance, high hardness and high abrasion and wear resistance are properties of cermet compositions particularly to provide high temperature resistant refractory coatings on metal substrates, for use as electrical insulation seals for thermionic converters. The compositions comprise a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride are also described.

Influence of Dy in solid solution on the degradation behavior of binary Mg-Dy alloys in cell culture medium.

PubMed

Yang, Lei; Ma, Liangong; Huang, Yuanding; Feyerabend, Frank; Blawert, Carsten; Höche, Daniel; Willumeit-Römer, Regine; Zhang, Erlin; Kainer, Karl Ulrich; Hort, Norbert

2017-06-01

Rare earth element Dy is one of the promising alloying elements for magnesium alloy as biodegradable implants. To understand the effect of Dy in solid solution on the degradation of Mg-Dy alloys in simulated physiological conditions, the present work studied the microstructure and degradation behavior of Mg-Dy alloys in cell culture medium. It is found the corrosion resistance enhances with the increase of Dy content in solid solution in Mg. This can be attributed to the formation of a relatively more corrosion resistant Dy-enriched film which decreases the anodic dissolution of Mg. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of solid solutions of perovskites

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

Dambekalne, M.Y.; Antonova, M.K.; Perro, I.T.

The authors carry out thermographic studies, using a derivatograph, in order to understand the nature of the processes taking place during the synthesis of solid solutions of perovskites. Based on the detailed studies on the phase transformations occurring in the charges of the PSN-PMN solid solutions and on the selection of the optimum conditions for carrying out their synthesis, the authors obtained a powder containing a minimum quantity of the undesirable pyrochlore phase and by sintering it using the hot pressing method, they produced single phase ceramic specimens containing the perovskite phase alone with a density close to the theoreticalmore » value and showing zero apparent porosity and water absorption.« less

Solid-Phase Nucleic Acid Sequence-Based Amplification and Length-Scale Effects during RNA Amplification.

PubMed

Ma, Youlong; Teng, Feiyue; Libera, Matthew

2018-06-05

Solid-phase oligonucleotide amplification is of interest because of possible applications to next-generation sequencing, multiplexed microarray-based detection, and cell-free synthetic biology. Its efficiency is, however, less than that of traditional liquid-phase amplification involving unconstrained primers and enzymes, and understanding how to optimize the solid-phase amplification process remains challenging. Here, we demonstrate the concept of solid-phase nucleic acid sequence-based amplification (SP-NASBA) and use it to study the effect of tethering density on amplification efficiency. SP-NASBA involves two enzymes, avian myeloblastosis virus reverse transcriptase (AMV-RT) and RNase H, to convert tethered forward and reverse primers into tethered double-stranded DNA (ds-DNA) bridges from which RNA - amplicons can be generated by a third enzyme, T7 RNA polymerase. We create microgels on silicon surfaces using electron-beam patterning of thin-film blends of hydroxyl-terminated and biotin-terminated poly(ethylene glycol) (PEG-OH, PEG-B). The tethering density is linearly related to the PEG-B concentration, and biotinylated primers and molecular beacon detection probes are tethered to streptavidin-activated microgels. While SP-NASBA is very efficient at low tethering densities, the efficiency decreases dramatically with increasing tethering density due to three effects: (a) a reduced hybridization efficiency of tethered molecular beacon detection probes; (b) a decrease in T7 RNA polymerase efficiency; (c) inhibition of T7 RNA polymerase activity by AMV-RT.

Mechanism of drug release from polymethacrylate-based extrudates and milled strands prepared by hot-melt extrusion.

PubMed

Albers, Jessica; Alles, Rainer; Matthée, Karin; Knop, Klaus; Nahrup, Julia Schulze; Kleinebudde, Peter

2009-02-01

The aim of the study was the formulation of solid dispersions of the poorly water-soluble drug celecoxib and a polymethacrylate carrier by hot-melt extrusion. The objectives were to elucidate the mechanism of drug release from obtained extrudates and milled strands addicted to the solid-state properties of the solid dispersions and to examine and eliminate stability problems occurring under storage, exposure of mechanical stress, and in vitro dissolution. Transparent extrudates containing up to 60% drug could be prepared with a temperature setting below the melting point of celecoxib. XRPD and DSC measurements indicated the formation of a glassy solid solution, where the drug is molecularly dispersed in the carrier. The amorphous state of the glassy solid solution could be maintained during the exposure of mechanical stress in a milling process, and was stable under storage for at least 6 months. Solid-state properties and SEM images of extrudates after dissolution indicated a carrier-controlled dissolution, whereby the drug is molecularly dispersed within the concentrated carrier layer. The glassy solid solution showed a 58-fold supersaturation in 0.1 N HCl within the first 10 min, which was followed by a recrystallization process. Recrystallization could be inhibited by an external addition of HPMC.

Line-driven winds revisited in the context of Be stars: Ω-slow solutions with high k values

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

Silaj, J.; Jones, C. E.; Curé, M.

2014-11-01

The standard, or fast, solutions of m-CAK line-driven wind theory cannot account for slowly outflowing disks like the ones that surround Be stars. It has been previously shown that there exists another family of solutions—the Ω-slow solutions—that is characterized by much slower terminal velocities and higher mass-loss rates. We have solved the one-dimensional m-CAK hydrodynamical equation of rotating radiation-driven winds for this latter solution, starting from standard values of the line force parameters (α, k, and δ), and then systematically varying the values of α and k. Terminal velocities and mass-loss rates that are in good agreement with those foundmore » in Be stars are obtained from the solutions with lower α and higher k values. Furthermore, the equatorial densities of such solutions are comparable to those that are typically assumed in ad hoc models. For very high values of k, we find that the wind solutions exhibit a new kind of behavior.« less

A multi-scale Lattice Boltzmann model for simulating solute transport in 3D X-ray micro-tomography images of aggregated porous materials

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxian; Crawford, John W.; Flavel, Richard J.; Young, Iain M.

2016-10-01

The Lattice Boltzmann (LB) model and X-ray computed tomography (CT) have been increasingly used in combination over the past decade to simulate water flow and chemical transport at pore scale in porous materials. Because of its limitation in resolution and the hierarchical structure of most natural soils, the X-ray CT tomography can only identify pores that are greater than its resolution and treats other pores as solid. As a result, the so-called solid phase in X-ray images may in reality be a grey phase, containing substantial connected pores capable of conducing fluids and solute. Although modified LB models have been developed to simulate fluid flow in such media, models for solute transport are relatively limited. In this paper, we propose a LB model for simulating solute transport in binary soil images containing permeable solid phase. The model is based on the single-relaxation time approach and uses a modified partial bounce-back method to describe the resistance caused by the permeable solid phase to chemical transport. We derive the relationship between the diffusion coefficient and the parameter introduced in the partial bounce-back method, and test the model against analytical solution for movement of a pulse of tracer. We also validate it against classical finite volume method for solute diffusion in a simple 2D image, and then apply the model to a soil image acquired using X-ray tomography at resolution of 30 μm in attempts to analyse how the ability of the solid phase to diffuse solute at micron-scale affects the behaviour of the solute at macro-scale after a volumetric average. Based on the simulated results, we discuss briefly the danger in interpreting experimental results using the continuum model without fully understanding the pore-scale processes, as well as the potential of using pore-scale modelling and tomography to help improve the continuum models.

Dynamic nuclear polarization methods in solids and solutions to explore membrane proteins and membrane systems.

PubMed

Cheng, Chi-Yuan; Han, Songi

2013-01-01

Membrane proteins regulate vital cellular processes, including signaling, ion transport, and vesicular trafficking. Obtaining experimental access to their structures, conformational fluctuations, orientations, locations, and hydration in membrane environments, as well as the lipid membrane properties, is critical to understanding their functions. Dynamic nuclear polarization (DNP) of frozen solids can dramatically boost the sensitivity of current solid-state nuclear magnetic resonance tools to enhance access to membrane protein structures in native membrane environments. Overhauser DNP in the solution state can map out the local and site-specific hydration dynamics landscape of membrane proteins and lipid membranes, critically complementing the structural and dynamics information obtained by electron paramagnetic resonance spectroscopy. Here, we provide an overview of how DNP methods in solids and solutions can significantly increase our understanding of membrane protein structures, dynamics, functions, and hydration in complex biological membrane environments.

Effect of Process Parameter on Barium Titanate Stannate (BTS) Materials Sintered at Low Sintering

NASA Astrophysics Data System (ADS)

Shukla, Alok; Bajpai, P. K.

2011-11-01

Ba(Ti1-xSnx)O3 solid solutions with (x = 0.15, 0.20, 0.30 and 0.40) are synthesized using conventional solid state reaction method. Formation of solid solutions in the range 0 ≤ x ≤0.40 is confirmed using X-ray diffraction technique. Single phase solid solutions with homogeneous grain distribution are observed at relatively low sintering by controlling process parameters viz. sintering time. Composition at optimized temperature (1150 °C) sintered by varying the sintering time, stabilize in cubic perovskite phase. The % experimental density increase with increasing the time of sintering instead of increasing sintering temperature. The lattice parameter increases by increasing the tin composition in the material. This demonstrates that process parameter optimization can lead to single phase at relatively lower sintering-a major advantage for the materials used as capacitor element in MLCC.

Cooking with Fire: The Mutagenicity- and PAH-Emission Factors of Solid-Fuel Cookstoves

EPA Science Inventory

Emissions from solid fuels used for cooking cause ~4 million premature deaths per year. Advanced solid-fuel cookstoves are a potential solution, but they should be assessed by appropriate performance indicators, including biological effects. We evaluated two categories of solid...

Nickel Nanocatalyst Ex-Solution from Ceria-Nickel Oxide Solid Solution for Low Temperature CO Oxidation.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2018-07-01

In this work, in situ growth of Ni nanocatalysts to attach onto the ceria (CeO2) surface through direct Ni ex-solution from the NiO-CeO2 solid solution in a reducing atmosphere at high temperatures with an aim to improve the catalytic activity, and stability for low temperature carbon monoxide (CO) oxidation reaction have been reported. The NiO-CeO2 solid solutions were prepared by solution combustion method, and the results of XRD and RAMAN showed that doping of Ni increases the oxygen vacancies due to charge compensation. Ni is clearly visible in XRD and TEM of Ni ex-solved sample (R-UCe5Ni10) after reduction of NiO-CeO2 (UCe5Ni10) sample by 5% H2/Ar reduction at 1000 °C. TEM analysis revealed a size of 9.2 nm of Ni nanoparticle that is ex-solved on the surface CeO2. This ex-solved sample showed very high catalytic activity (T50 ~ 110 °C), and stability (100 h) for CO oxidation reaction as compared to prepared solid solution samples. This is due to the highly active metallic nano-phase which is ex-solved on the surface of CeO2 and strongly adherent to the support. The apparent activation energy Ni ex-solved sample is found out to be 48.4 kJ mol-1. Thus, the above Ni ex-solved sample shows a practical applicability for the CO reaction.

On the problem of resonance assignments in solid state NMR of uniformly 15N, 13C-labeled proteins

NASA Astrophysics Data System (ADS)

Tycko, Robert

2015-04-01

Determination of accurate resonance assignments from multidimensional chemical shift correlation spectra is one of the major problems in biomolecular solid state NMR, particularly for relative large proteins with less-than-ideal NMR linewidths. This article investigates the difficulty of resonance assignment, using a computational Monte Carlo/simulated annealing (MCSA) algorithm to search for assignments from artificial three-dimensional spectra that are constructed from the reported isotropic 15N and 13C chemical shifts of two proteins whose structures have been determined by solution NMR methods. The results demonstrate how assignment simulations can provide new insights into factors that affect the assignment process, which can then help guide the design of experimental strategies. Specifically, simulations are performed for the catalytic domain of SrtC (147 residues, primarily β-sheet secondary structure) and the N-terminal domain of MLKL (166 residues, primarily α-helical secondary structure). Assuming unambiguous residue-type assignments and four ideal three-dimensional data sets (NCACX, NCOCX, CONCA, and CANCA), uncertainties in chemical shifts must be less than 0.4 ppm for assignments for SrtC to be unique, and less than 0.2 ppm for MLKL. Eliminating CANCA data has no significant effect, but additionally eliminating CONCA data leads to more stringent requirements for chemical shift precision. Introducing moderate ambiguities in residue-type assignments does not have a significant effect.

75 FR 43204 - Notice of Realty Action: Recreation and Public Purposes Act Classification for Conveyance of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-23

... any circumstances if such portion has been used for solid waste disposal or for any other purpose that... termination of the segregation. Detailed information concerning the proposed conveyance, including the...

NMR solution structure of the mitochondrial F1beta presequence from Nicotiana plumbaginifolia.

PubMed

Moberg, Per; Nilsson, Stefan; Ståhl, Annelie; Eriksson, Anna-Carin; Glaser, Elzbieta; Mäler, Lena

2004-03-05

We have isolated, characterized and determined the three-dimensional NMR solution structure of the presequence of ATPsynthase F1beta subunit from Nicotiana plumbaginifolia. A general method for purification of presequences is presented. The method is based on overexpression of a mutant precursor containing a methionine residue introduced at the processing site, followed by CNBr-cleavage and purification of the presequence on a cation-exchange column. The F1beta presequence, 53 amino acid residues long, retained its native properties as evidenced by inhibition of in vitro mitochondrial import and processing at micromolar concentrations. CD spectroscopy revealed that the F1beta presequence formed an alpha-helical structure in membrane mimetic environments such as SDS and DPC micelles (approximately 50% alpha-helix), and in acidic phospholipid bicelles (approximately 60% alpha-helix). The NMR solution structure of the F1beta presequence in SDS micelles was determined on the basis of 518 distance and 21 torsion angle constraints. The structure was found to contain two helices, an N-terminal amphipathic alpha-helix (residues 4-15) and a C-terminal alpha-helix (residues 43-53), separated by a largely unstructured 27 residue long internal domain. The N-terminal amphipathic alpha-helix forms the putative Tom20 receptor binding site, whereas the C-terminal alpha-helix is located upstream of the mitochondrial processing peptidase cleavage site.

Damage accumulation in ion-irradiated Ni-based concentrated solid-solution alloys

DOE PAGES

Ullah, Mohammad W.; Aidhy, Dilpuneet S.; Zhang, Yanwen; ...

2016-03-05

We investigate Irradiation-induced damage accumulation in Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2 alloys by using molecular dynamics simulations to assess possible enhanced radiation-resistance in these face-centered cubic (fcc), single-phase, concentrated solid-solution alloys, as compared with pure fcc Ni.

Preparation and Analysis of Solid Solutions in the Potassium Perchlorate-Permanganate System.

ERIC Educational Resources Information Center

Johnson, Garrett K.

1979-01-01

Describes an experiment, designed for and tested in an advanced inorganic laboratory methods course for college seniors and graduate students, that prepares and analyzes several samples in the nearly ideal potassium perchlorate-permanganate solid solution series. The results are accounted for by a theoretical treatment based upon aqueous…

Hydration mechanisms of two polymorphs of synthetic ye'elimite

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

Cuesta, A.; Álvarez-Pinazo, G.; Sanfélix, S.G.

2014-09-15

Ye'elimite is the main phase in calcium sulfoaluminate cements and also a key phase in sulfobelite cements. However, its hydration mechanism is not well understood. Here we reported new data on the hydration behavior of ye'elimite using synchrotron and laboratory powder diffraction coupled to the Rietveld methodology. Both internal and external standard methodologies have been used to determine the overall amorphous contents. We have addressed the standard variables: water-to-ye'elimite ratio and additional sulfate sources of different solubilities. Moreover, we report a deep study of the role of the polymorphism of pure ye'elimites. The hydration behavior of orthorhombic stoichiometric and pseudo-cubicmore » solid-solution ye'elimites is discussed. In the absence of additional sulfate sources, stoichiometric-ye'elimite reacts slower than solid-solution-ye'elimite, and AFm-type phases are the main hydrated crystalline phases, as expected. Moreover, solid-solution-ye'elimite produces higher amounts of ettringite than stoichiometric-ye'elimite. However, in the presence of additional sulfates, stoichiometric-ye'elimite reacts faster than solid-solution-ye'elimite.« less

Solid Solution Photocatalyst with Spontaneous Polarization Exhibiting Low Recombination Toward Efficient CO2 Photoreduction.

PubMed

Zhou, Peng; Wang, Xin; Yan, Shicheng; Zou, Zhigang

2016-08-23

Decreasing the recombination of photogenerated carriers is a major challenge for efficiently converting solar energy into chemical energy by photocatalysis. Here, we have demonstrated that growth of a polar GaN:ZnO solid solution single crystal along its polarization axis is beneficial to efficient separation of photogenerated carriers, owing to the periodic potential barriers and wells generated from the periodically positive and negative atom arrangements in crystal structure. Local charge imbalance caused by replacing Ga(3+) with Zn(2+) leads to a polarization vector in the {0 0 0 1} planes of GaN:ZnO solid solution, thus forming a 1 D electron transport path along [2 1‾  1‾  0] in the {0 0 0 1} planes of GaN:ZnO solid solution to decrease recombination. Shorting the hole-transport distance by synthesizing porous nanoplates can further decrease recombination under the polarization field and improve the performance of polar photocatalyst in photoreduction of CO2 into CH4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1- x nanoplate solid solutions

NASA Astrophysics Data System (ADS)

Xu, Huan-Yan; Han, Xu; Tan, Qu; Wu, Ke-Jia; Qi, Shu-Yan

2017-06-01

In this study, a facile alcoholysis method was developed to synthesize BiOCl x Br1- x nanoplates at room temperature and atmospheric pressure. In this route, strong acid or alkaline environment was absolutely avoided to realize the high exposure of {001} crystal facets. The regular changes in XRD peaks and cell parameters as a function of the Br content strongly declared that the obtained BiOCl x Br1- x products belonged to a group of solid solutions. The 2D nanosheets with in-plane wrinkles were clearly observed in TEM images. Interestingly, as the Br content increased, band gaps of BiOCl x Br1- x solid solutions gradually decreased. The photocatalytic degradation of RhB under simulated sunlight irradiation indicated that BiOCl0.5Br0.5 had the best photocatalytic activity. From the viewpoint of crystal chemistry, the photocatalytic activity of BiOCl x Br1- x solid solutions was closely related with the exposure amount of {001} facets, interlayer spacing of (001) plane and energy-level position of valence band.

Mechanochemical synthesis and physico-chemical investigations of new materials for gas sensors

NASA Astrophysics Data System (ADS)

Shubenkova, E. G.

2018-01-01

Solid solutions of the InSb-ZnTe semiconductor system containing up to 20 mol.% of ZnTe were synthesized for the first time. The role of mechanochemical treatment in the process of obtaining solid solutions of this system is shown. Solid solutions in the InSb-ZnTe system have been identified by Raman spectroscopy, and the optical properties of its components have been studied. On the basis of an analysis of the anti-stokes spectral radiation distribution the solid solutions formation was identified both on the dependence of the spectral distribution maximum’s shift on the composition of the InSb1-x-ZnTex system, and by estimating the radiation intensity of the initial binary semiconductors at frequencies corresponding to the LO- and TO- vibrations of the binary compounds crystal lattice. The values of the band gap for InSb, (InSb)0.95(ZnTe)0.05 and (InSb)0.9(ZnTe)0.1 were calculated, their values were 0.22 eV, 0.30 eV and 0.38 eV, respectively.

Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

PubMed

Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

2013-11-01

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of anionic substitution on the electrolyte electroreflectance study of band edge transitions in single crystal Cu2ZnSn(SxSe1-x)4 solid solutions

NASA Astrophysics Data System (ADS)

Levcenco, S.; Dumcenco, D.; Wang, Y. P.; Huang, Y. S.; Ho, C. H.; Arushanov, E.; Tezlevan, V.; Tiong, K. K.

2012-06-01

Single crystals of Cu2ZnSn(SxSe1-x)4 (CZTSSe) solid solutions were grown by chemical vapor transport technique using iodine trichloride as a transport agent. As confirmed by X-ray investigations, the as-grown CZTSSe solid solutions are single phase and crystallized in kesterite structure. The lattice parameters of CZTSSe were determined and the S contents of the obtained crystals were estimated by Vegard's law. The composition dependent band gaps of CZTSSe solid solutions were studied by electrolyte electroreflectance (EER) measurements at room temperature. From a detailed lineshape fit of the EER spectra, the band gaps of CZTSSe were determined accurately and were found to decrease almost linearly with the increase of Se content, which agreed well with the recent theoretical first-principle calculations by S. Chen, A. Walsh, J.H. Yang, X.G. Gong, L. Sun, P. X. Yang, J.H. Chu, S.H. Wei, Phys. Rev. B 83 (2011) 125201 (5pp).

The terminal area automated path generation problem

NASA Technical Reports Server (NTRS)

Hsin, C.-C.

1977-01-01

The automated terminal area path generation problem in the advanced Air Traffic Control System (ATC), has been studied. Definitions, input, output and the interrelationships with other ATC functions have been discussed. Alternatives in modeling the problem have been identified. Problem formulations and solution techniques are presented. In particular, the solution of a minimum effort path stretching problem (path generation on a given schedule) has been carried out using the Newton-Raphson trajectory optimization method. Discussions are presented on the effect of different delivery time, aircraft entry position, initial guess on the boundary conditions, etc. Recommendations are made on real-world implementations.

[Formulation and special investigations of innovative intraoral solid dosage forms.

PubMed

Kristo, K; kATONA, B; Piukovics, P; Olah, I; Sipos, B; Sipos, S E; Sovany, T; Hodi, K; Ifi Regdon, G

During our work, we summarized the types of solid dosage forms which were in the focus of attention in the last years because of their innovative pharmaceutical technology solution and simple use. The biopharmaceutics of solid dosage forms for intraoral use and the advantages of the use of these dosages forms were presented in general. However, these dosage forms cannot always be prepared with conventional pharmaceutical processes, therefore the special pharmaceutical solutions which can be applied for their preparation were presented. In addition to testing the European Pharmacopoeia dosage forms, the special tests which can be applied for the characterization of innovative solid dosage forms were highlighted.

Process for desulfurizing petroleum feedstocks

DOEpatents

Gordon, John Howard; Alvare, Javier

2014-06-10

A process for upgrading an oil feedstock includes reacting the oil feedstock with a quantity of an alkali metal, wherein the reaction produces solid materials and liquid materials. The solid materials are separated from the liquid materials. The solid materials may be washed and heat treated by heating the materials to a temperature above 400.degree. C. The heat treating occurs in an atmosphere that has low oxygen and water content. Once heat treated, the solid materials are added to a solution comprising a polar solvent, where sulfide, hydrogen sulfide or polysulfide anions dissolve. The solution comprising polar solvent is then added to an electrolytic cell, which during operation, produces alkali metal and sulfur.

Formation of III–V ternary solid solutions on GaAs and GaSb plates via solid-phase substitution reactions

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

Vasil’ev, V. I.; Gagis, G. S., E-mail: galina.gagis@gmail.com; Kuchinskii, V. I.

2015-07-15

Processes are considered in which ultrathin layers of III–V ternary solid solutions are formed via the delivery of Group-V element vapors to GaAs and GaSb semiconductor plates, with solid-phase substitution reactions occurring in the surface layers of these plates. This method can form defect-free GaAs{sup 1–x}P{sup x}, GaAs{sup x}Sb{sup 1–x}, and GaP{sup x}Sb{sup 1–x} layers with thicknesses of 10–20 nm and a content x of the embedded components of up to 0.04.

Possibility of adjusting the photoluminescence spectrum of Ca scheelites to the emission spectrum of incandescent lamps: [ nCaWO4-(1- n)CaMoO4]: Eu3+ solid solutions

NASA Astrophysics Data System (ADS)

Bakovets, V. V.; Zolotova, E. S.; Antonova, O. V.; Korol'kov, I. V.; Yushina, I. V.

2016-12-01

The specific features of the photoluminescence of [ nCaWO4-(1- n)CaMoO4]:Eu3+ solid solutions with the scheelite structure are examined using X-ray phase analysis and photoluminescence, Raman scattering, and diffuse reflectance spectroscopy. The studied features are associated with a change in the long- and short-range orders of the crystal lattice upon variations in the composition of solutions in the range n = 0-1.0 (with a pitch of 0.2) at a concentration of red photoluminescence activator Eu3+ of 2 mol %. The mechanism of the modification of photoluminescence of solid solutions upon variations in their composition has been discussed. Anomalies in the variations in parameters of the crystal lattice, its short-range order, and luminescence spectra have been observed in the transition from pure compounds CaMoO4:Eu3+ and CaWO4:Eu3+ to solutions; the concentration of Eu3+ ions in the centrosymmetric localization increases (decreases) in the transition from the molybdate (tungstate). It has been demonstrated that the spectral radiant emittance of solid solution [0.4CaWO4-0.6CaMoO4]:Eu3+ (2 mol %) is the closest to that of an incandescent lamp.

Synthesis and photocatalytic degradation study of methylene blue dye under visible light irradiation by Fe1-xBixVO4 solid solutions (0 ≤ x ≤ 1.0)

NASA Astrophysics Data System (ADS)

Bera, Ganesh; Reddy, V. R.; Mal, Priyanath; Das, Pradip; Turpu, G. R.

2018-05-01

The novel hetero-structures Fe1-xBixVO4 solid solutions (0 ≤ x ≤ 1.0) with the two dissimilar end member of FeVO4 - BiVO4, were successfully synthesized by the standard solid state reaction method. The structural and chemical properties of as prepared photo-catalyst samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and UV-visible absorption spectroscopy techniques. It is confirmed from the results of XRD, Raman and FT-IR that FeVO4 and BiVO4 are in triclinic (space group P-1 (2)) and monoclinic (space group I2/b (15)) phases respectively. The Bi incorporation into Fe site of FeVO4 emerges as hetero-structures of both the end members of the solid solutions. In addition, the photocatalytic activity in the degradation of methylene blue (MB) dye under visible light irradiation was carried out through UV-visible spectroscopy measurement of photo-catalysts FeVO4, BiVO4 and mixed phases of both photo-catalyst. The results indicate that under visible light irradiation the photocatalytic activity of mixed phases were very effective and higher than the both single phases of the solid solutions. The composition x= 0.25 exhibits an excellent photocatalytic property for the degradation of MB solution under visible light irradiation rather than other.

Enhancement of dissolution rate through eutectic mixture and solid solution of posaconazole and benznidazole.

PubMed

Figueirêdo, Camila Bezerra Melo; Nadvorny, Daniela; de Medeiros Vieira, Amanda Carla Quintas; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José; Lee, Ping I; de La Roca Soares, Monica Felts

2017-06-15

Benznidazole (BNZ), the only commercialized antichagasic drug, and the antifungal compound posaconazole (PCZ) have shown synergistic action in the therapy of Chagas disease, however both active pharmaceutical ingredients (APIs) exhibit low aqueous solubility potentially limiting their bioavailability and therapeutic efficacy. In this paper, we report for the first time the formation of a eutectic mixture as well as an amorphous solid solution of PCZ and BNZ (at the same characteristic ratio of 80:20wt%), which provided enhanced solubility and dissolution rate for both APIs. This eutectic system was characterized by DSC and the melting points obtained were used for the construction of a phase diagram. The preservation of the characteristic PXRD patterns and the IR spectra of the parent APIs, and the visualization of a characteristic eutectic lamellar crystalline microstructure using Confocal Raman Microscopy confirm this system as a true eutectic mixture. The PXRD result also confirms the amorphous nature of the prepared solid solution. Theoretical chemical analyses indicate the predominance of π-stacking interactions in the amorphous solid solution, whereas an electrostatic interaction between the APIs is responsible for maintaining the alternating lamellar crystalline microstructure in the eutectic mixture. Both the eutectic mixture and the amorphous solid solution happen to have a characteristic PCZ to BNZ ratio similar to that of their pharmacological doses for treating Chagas disease, thus providing a unique therapeutic combination dose with enhanced apparent solubility and dissolution rate. Copyright © 2017 Elsevier B.V. All rights reserved.

Properties of solid solutions, doped film, and nanocomposite structures based on zinc oxide

NASA Astrophysics Data System (ADS)

Lashkarev, G. V.; Shtepliuk, I. I.; Ievtushenko, A. I.; Khyzhun, O. Y.; Kartuzov, V. V.; Ovsiannikova, L. I.; Karpyna, V. A.; Myroniuk, D. V.; Khomyak, V. V.; Tkach, V. N.; Timofeeva, I. I.; Popovich, V. I.; Dranchuk, N. V.; Khranovskyy, V. D.; Demydiuk, P. V.

2015-02-01

A study of the properties of materials based on the wide bandgap zinc oxide semiconductor, which are promising for application in optoelectronics, photovoltaics and nanoplasmonics. The structural and optical properties of solid solution Zn1-xCdxO films with different cadmium content, are studied. The samples are grown using magnetron sputtering on sapphire backing. Low-temperature photoluminescence spectra revealed emission peaks associated with radiative recombination processes in those areas of the film that have varying amounts of cadmium. X-ray phase analysis showed the presence of a cadmium oxide cubic phase in these films. Theoretical studies of the solid solution thermodynamic properties allowed for a qualitative interpretation of the observed experimental phenomena. It is established that the growth of the homogeneous solid solution film is possible only at high temperatures, whereas regions of inhomogeneous composition can be narrowed through elastic deformation, caused by the mismatch of the film-backing lattice constants. The driving forces of the spinodal decomposition of the Zn1-xCdxO system are identified. Fullerene-like clusters of Znn-xCdxOn are used to calculate the bandgap and the cohesive energy of ZnCdO solid solutions. The properties of transparent conductive ZnO films, doped with Group III donor impurities (Al, Ga, In), are examined. It is shown that oxygen vacancies are responsible for the hole trap centers in the zinc oxide photoconductivity process. We also examine the photoluminescence properties of metal-ZnO nanocomposite structures, caused by surface plasmons.

(Nbx, Zr1-x)4AlC3 MAX Phase Solid Solutions: Processing, Mechanical Properties, and Density Functional Theory Calculations.

PubMed

Lapauw, Thomas; Tytko, Darius; Vanmeensel, Kim; Huang, Shuigen; Choi, Pyuck-Pa; Raabe, Dierk; Caspi, El'ad N; Ozeri, Offir; To Baben, Moritz; Schneider, Jochen M; Lambrinou, Konstantina; Vleugels, Jozef

2016-06-06

The solubility of zirconium (Zr) in the Nb4AlC3 host lattice was investigated by combining the experimental synthesis of (Nbx, Zr1-x)4AlC3 solid solutions with density functional theory calculations. High-purity solid solutions were prepared by reactive hot pressing of NbH0.89, ZrH2, Al, and C starting powder mixtures. The crystal structure of the produced solid solutions was determined using X-ray and neutron diffraction. The limited Zr solubility (maximum of 18.5% of the Nb content in the host lattice) in Nb4AlC3 observed experimentally is consistent with the calculated minimum in the energy of mixing. The lattice parameters and microstructure were evaluated over the entire solubility range, while the chemical composition of (Nb0.85, Zr0.15)4AlC3 was mapped using atom probe tomography. The hardness, Young's modulus, and fracture toughness at room temperature as well as the high-temperature flexural strength and E-modulus of (Nb0.85, Zr0.15)4AlC3 were investigated and compared to those of pure Nb4AlC3. Quite remarkably, an appreciable increase in fracture toughness was observed from 6.6 ± 0.1 MPa/m(1/2) for pure Nb4AlC3 to 10.1 ± 0.3 MPa/m(1/2) for the (Nb0.85, Zr0.15)4AlC3 solid solution.

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

PubMed

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Nastar, Maylise

2016-06-01

We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

Analytical close-form solutions to the elastic fields of solids with dislocations and surface stress

NASA Astrophysics Data System (ADS)

Ye, Wei; Paliwal, Bhasker; Ougazzaden, Abdallah; Cherkaoui, Mohammed

2013-07-01

The concept of eigenstrain is adopted to derive a general analytical framework to solve the elastic field for 3D anisotropic solids with general defects by considering the surface stress. The formulation shows the elastic constants and geometrical features of the surface play an important role in determining the elastic fields of the solid. As an application, the analytical close-form solutions to the stress fields of an infinite isotropic circular nanowire are obtained. The stress fields are compared with the classical solutions and those of complex variable method. The stress fields from this work demonstrate the impact from the surface stress when the size of the nanowire shrinks but becomes negligible in macroscopic scale. Compared with the power series solutions of complex variable method, the analytical solutions in this work provide a better platform and they are more flexible in various applications. More importantly, the proposed analytical framework profoundly improves the studies of general 3D anisotropic materials with surface effects.

Reactive solute transport in streams: 1. Development of an equilibrium- based model

USGS Publications Warehouse

Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

1996-01-01

An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4}: Novel keesterite type solid solutions

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

Lopez-Vergara, F., E-mail: fer_martina@u.uchile.cl; Galdamez, A., E-mail: agaldamez@uchile.cl; Manriquez, V.

2013-02-15

A new family of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} chalcogenides has been synthesized by conventional solid-state reactions at 850 Degree-Sign C. The reactions products were characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray analysis (SEM-EDS), Raman spectroscopy and magnetic susceptibility. The crystal structures of two members of the solid solution series Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4} have been determined by single-crystal X-ray diffraction. Both phases crystallize in the tetragonal keesterite-type structure (space group I4{sup Macron }). The distortions of the tetrahedral volume of Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4}more » were calculated and compared with the corresponding differences in the Cu{sub 2}MnSnS{sub 4} (stannite-type) end-member. The compounds show nearly the same Raman spectral features. Temperature-dependent magnetization measurements (ZFC/FC) and high-temperature susceptibility indicate that these solid solutions are antiferromagnetic. - Graphical abstract: View along [100] of the Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} structure showing tetrahedral units and magnetic measurement ZFC-FC at 500 Oe. The insert shows the 1/{chi}-versus-temperature plot fitted by a Curie-Weiss law. Highlights: Black-Right-Pointing-Pointer Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} solid solutions belong to the family of compounds adamantine. Black-Right-Pointing-Pointer Resolved single crystals of the solid solutions have space group I4{sup Macron }. Black-Right-Pointing-Pointer The distortion of the tetrahedral volume of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} were calculated. Black-Right-Pointing-Pointer These solid solutions are antiferromagnetic.« less

The nature of catalyst particles and growth mechanisms of GaN nanowires grown by Ni-assisted metal-organic chemical vapor deposition.

PubMed

Weng, Xiaojun; Burke, Robert A; Redwing, Joan M

2009-02-25

The structure and chemistry of the catalyst particles that terminate GaN nanowires grown by Ni-assisted metal-organic chemical vapor deposition were investigated using a combination of electron diffraction, high-resolution transmission electron microscopy, and x-ray energy dispersive spectrometry. The crystal symmetry, lattice parameter, and chemical composition obtained reveal that the catalyst particles are Ni(3)Ga with an ordered L 1(2) structure. The results suggest that the catalyst is a solid particle during growth and therefore favor a vapor-solid-solid mechanism for the growth of GaN nanowires under these conditions.

Structural studies of TiC{sub 1−x}O{sub x} solid solution by Rietveld refinement and first-principles calculations

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

Jiang, Bo, E-mail: youqin5912@yahoo.com.cn; Hou, Na; Huang, Shanyan

2013-08-15

The lattice parameters, structural stability and electronic structure of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution were investigated by Rietveld refinement and first-principles calculations. Series of TiC{sub 1−x}O{sub x} were precisely synthesized by sintering process under the vacuum. Rietveld refinement results of XRD patterns show the properties of continuous solid solution in TiC{sub 1−x}O{sub x} over the whole composition range. The lattice parameters vary from 0.4324 nm to 0.4194 nm decreasing with increasing oxygen concentration. Results of first-principles calculations reveal that the disorder C/O structure is stable than the order C/O structure. Further investigations of the vacancy in Ti{submore » 1−Va}(C{sub 1−x}O{sub x}){sub 1−Va} solid solution present that the structure of vacancy segregated in TiO-part is more stable than the disorder C/O structure, which can be ascribed to the Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy via the analysis of the electron density difference plots and PDOS. - Graphical abstract: XRD of series of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution prepared by adjusting the proportion of TiO in the starting material. Highlights: • Titanium oxycarbides were obtained by sintering TiO and TiC under carefully controlled conditions. • Rietveld refinement results show continuous solid solution with FCC structure in TiC{sub 1−x}O{sub x}. • The disorder C/O structure is stable than the order C/O structure. • Introduction of vacancy segregated in TiO-part is more stable than disorder C/O structure. • Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy enhance structural stability.« less

Roles of Bi, M and VO{sub 4} tetrahedron in photocatalytic properties of novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions for overall water splitting

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

Liu Hui; Research Center for Combustion and Environment Technology, Shanghai Jiao Tong University, shanghai 200240; Faculty of Engineering Sciences, Kyushu University, Fukuoka 816-8580

2012-02-15

Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (BMV; M=La, Eu, Sm and Y) solid solutions were prepared and studied in this paper. All the samples were proved to produce H{sub 2} and O{sub 2} simultaneously from pure water under the irradiation of UV light. M-O bond lengths were proved to increase with M cations by refining cell parameters and atomic positions. Besides, band gaps, energy gaps and photocatalytic activities of BMV also changed with M cations. Both of M-O and V-O bond lengths were suggested to account for this phenomenon. Inactive A{sub 0.5}Y{sub 0.5}VO{sub 4} (A=La, Ce) for water splitting proved incorporationmore » of Bi rather than distortion of VO{sub 4} tetrahedron was a critical factor for improving efficiency of overall water splitting by facilitating the generation of electron and hole with lighter effective masses. Replacement of Bi by M cations not only gave indirect effect on band structure but also raised position of conduction band minimum to meet requirement of H{sub 2} production. - Graphical abstract: Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions showed the high and stable photocatalytic activities for overall water splitting with their crystal radii of M elements. Highlights: Black-Right-Pointing-Pointer BMV solid solutions were novel highly efficient V-based photocatalysts for overall water splitting. Black-Right-Pointing-Pointer Photocatalytic activity of BMV solid solution related to the effective ionic radii of M cations. Black-Right-Pointing-Pointer Incorporation of Bi is one of key factors for the highly efficient activity of BMV solid solution. Black-Right-Pointing-Pointer Incorporation of Y is dispensable for H{sub 2} production.« less

Layered composites made from bimetallic strips produced by plasma spraying of TiAl on niobium

NASA Astrophysics Data System (ADS)

Burmistrov, V. I.; Antonova, A. V.; Povarova, K. B.; Bannykh, I. O.

2007-12-01

The production and structure of a multilayer TiAl/Nb composite material made from bimetallic TiAl/Nb strips fabricated by plasma spraying of TiAl granules onto niobium plates are studied. Here, 3-mm-and 2-mm-thick plates of a layered composite material (LCM) are produced by hot isostatic pressing of a stack of 35 bimetallic plates followed by hot rolling (the total degree of reduction is 78.6 and 85.7%, respectively). The LCM consists of discontinuous TiAl layers separated by niobium layers, and the adhesion between the layers is good. Diffusional intermediate layers form at the TiAl/Nb interfaces in the 3-mm-thick LCM and consist of the following two solid solutions: an α2-Ti3Al-based solid solution contains up to 28 at % Nb, and a niobiumbased solid solution contains up to 27 at % Ti and 32 at % Al. The diffusional intermediate layers in the 2-mmthick LCM plates consist of an α2-Ti3Al-based solid solution with up to 16.0 at % Nb; a τ-Ti3Al2Nb-or Ti4Al3Nb-based solid solution with 51.5 at % Ti, 32 at % Al, and 16.5 at % Nb; and a niobium-based solid solution with up to 22 at % Ti and 30.5 at % Al. When a bimetallic TiAl/Nb strip is fabricated by plasma spraying of granules of the Ti-48 at % Al alloy, this alloy is depleted of aluminum to 42 45 at %, and the fraction of the α2-Ti3Al phase in the sprayed layer increases. When the LCM is produced by hot isostatic pressing followed by hot rolling, the layer of plain niobium (Nb1) dissolves up to 5 at % Ti and 7 at % Al.

Electric terminal performance and characterization of solid oxide fuel cells and systems

NASA Astrophysics Data System (ADS)

Lindahl, Peter Allan

Solid Oxide Fuel Cells (SOFCs) are electrochemical devices which can effect efficient, clean, and quiet conversion of chemical to electrical energy. In contrast to conventional electricity generation systems which feature multiple discrete energy conversion processes, SOFCs are direct energy conversion devices. That is, they feature a fully integrated chemical to electrical energy conversion process where the electric load demanded of the cell intrinsically drives the electrochemical reactions and associated processes internal to the cell. As a result, the cell's electric terminals provide a path for interaction between load side electric demand and the conversion side processes. The implication of this is twofold. First, the magnitude and dynamic characteristics of the electric load demanded of the cell can directly impact the long-term efficacy of the cell's chemical to electrical energy conversion. Second, the electric terminal response to dynamic loads can be exploited for monitoring the cell's conversion side processes and used in diagnostic analysis and degradation-mitigating control schemes. This dissertation presents a multi-tier investigation into this electric terminal based performance characterization of SOFCs through the development of novel test systems, analysis techniques and control schemes. First, a reference-based simulation system is introduced. This system scales up the electric terminal performance of a prototype SOFC system, e.g. a single fuel cell, to that of a full power-level stack. This allows realistic stack/load interaction studies while maintaining explicit ability for post-test analysis of the prototype system. Next, a time-domain least squares fitting method for electrochemical impedance spectroscopy (EIS) is developed for reduced-time monitoring of the electrochemical and physicochemical mechanics of the fuel cell through its electric terminals. The utility of the reference-based simulator and the EIS technique are demonstrated through their combined use in the performance testing of a hybrid-source power management (HSPM) system designed to allow in-situ EIS monitoring of a stack under dynamic loading conditions. The results from the latter study suggest that an HSPM controller allows an opportunity for in-situ electric terminal monitoring and control-based mitigation of SOFC degradation. As such, an exploration of control-based SOFC degradation mitigation is presented and ideas for further work are suggested.

The solution structures of the cucumber mosaic virus and tomato aspermy virus coat proteins explored with molecular dynamics simulations.

PubMed

Gellért, Akos; Balázs, Ervin

2010-02-26

The three-dimensional structures of two cucumovirus coat proteins (CP), namely Cucumber mosaic virus (CMV) and Tomato aspermy virus (TAV), were explored by molecular dynamics (MD) simulations. The N-terminal domain and the C-terminal tail of the CPs proved to be intrinsically unstructured protein regions in aqueous solution. The N-terminal alpha-helix had a partially unrolled conformation. The thermal factor analysis of the CP loop regions demonstrated that the CMV CP had more flexible loop regions than the TAV CP. The principal component analysis (PCA) of the MD trajectories showed that the first three eigenvectors represented the three main conformational motions in the CPs. The first motion components with the highest variance contribution described an opening movement between the hinge and the N-terminal domain of both CPs. The second eigenvector showed a closing motion, while the third eigenvector represented crosswise conformational fluctuations. These new findings, together with previous results, suggest that the hinge region of CPs plays a central role in the recognition and binding of viral RNA. Copyright 2009 Elsevier Inc. All rights reserved.

A New IMS Based Inter-working Solution

NASA Astrophysics Data System (ADS)

Zhu, Zhongwen; Brunner, Richard

With the evolution of third generation network, more and more multimedia services are developed and deployed. Any new service to be deployed in IMS network is required to inter-work with existing Internet communities or legacy terminal users in order to appreciate the end users, who are the main drivers for the service to succeed. The challenge for Inter-working between IMS (IP Multimedia Subsystem) and non-IMS network is “how to handle recipient’s address”. This is because each network has its own routable address schema. For instance, the address for Google Talk user is xmpp:xyz@google.com, which is un-routable in IMS network. Hereafter a new Inter-working (IW) solution between IMS and non-IMS network is proposed for multimedia services that include Instant Messaging, Chat, and File transfer, etc. It is an end-to-end solution built on IMS infrastructure. The Public Service Identity (PSI) defined in 3GPP standard (3rd Generation Partnership Project) is used to allow terminal clients to allocate this IW service. When sending the SIP (Session Initial Protocol) request out for multimedia services, the terminal includes the recipient’s address in the payload instead of the “Request-URI” header. In the network, the proposed solution provides the mapping rules between different networks in MM-IW (Multimedia IW). The detailed technical description and the corresponding use cases are present. The comparison with other alternatives is made. The benefits of the proposed solution are highlighted.

Normal and anomalous nuclear spin-lattice relaxation at high temperatures in Sc-H(D), Y-H, and Lu-H solid solutions

NASA Astrophysics Data System (ADS)

Barnes, R. G.; Han, J.-W.; Torgeson, D. R.; Baker, D. B.; Conradi, M. S.; Norberg, R. E.

1995-02-01

We report the results of measurements of the proton (1H) spin-lattice relaxation rate R1 at high temperatures (to ~1400 K) in the hcp (α) solid-solution phases of the Sc-H, Y-H, and Lu-H systems, and of R1(45Sc) in Sc-H and Sc-D solid solutions. The latter measurements show unambiguous evidence of an anomalous increase at ~1000 K, whereas R1(1H) shows no such increase at any temperature. This behavior of R1(1H) contrasts with that in the bcc V-H, etc., solid solutions where anomalous relaxation occurs below ~1000 K, and in all investigated metal dihydride phases, MH2-x. The anomalous R1(1H) behavior in α-VHx, α-NbHx, etc., may be understood in terms of fast spin relaxation in the H2 gas in equilibrium with the solid, mediated by fast gas-solid exchange of hydrogen. However, in the present systems, α-ScHx, α-YHx, etc., the H2 gas pressure in equilibrium with the hcp systems is extremely low, resulting in negligible H2 concentration in the gas phase, and consequently a negligible contribution to R1(1H). In contrast, some of the present measurements indicate that the R1(45Sc) anomaly does result from the hydrogen content of the metal, but the mechanism remains unexplained.

Second-Sphere Effects in Dinuclear FeIIIZnII Hydrolase Biomimetics: Tuning Binding and Reactivity Properties.

PubMed

Camargo, Tiago Pacheco; Neves, Ademir; Peralta, Rosely A; Chaves, Cláudia; Maia, Elene C P; Lizarazo-Jaimes, Edgar H; Gomes, Dawidson A; Bortolotto, Tiago; Norberto, Douglas R; Terenzi, Hernán; Tierney, David L; Schenk, Gerhard

2018-01-02

Herein, we report the synthesis and characterization of two dinuclear Fe III Zn II complexes [Fe III Zn II LP1] (1) and [Fe III Zn II LP2] (2), in which LP1 and LP2 are conjugated systems containing one and two pyrene groups, respectively, connected via the diamine -HN(CH 2 ) 4 NH- spacer to the well-known N 5 O 2 -donor H 2 L ligand (H 2 L = 2-bis{[(2-pyridylmethyl)aminomethyl]-6-[(2-hydroxybenzyl)(2-pyridylmethyl)]aminomethyl}-4-methylphenol). The complex [Fe III Zn II L1] (3), in which H 2 L was modified to H 2 L1, with a carbonyl group attached to the terminal phenol group, was included in this study for comparison purposes. 1 Both complexes 1 and 2 were satisfactorily characterized in the solid state and in solution. Extended X-ray absorption fine structure data for 1 and 3 in an acetonitrile solution show that the multiply bridged structure seen in the solid state of 3 is retained in solution. Potentiometric and UV-vis titration of 1 and 2 show that electrostatic interaction between the protonated amino groups and coordinated water molecules significantly decreases the pK a of the iron(III)-bound water compared to those of 3. On the other hand, catalytic activity studies using 1 and 2 in the hydrolysis of the activated substrate bis(2,4-dinitrophenyl)phosphate (BDNPP) resulted in a significant increase in the association of the substrate (K ass ≅ 1/K M ) compared to that of 3 because of electrostatic and hydrophobic interactions between BDNPP and the side-chain diaminopyrene of the ligands H 2 LP1 and H 2 LP2. In addition, the introduction of the pyrene motifs in 1 and 2 enhanced their activity toward DNA and as effective antitumor drugs, although the biochemical mechanism of the latter effect is currently under investigation. These complexes represent interesting examples of how to promote an increase in the activity of traditional artificial metal nucleases by introducing second-coordination-sphere effects.

Convergent Synthesis of N-Linked Glycopeptides via Aminolysis of ω-Asp p-Nitrophenyl Thioesters in Solution.

PubMed

Du, Jing-Jing; Gao, Xiao-Fei; Xin, Ling-Ming; Lei, Ze; Liu, Zheng; Guo, Jun

2016-10-07

An efficient N-linked glycosylation reaction between glycosylamines and p-nitrophenyl thioester peptides has been developed. The reaction conditions are mild and compatible with the C-terminal free carboxylic acid group and the unprotected N-linked sialyloligosaccharide. By means of this convergent strategy, a versatile N-glycopeptide fragment containing an N-terminal Thz and a C-terminal thioester was readily prepared, which is available for the synthesis of long glycopeptides and glycoproteins using the protocol of native chemical ligation.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Room-temperature synthesis of Zn(0.80)Cd(0.20)S solid solution with a high visible-light photocatalytic activity for hydrogen evolution.

PubMed

Wang, Dong-Hong; Wang, Lei; Xu, An-Wu

2012-03-21

Visible light photocatalytic H(2) production from water splitting is of great significance for its potential applications in converting solar energy into chemical energy. In this study, a series of Zn(1-x)Cd(x)S solid solutions with a nanoporous structure were successfully synthesized via a facile template-free method at room temperature. The obtained solid solutions were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and N(2) adsorption-desorption analysis. The solid solutions show efficient photocatalytic activity for H(2) evolution from aqueous solutions containing sacrificial reagents S(2-) and SO(3)(2-) under visible-light irradiation without a Pt cocatalyst, and loading of the Pt cocatalyst further improves the visible-light photocatalytic activity. The optimal photocatalyst with x = 0.20 prepared at pH = 7.3 displays the highest activity for H(2) evolution. The bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S nanoparticles exhibit a high H(2) evolution rate of 193 μmol h(-1) and 458 μmol h(-1) under visible-light irradiation (λ ≥ 420 nm), respectively. In addition, the bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S catalysts show a high H(2) evolution rate of 252 and 640 μmol h(-1) under simulated solar light irradiation, respectively. Moreover, the Zn(0.80)Cd(0.20)S catalyst displays a high photocatalytic stability for H(2) evolution under long-term light irradiation. The incorporation of Cd in the solid solution leads to the visible light absorption, and the high content of Zn in the solid solution results in a relatively negative conduction band, a modulated band gap and a rather wide valence bandwidth, which are responsible for the excellent photocatalytic performance of H(2) production and for the high photostability. This journal is © The Royal Society of Chemistry 2012

Intermediate couplings: NMR at the solids-liquids interface

NASA Astrophysics Data System (ADS)

Spence, Megan

2006-03-01

Anisotropic interactions like dipolar couplings and chemical shift anisotropy have long offered solid-state NMR spectroscopists valuable structural information. Recently, solution-state NMR structural studies have begun to exploit residual dipolar couplings of biological molecules in weakly anisotropic solutions. These residual couplings are about 0.1% of the coupling magnitudes observed in the solid state, allowing simple, high-resolution NMR spectra to be retained. In this work, we examine the membrane-associated opioid, leucine enkephalin (lenk), in which the ordering is ten times larger than that for residual dipolar coupling experiments, requiring a combination of solution-state and solid-state NMR techniques. We adapted conventional solid-state NMR techniques like adiabatic cross- polarization and REDOR for use with such a system, and measured small amide bond dipolar couplings in order to determine the orientation of the amide bonds (and therefore the peptide) with respect to the membrane surface. However, the couplings measured indicate large structural rearrangements on the surface and contradict the published structures obtained by NOESY constraints, a reminder that such methods are of limited use in the presence of large-scale dynamics.

Practical solutions for reducing container ships' waiting times at ports using simulation model

NASA Astrophysics Data System (ADS)

Sheikholeslami, Abdorreza; Ilati, Gholamreza; Yeganeh, Yones Eftekhari

2013-12-01

The main challenge for container ports is the planning required for berthing container ships while docked in port. Growth of containerization is creating problems for ports and container terminals as they reach their capacity limits of various resources which increasingly leads to traffic and port congestion. Good planning and management of container terminal operations reduces waiting time for liner ships. Reducing the waiting time improves the terminal's productivity and decreases the port difficulties. Two important keys to reducing waiting time with berth allocation are determining suitable access channel depths and increasing the number of berths which in this paper are studied and analyzed as practical solutions. Simulation based analysis is the only way to understand how various resources interact with each other and how they are affected in the berthing time of ships. We used the Enterprise Dynamics software to produce simulation models due to the complexity and nature of the problems. We further present case study for berth allocation simulation of the biggest container terminal in Iran and the optimum access channel depth and the number of berths are obtained from simulation results. The results show a significant reduction in the waiting time for container ships and can be useful for major functions in operations and development of container ship terminals.

Effect of sodium chloride on the structure and stability of spider silk's N-terminal protein domain.

PubMed

Gronau, Greta; Qin, Zhao; Buehler, Markus J

2013-03-01

A spider's ability to store silk protein solutions at high concentration is believed to be related to the protein's terminal domains. It has been suggested that a shift in salt concentration and pH can have a significant influence on the assembly process. Based on experimental data, a model has been proposed in which the N-terminal domain exists as a monomer during storage and assembles into a homodimer upon spinning. Here we perform a systematic computational study using atomistic, coarse-grained and well-tempered metadynamics simulation to understand how the NaCl concentration in the solution affects the N-terminal domain of the silk protein. Our results show that a high salt concentration, as found during storage, weakens key salt bridges between the monomers, inducing a loss in bond energy by 28.6% in a single salt bridge. As a result dimer formation is less likely as 35.5% less energy is required to unfold the dimer by mechanical force. Conversely, homodimer formation appears to be more likely at low salt concentrations as the salt bridge stays at the lower energy state. The link between salt concentration, structure and stability of the N-terminal domain provides a possible mechanism that prevents premature fiber formation during storage.

Effect of sodium chloride on the structure and stability of spider silk’s N-terminal protein domain

PubMed Central

Gronau, Greta; Qin, Zhao; Buehler, Markus J.

2013-01-01

A spider’s ability to store silk protein solutions at high concentration is believed to be related to the protein’s terminal domains. It has been suggested that a shift in salt concentration and pH can have a significant influence on the assembly process. Based on experimental data, a model has been proposed in which the N-terminal domain exists as a monomer during storage and assembles into a homodimer upon spinning. Here we perform a systematic computational study using atomistic, coarse-grained and well-tempered metadynamics simulation to understand how the NaCl concentration in the solution affects the N-terminal domain of the silk protein. Our results show that a high salt concentration, as found during storage, weakens key salt bridges between the monomers, inducing a loss in bond energy by 28.6% in a single salt bridge. As a result dimer formation is less likely as 35.5% less energy is required to unfold the dimer by mechanical force. Conversely, homodimer formation appears to be more likely at low salt concentrations as the salt bridge stays at the lower energy state. The link between salt concentration, structure and stability of the N-terminal domain provides a possible mechanism that prevents premature fiber formation during storage. PMID:23833703

Structural insights into the human RyR2 N-terminal region involved in cardiac arrhythmias

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

Borko, Ľubomír; Bauerová-Hlinková, Vladena, E-mail: vladena.bauerova@savba.sk; Hostinová, Eva

2014-11-01

X-ray and solution structures of the human RyR2 N-terminal region were obtained under near-physiological conditions. The structure exhibits a unique network of interactions between its three domains, revealing an important stabilizing role of the central helix. Human ryanodine receptor 2 (hRyR2) mediates calcium release from the sarcoplasmic reticulum, enabling cardiomyocyte contraction. The N-terminal region of hRyR2 (amino acids 1–606) is the target of >30 arrhythmogenic mutations and contains a binding site for phosphoprotein phosphatase 1. Here, the solution and crystal structures determined under near-physiological conditions, as well as a homology model of the hRyR2 N-terminal region, are presented. The N-terminusmore » is held together by a unique network of interactions among its three domains, A, B and C, in which the central helix (amino acids 410–437) plays a prominent stabilizing role. Importantly, the anion-binding site reported for the mouse RyR2 N-terminal region is notably absent from the human RyR2. The structure concurs with the differential stability of arrhythmogenic mutations in the central helix (R420W, I419F and I419F/R420W) which are owing to disparities in the propensity of mutated residues to form energetically favourable or unfavourable contacts. In solution, the N-terminus adopts a globular shape with a prominent tail that is likely to involve residues 545–606, which are unresolved in the crystal structure. Docking the N-terminal domains into cryo-electron microscopy maps of the closed and open RyR1 conformations reveals C{sup α} atom movements of up to 8 Å upon channel gating, and predicts the location of the leucine–isoleucine zipper segment and the interaction site for spinophilin and phosphoprotein phosphatase 1 on the RyR surface.« less

Numerical solution of a coupled pair of elliptic equations from solid state electronics

NASA Technical Reports Server (NTRS)

Phillips, T. N.

1983-01-01

Iterative methods are considered for the solution of a coupled pair of second order elliptic partial differential equations which arise in the field of solid state electronics. A finite difference scheme is used which retains the conservative form of the differential equations. Numerical solutions are obtained in two ways, by multigrid and dynamic alternating direction implicit methods. Numerical results are presented which show the multigrid method to be an efficient way of solving this problem.

Improvements in geothermal electric power and silica production

DOEpatents

Hill, J.H.; Fulk, M.M.

Electricity is generated from hot geothermal solution by extracting heat therefrom, mineral solids which form in a so cooled geothermal solution are separated to recover minerals and facilitate reinjection of the solution into the ground. The separated solids are treated to recover silica by addition of an acid (amorphous silica precipitates) or a base (other minerals precipitate and soulble silicates are formed which are subsequently precipitated by acid neutralization). If desired, after silica is separated, other minerals can be separated and recovered.

Characterizing the Solid-Solution Coefficient and Plant Uptake Factor of As, Cd and Pb in California Croplands

USDA-ARS?s Scientific Manuscript database

In risk assessment models, the solid-solution partition coefficient (Kd), and plant uptake factor (PUF), are often employed to model the fate and transport of trace elements in soils. The trustworthiness of risk assessments depends on the reliability of the parameters used. In this study, we exami...

Extending atomistic simulation timescale in solid/liquid systems: crystal growth from solution by a parallel-replica dynamics and continuum hybrid method.

PubMed

Lu, Chun-Yaung; Voter, Arthur F; Perez, Danny

2014-01-28

Deposition of solid material from solution is ubiquitous in nature. However, due to the inherent complexity of such systems, this process is comparatively much less understood than deposition from a gas or vacuum. Further, the accurate atomistic modeling of such systems is computationally expensive, therefore leaving many intriguing long-timescale phenomena out of reach. We present an atomistic/continuum hybrid method for extending the simulation timescales of dynamics at solid/liquid interfaces. We demonstrate the method by simulating the deposition of Ag on Ag (001) from solution with a significant speedup over standard MD. The results reveal specific features of diffusive deposition dynamics, such as a dramatic increase in the roughness of the film.

Structural Changes Associated with Transthyretin Misfolding and Amyloid Formation Revealed by Solution and Solid-State NMR

DOE PAGES

Lim, Kwang Hun; Dasari, Anvesh K. R.; Hung, Ivan; ...

2016-03-21

Elucidation of structural changes involved in protein misfolding and amyloid formation is crucial for unraveling the molecular basis of amyloid formation. We report structural analyses of the amyloidogenic intermediate and amyloid aggregates of transthyretin using solution and solid-state nuclear magnetic resonance (NMR) spectroscopy. These NMR solution results show that one of the two main β-sheet structures (CBEF β-sheet) is maintained in the aggregation-competent intermediate, while the other DAGH β-sheet is more flexible on millisecond time scales. Magic-angle-spinning solid-state NMR revealed that AB loop regions interacting with strand A in the DAGH β-sheet undergo conformational changes, leading to the destabilized DAGHmore » β-sheet.« less

A Novel Solid-Phase Site-Specific PEGylation Enhances the In Vitro and In Vivo Biostabilty of Recombinant Human Keratinocyte Growth Factor 1

PubMed Central

Zhang, Jingui; Zhang, Yi; Zhang, Youting; Ye, Chaohui; Wang, Xiaojie; Ilghari, Dariush; Li, Xiaokun

2012-01-01

Keratinocyte growth factor 1 (KGF-1) has proven useful in the treatment of pathologies associated with dermal adnexae, liver, lung, and the gastrointestinal tract diseases. However, poor stability and short plasma half-life of the protein have restricted its therapeutic applications. While it is possible to improve the stability and extend the circulating half-life of recombinant human KGF-1 (rhKGF-1) using solution-phase PEGylation, such preparations have heterogeneous structures and often low specific activities due to multiple and/or uncontrolled PEGylation. In the present study, a novel solid-phase PEGylation strategy was employed to produce homogenous mono-PEGylated rhKGF-1. RhKGF-1 protein was immobilized on a Heparin-Sepharose column and then a site-selective PEGylation reaction was carried out by a reductive alkylation at the N-terminal amino acid of the protein. The mono-PEGylated rhKGF-1, which accounted for over 40% of the total rhKGF-1 used in the PEGylation reaction, was purified to homogeneity by SP Sepharose ion-exchange chromatography. Our biophysical and biochemical studies demonstrated that the solid-phase PEGylation significantly enhanced the in vitro and in vivo biostability without affecting the over all structure of the protein. Furthermore, pharmacokinetic analysis showed that modified rhKGF-1 had considerably longer plasma half-life than its intact counterpart. Our cell-based analysis showed that, similar to rhKGF-1, PEGylated rhKGF-1 induced proliferation in NIH 3T3 cells through the activation of MAPK/Erk pathway. Notably, PEGylated rhKGF-1 exhibited a greater hepatoprotection against CCl4-induced injury in rats compared to rhKGF-1. PMID:22574160

Analysis of Full-Test tools and their limitations as applied to terminal junction blocks

NASA Technical Reports Server (NTRS)

Smith, J. L.

1983-01-01

Discovery of unlocked contacts in Deutsch Block terminal junctions in Solid Rocket Booster flight hardware prompted an investigation into pull test techniques to help insure against possible failures. Internal frictional forces between socket and pin and between wire and grommet were examined. Pull test force must be greater than internal friction yet less than the crimp strength of the pin or socket. For this reason, a 100 percent accurate test is impossible. Test tools were evaluated. Available tools are adequate for pull testing.

Characterization of the Terminal Iron(IV) Imides {[PhBPtBu2(pz’)]FeIV≡NAd}+

PubMed Central

Thomas, Christine M.; Mankad, Neal P.; Peters, Jonas C.

2008-01-01

New hybrid bis(phosphine)(pyrazole)borate tripodal ligands ([PhBPtBu2(pz’)]−) are reported that support pseudotetrahedral iron in the oxidation states +1, +2, +3, and +4. The higher oxidation states are stabilized by a terminal Fe≡NR linkage. Of particular interest is the generation and thorough characterization of an S = 1 FeIV≡NR+ imide cation using this new ligand system. The latter species can be observed electrochemically and spectroscopically, and its solid-state crystal structure is reported. PMID:16608321

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

1990-01-01

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

Lubrication of rigid ellipsida solids

NASA Technical Reports Server (NTRS)

Hamrock, B. J.; Dowson, D.

1982-01-01

The influence of geometry on the isothermal hydrodynamic film separating two rigid solids was investigated. The minimum film thickness is derived for fully flooded conjunctions by using the Reynolds boundary conditions. It was found that the minimum film thickness had the same speed, viscosity, and load dependence as Kapitza' classical solution. However, the incorporation of Reynolds boundary conditions resulted in an additional geometry effect. Solutions using the parabolic film approximation are compared by using the exact expression for the film in the analysis. Contour plots are known that indicate in detail the pressure developed between the solids.

Crystal Violet Lactone Salicylaldehyde Hydrazone Zn(II) Complex: a Reversible Photochromic Material both in Solution and in Solid Matrix

PubMed Central

Li, Kai; Li, Yuanyuan; Tao, Jing; Liu, Lu; Wang, Lili; Hou, Hongwei; Tong, Aijun

2015-01-01

Crystal violet lactone (CVL) is a classic halochromic dye which has been widely used as chromogenic reagent in thermochromic and piezochromic systems. In this work, a very first example of CVL-based reversible photochromic compound was developed, which showed distinct color change upon UV-visible light irradiation both in solution and in solid matrix. Moreover, metal complex of CVL salicylaldehyde hydrozone was facilely synthesized, exhibiting reversible photochromic properties with good fatigue resistance. It was served as promising solid material for photo-patterning. PMID:26412101

Three-dimensional finite element analysis of acoustic instability of solid propellant rocket motors

NASA Technical Reports Server (NTRS)

Hackett, R. M.; Juruf, R. S.

1976-01-01

A three dimensional finite element solution of the acoustic vibration problem in a solid propellant rocket motor is presented. The solution yields the natural circular frequencies of vibration and the corresponding acoustic pressure mode shapes, considering the coupled response of the propellant grain to the acoustic oscillations occurring in the motor cavity. The near incompressibility of the solid propellant is taken into account in the formulation. A relatively simple example problem is solved in order to illustrate the applicability of the analysis and the developed computer code.

9-Fluorenylmethyloxycarbonyl/ tbutyl-based convergent protein synthesis.

PubMed

Barlos, K; Gatos, D

1999-01-01

Besides linear solid phase peptide synthesis, segment condensation in solution and chemical ligation, convergent peptide synthesis (CPS) was developed in order to enable the efficient preparation of complex peptides and small proteins. According to this synthetic strategy, solid phase synthesized and suitably protected peptide fragments corresponding to the entire peptide/protein-sequence are condensed on a solid support or in solution, to the target protein. This review summarizes CPS performed utilizing the mild 9-fluorenylmethyloxycarbonyl/tbutyloxycarbonyl-based protecting scheme for the amino acids. Copyright 1999 John Wiley & Sons, Inc.

Fluorescence from polystyrene - Photochemical processes in polymeric systems, 7

NASA Technical Reports Server (NTRS)

Gupta, M. C.; Gupta, A.

1983-01-01

Results are presented for measurements of the fluorescence spectra of polystyrene in dilute solution and in pure solid films. It is determined that a major potential source of experimental error is the concurrent photooxidative degradation in air which may obscure fluorescence emission from monomeric sites in solid films at 25 C. The fluorescence spectra of oriented films are evaluated in terms of the monomer to excimer fluorescence intensity ratio and the excimer 'red shift'. The monomer to excimer fluorescence intensity ratio is determined to be significantly higher in fluid solution than in solid film.

Solid organ fabrication: comparison of decellularization to 3D bioprinting.

PubMed

Jung, Jangwook P; Bhuiyan, Didarul B; Ogle, Brenda M

2016-01-01

Solid organ fabrication is an ultimate goal of Regenerative Medicine. Since the introduction of Tissue Engineering in 1993, functional biomaterials, stem cells, tunable microenvironments, and high-resolution imaging technologies have significantly advanced efforts to regenerate in vitro culture or tissue platforms. Relatively simple flat or tubular organs are already in (pre)clinical trials and a few commercial products are in market. The road to more complex, high demand, solid organs including heart, kidney and lung will require substantive technical advancement. Here, we consider two emerging technologies for solid organ fabrication. One is decellularization of cadaveric organs followed by repopulation with terminally differentiated or progenitor cells. The other is 3D bioprinting to deposit cell-laden bio-inks to attain complex tissue architecture. We reviewed the development and evolution of the two technologies and evaluated relative strengths needed to produce solid organs, with special emphasis on the heart and other tissues of the cardiovascular system.

Technical note: Use of a digital and an optical Brix refractometer to estimate total solids in milk replacer solutions for calves.

PubMed

Floren, H K; Sischo, W M; Crudo, C; Moore, D A

2016-09-01

The Brix refractometer is used on dairy farms and calf ranches for colostrum quality (estimation of IgG concentration), estimation of serum IgG concentration in neonatal calves, and nonsalable milk evaluation of total solids for calf nutrition. Another potential use is to estimate the total solids concentrations of milk replacer mixes as an aid in monitoring feeding consistency. The purpose of this study was to evaluate the use of Brix refractometers to estimate total solids in milk replacer solutions and evaluate different replacer mixes for osmolality. Five different milk replacer powders (2 milk replacers with 28% crude protein and 25% fat and 3 with 22% crude protein and 20% fat) were mixed to achieve total solids concentrations from approximately 5.5 to 18%, for a total of 90 different solutions. Readings from both digital and optical Brix refractometers were compared with total solids. The 2 types of refractometers' readings correlated well with one another. The digital and optical Brix readings were highly correlated with the total solids percentage. A value of 1.08 to 1.47 would need to be added to the Brix reading to estimate the total solids in the milk replacer mixes with the optical and digital refractometers, respectively. Osmolality was correlated with total solids percentage of the mixes, but the relationship was different depending on the type of milk replacer. The Brix refractometer can be beneficial in estimating total solids concentration in milk replacer mixes to help monitor milk replacer feeding consistency. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Termination of nanoscale zero-valent iron reactivity by addition of bromate as a reducing reactivity competitor

NASA Astrophysics Data System (ADS)

Mines, Paul D.; Kaarsholm, Kamilla M. S.; Droumpali, Ariadni; Andersen, Henrik R.; Lee, Wontae; Hwang, Yuhoon

2017-09-01

Remediation of contaminated groundwater by nanoscale zero-valent iron (nZVI) is widely becoming a leading environmentally friendly solution throughout the globe. Since a wide range of various nZVI-containing materials have been developed for effective remediation, it is necessary to determine an appropriate way to terminate the reactivity of any nZVI-containing material for a practical experimental procedure. In this study, bimetallic Ni/Fe-NPs were prepared to enhance overall reduction kinetics owing to the catalytic reactivity of nickel on the surface of nZVI. We have tested several chemical strategies in order to terminate nZVI reactivity without altering the concentration of volatile compounds in the solution. The strategies include surface passivation in alkaline conditions by addition of carbonate, and consumption of nZVI by a reaction competitor. Four halogenated chemicals, trichloroethylene, 1,1,1-trichloroethane, atrazine, and 4-chlorophenol, were selected and tested as model groundwater contaminants. Addition of carbonate to passivate the nZVI surface was not effective for trichloroethylene. Nitrate and then bromate were applied to competitively consume nZVI by their faster reduction kinetics. Bromate proved to be more effective than nitrate, subsequently terminating nZVI reactivity for all four of the tested halogenated compounds. Furthermore, the suggested termination method using bromate was successfully applied to obtain trichloroethylene reduction kinetics. Herein, we report the simple and effective method to terminate the reactivity of nZVI by addition of a reducing reactivity competitor.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1998-01-01

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

Formation of the racemic compound of ephedrine base from a physical mixture of its enantiomers in the solid, liquid, solution, or vapor state.

PubMed

Duddu, S P; Grant, D J

1992-08-01

Physical mixtures (conglomerates) of the two enantiomers of ephedrine base, each containing 0.5% (w/w) of water, were observed to be converted to the 1:1 racemic compound in the solid, liquid, solution, or vapor state. From a geometrically mixed racemic conglomerate of particle size 250-300 microns (50-60 mesh), the formation of the racemic compound follows second-order kinetics (first order with respect to each enantiomer), with a rate constant of 392 mol-1 hr-1 at 22 degrees C. The reaction appears to proceed via the vapor phase as indicated by the growth of the crystals of the racemic compound between diametrically separated crystals of the two enantiomers in a glass petri dish. The observed kinetics of conversion in the solid state are explained by a homogeneous reaction model via the vapor and/or liquid states. Formation of the racemic compound from the crystals of ephedrine enantiomers in the solution state may explain why Schmidt et al. (Pharm. Res. 5:391-395, 1988) observed a consistently lower aqueous solubility of the mixture than of the pure enantiomers. The solid phase in equilibrium with the solution at the end of the experiment was found to be the racemic compound, whose melting point and heat of fusion are higher than those of the enantiomers. An association reaction, of measurable rate, between the opposite enantiomers in a binary mixture in the solid, liquid, solution, or vapor state to form the racemic compound may be more common than is generally realized.

Recovery of soluble chloride salts from the wastewater generated during the washing process of municipal solid wastes incineration fly ash.

PubMed

Tang, Hailong; Erzat, Aris; Liu, Yangsheng

2014-01-01

Water washing is widely used as the pretreatment method to treat municipal solid waste incineration fly ash, which facilitates the further solidification/stabilization treatment or resource recovery of the fly ash. The wastewater generated during the washing process is a kind of hydrosaline solution, usually containing high concentrations of alkali chlorides and sulphates, which cause serious pollution to environment. However, these salts can be recycled as resources instead of discharge. This paper explored an effective and practical recovery method to separate sodium chloride, potassium chloride, and calcium chloride salts individually from the hydrosaline water. In laboratory experiments, a simulating hydrosaline solution was prepared according to composition of the waste washing water. First, in the three-step evaporation-crystallization process, pure sodium chloride and solid mixture of sodium and potassium chlorides were obtained separately, and the remaining solution contained potassium and calcium chlorides (solution A). And then, the solid mixture was fully dissolved into water (solution B obtained). Finally, ethanol was added into solutions A and B to change the solubility of sodium, potassium, and calcium chlorides within the mixed solvent of water and ethanol. During the ethanol-adding precipitation process, each salt was separated individually, and the purity of the raw production in laboratory experiments reached about 90%. The ethanol can be recycled by distillation and reused as the solvent. Therefore, this technology may bring both environmental and economic benefits.

Rail Mounted Gantry Crane Scheduling Optimization in Railway Container Terminal Based on Hybrid Handling Mode

PubMed Central

Zhu, Xiaoning

2014-01-01

Rail mounted gantry crane (RMGC) scheduling is important in reducing makespan of handling operation and improving container handling efficiency. In this paper, we present an RMGC scheduling optimization model, whose objective is to determine an optimization handling sequence in order to minimize RMGC idle load time in handling tasks. An ant colony optimization is proposed to obtain near optimal solutions. Computational experiments on a specific railway container terminal are conducted to illustrate the proposed model and solution algorithm. The results show that the proposed method is effective in reducing the idle load time of RMGC. PMID:25538768

A comparative study of an ABC and an artificial absorber for truncating finite element meshes

NASA Technical Reports Server (NTRS)

Oezdemir, T.; Volakis, John L.

1993-01-01

The type of mesh termination used in the context of finite element formulations plays a major role on the efficiency and accuracy of the field solution. The performance of an absorbing boundary condition (ABC) and an artificial absorber (a new concept) for terminating the finite element mesh was evaluated. This analysis is done in connection with the problem of scattering by a finite slot array in a thick ground plane. The two approximate mesh truncation schemes are compared with the exact finite element-boundary integral (FEM-BI) method in terms of accuracy and efficiency. It is demonstrated that both approximate truncation schemes yield reasonably accurate results even when the mesh is extended only 0.3 wavelengths away from the array aperture. However, the artificial absorber termination method leads to a substantially more efficient solution. Moreover, it is shown that the FEM-BI method remains quite competitive with the FEM-artificial absorber method when the FFT is used for computing the matrix-vector products in the iterative solution algorithm. These conclusions are indeed surprising and of major importance in electromagnetic simulations based on the finite element method.

Solid aerosol generator

DOEpatents

Prescott, Donald S.; Schober, Robert K.; Beller, John

1992-01-01

An improved solid aerosol generator used to produce a gas borne stream of dry, solid particles of predetermined size and concentration. The improved solid aerosol generator nebulizes a feed solution of known concentration with a flow of preheated gas and dries the resultant wet heated aerosol in a grounded, conical heating chamber, achieving high recovery and flow rates.

Regulation of solid waste management at Brazilian ports: analysis and proposals for Brazil in light of the European experience.

PubMed

Jaccoud, Cristiane; Magrini, Alessandra

2014-02-15

With a coastline of 8500 km, Brazil has 34 public ports and various private terminals, which together in 2012 handled 809 million tonnes of goods. The solid wastes produced (from port activities, ships and cargoes) pose a highly relevant problem, both due to the quantity and diversity, requiring a complex and integrated set of practices resulting from legal requirements and proactive initiatives. The main Brazilian law on solid waste management is recent (Law 12,305/2010) and the specific rules on solid waste in ports are badly in need of revision to meet the challenges caused by expansion of the sector and to harmonize them with the best global practices. This paper analyzes the current legal/regulatory framework for solid waste management at Brazilian ports and compares this structure with the practice in Europe. At the end, we suggest initiatives to improve the regulation of solid wastes at Brazilian ports. Copyright © 2014 Elsevier Ltd. All rights reserved.

Propulsion engineering study for small-scale Mars missions

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

Whitehead, J.

1995-09-12

Rocket propulsion options for small-scale Mars missions are presented and compared, particularly for the terminal landing maneuver and for sample return. Mars landing has a low propulsive {Delta}v requirement on a {approximately}1-minute time scale, but at a high acceleration. High thrust/weight liquid rocket technologies, or advanced pulse-capable solids, developed during the past decade for missile defense, are therefore more appropriate for small Mars landers than are conventional space propulsion technologies. The advanced liquid systems are characterize by compact lightweight thrusters having high chamber pressures and short lifetimes. Blowdown or regulated pressure-fed operation can satisfy the Mars landing requirement, but hardwaremore » mass can be reduced by using pumps. Aggressive terminal landing propulsion designs can enable post-landing hop maneuvers for some surface mobility. The Mars sample return mission requires a small high performance launcher having either solid motors or miniature pump-fed engines. Terminal propulsion for 100 kg Mars landers is within the realm of flight-proven thruster designs, but custom tankage is desirable. Landers on a 10 kg scale also are feasible, using technology that has been demonstrated but not previously flown in space. The number of sources and the selection of components are extremely limited on this smallest scale, so some customized hardware is required. A key characteristic of kilogram-scale propulsion is that gas jets are much lighter than liquid thrusters for reaction control. The mass and volume of tanks for inert gas can be eliminated by systems which generate gas as needed from a liquid or a solid, but these have virtually no space flight history. Mars return propulsion is a major engineering challenge; earth launch is the only previously-solved propulsion problem requiring similar or greater performance.« less

Exact Solution of the Two-Level System and the Einstein Solid in the Microcanonical Formalism

ERIC Educational Resources Information Center

Bertoldi, Dalia S.; Bringa, Eduardo M.; Miranda, E. N.

2011-01-01

The two-level system and the Einstein model of a crystalline solid are taught in every course of statistical mechanics and they are solved in the microcanonical formalism because the number of accessible microstates can be easily evaluated. However, their solutions are usually presented using the Stirling approximation to deal with factorials. In…

Modifying Optical Properties of ZnO Films by Forming Zn[subscript 1-x] Co[subscript x]O Solid Solutions via Spray Pyrolysis

ERIC Educational Resources Information Center

Bentley, Anne K.; Weaver, Gabriela C.; Russell, Cianan B.; Fornes, William L.; Choi, Kyoung-Shin; Shih, Susan M.

2007-01-01

A simple and cost-effective experiment for the development and characterization of semiconductors using Uv-vis spectroscopy is described. The study shows that the optical properties of ZnO films can be easily modified by forming Zn[subscript 1-x] Co[subscript x]O solid solutions via spray pyrolysis.

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions

NASA Astrophysics Data System (ADS)

Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; Chen, Guoying

2015-01-01

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature LixMn1.5Ni0.5O4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of LixMn1.5Ni0.5O4 (0 <= x <= 1) cathode material consisting of three cubic phases: LiMn1.5Ni0.5O4 (Phase I), Li0.5Mn1.5Ni0.5O4 (Phase II) and Mn1.5Ni0.5O4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. The work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.

Method for polymer synthesis in a reaction well

DOEpatents

Brennan, Thomas M.

1998-01-01

A method of synthesis for building a polymer chain, oligonucleotides in particular, by sequentially adding monomer units to at least one solid support for growing and immobilizing a polymer chain thereon in a liquid reagent solution. The method includes the step of: A) depositing a liquid reagent in a reaction well (26) in contact with at least one solid support and at least one monomer unit of the polymer chain affixed to the solid support. The well (26) includes at least one orifice (74) extending into the well (26), and is of a size and dimension to form a capillary liquid seal to retain the reagent solution in the well (26) to enable polymer chain growth on the solid support. The method further includes the step of B) expelling the reagent solution from the well (26), while retaining the polymer chain therein. This is accomplished by applying a first gas pressure to the reaction well such that a pressure differential between the first gas pressure and a second gas pressure exerted on an exit (80) of the orifice (74) exceeds a predetermined amount sufficient to overcome the capillary liquid seal and expel the reagent solution from the well (26) through the orifice exit (80).

Method for polymer synthesis in a reaction well

DOEpatents

Brennan, T.M.

1998-09-29

A method of synthesis is described for building a polymer chain, oligonucleotides in particular, by sequentially adding monomer units to at least one solid support for growing and immobilizing a polymer chain thereon in a liquid reagent solution. The method includes the step of: (A) depositing a liquid reagent in a reaction well in contact with at least one solid support and at least one monomer unit of the polymer chain affixed to the solid support. The well includes at least one orifice extending into the well, and is of a size and dimension to form a capillary liquid seal to retain the reagent solution in the well to enable polymer chain growth on the solid support. The method further includes the step of (B) expelling the reagent solution from the well, while retaining the polymer chain therein. This is accomplished by applying a first gas pressure to the reaction well such that a pressure differential between the first gas pressure and a second gas pressure exerted on an exit of the orifice exceeds a predetermined amount sufficient to overcome the capillary liquid seal and expel the reagent solution from the well through the orifice exit. 9 figs.

Composition design for Laves phase-related body-centered cubic-V solid solution alloys with large hydrogen storage capacities.

PubMed

Wang, H B; Wang, Q; Dong, C; Yuan, L; Xu, F; Sun, L X

2008-03-19

This paper analyzes the characteristics of alloy compositions with large hydrogen storage capacities in Laves phase-related body-centered cubic (bcc) solid solution alloy systems using the cluster line approach. Since a dense-packed icosahedral cluster A(6)B(7) characterizes the local structure of AB(2) Laves phases, in an A-B-C ternary system, such as Ti-Cr (Mn, Fe)-V, where A-B forms AB(2) Laves phases while A-C and B-C tend to form solid solutions, a cluster line A(6)B(7)-C is constructed by linking A(6)B(7) to C. The alloy compositions with large hydrogen storage capacities are generally located near this line and are approximately expressed with the cluster-plus-glue-atom model. The cluster line alloys (Ti(6)Cr(7))(100-x)V(x) (x = 2.5-70 at.%) exhibit different structures and hence different hydrogen storage capacities with increasing V content. The alloys (Ti(6)Cr(7))(95)V(5) and Ti(30)Cr(40)V(30) with bcc solid solution structure satisfy the cluster-plus-glue-atom model.

Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

DOE PAGES

Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

2015-01-31

Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

Thermoelectric SnS and SnS-SnSe solid solutions prepared by mechanical alloying and spark plasma sintering: Anisotropic thermoelectric properties

PubMed Central

Asfandiyar; Wei, Tian-Ran; Li, Zhiliang; Sun, Fu-Hua; Pan, Yu; Wu, Chao-Feng; Farooq, Muhammad Umer; Tang, Huaichao; Li, Fu; Li, Bo; Li, Jing-Feng

2017-01-01

P–type SnS compound and SnS1−xSex solid solutions were prepared by mechanical alloying followed by spark plasma sintering (SPS) and their thermoelectric properties were then studied in different compositions (x = 0.0, 0.2, 0.5, 0.8) along the directions parallel (//) and perpendicular (⊥) to the SPS–pressurizing direction in the temperature range 323–823 Κ. SnS compound and SnS1−xSex solid solutions exhibited anisotropic thermoelectric performance and showed higher power factor and thermal conductivity along the direction ⊥ than the // one. The thermal conductivity decreased with increasing contents of Se and fell to 0.36 W m−1 K−1 at 823 K for the composition SnS0.5Se0.5. With increasing selenium content (x) the formation of solid solutions substantially improved the electrical conductivity due to the increased carrier concentration. Hence, the optimized power factor and reduced thermal conductivity resulted in a maximum ZT value of 0.64 at 823 K for SnS0.2Se0.8 along the parallel direction. PMID:28240324

Thermoelectric SnS and SnS-SnSe solid solutions prepared by mechanical alloying and spark plasma sintering: Anisotropic thermoelectric properties.

PubMed

Asfandiyar; Wei, Tian-Ran; Li, Zhiliang; Sun, Fu-Hua; Pan, Yu; Wu, Chao-Feng; Farooq, Muhammad Umer; Tang, Huaichao; Li, Fu; Li, Bo; Li, Jing-Feng

2017-02-27

P-type SnS compound and SnS 1-x Se x solid solutions were prepared by mechanical alloying followed by spark plasma sintering (SPS) and their thermoelectric properties were then studied in different compositions (x = 0.0, 0.2, 0.5, 0.8) along the directions parallel (//) and perpendicular (⊥) to the SPS-pressurizing direction in the temperature range 323-823 Κ. SnS compound and SnS 1-x Se x solid solutions exhibited anisotropic thermoelectric performance and showed higher power factor and thermal conductivity along the direction ⊥ than the // one. The thermal conductivity decreased with increasing contents of Se and fell to 0.36 W m -1  K -1 at 823 K for the composition SnS 0.5 Se 0.5 . With increasing selenium content (x) the formation of solid solutions substantially improved the electrical conductivity due to the increased carrier concentration. Hence, the optimized power factor and reduced thermal conductivity resulted in a maximum ZT value of 0.64 at 823 K for SnS 0.2 Se 0.8 along the parallel direction.

Calculation of skin-stiffener interface stresses in stiffened composite panels

NASA Technical Reports Server (NTRS)

Cohen, David; Hyer, Michael W.

1987-01-01

A method for computing the skin-stiffener interface stresses in stiffened composite panels is developed. Both geometrically linear and nonlinear analyses are considered. Particular attention is given to the flange termination region where stresses are expected to exhibit unbounded characteristics. The method is based on a finite-element analysis and an elasticity solution. The finite-element analysis is standard, while the elasticity solution is based on an eigenvalue expansion of the stress functions. The eigenvalue expansion is assumed to be valid in the local flange termination region and is coupled with the finite-element analysis using collocation of stresses on the local region boundaries. Accuracy and convergence of the local elasticity solution are assessed using a geometrically linear analysis. Using this analysis procedure, the influence of geometric nonlinearities and stiffener parameters on the skin-stiffener interface stresses is evaluated.

In situ polymerization of monomers for polyphenylquinoxaline/graphite

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1973-01-01

Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

Solid-phase microextraction for qualitative and quantitative determination of migrated degradation products of antioxidants in an organic aqueous solution.

PubMed

Burman, Lina; Albertsson, Ann-Christine; Höglund, Anders

2005-07-08

Low molecular weight aromatic substances may migrate out from plastic packaging to their contents, especially if they consist of organic aqueous solutions or oils. It is, therefore, extremely important to be able to identify and quantify any migrated substances in such solutions, even at very low concentrations. We have in this work investigated and evaluated the use of solid-phase microextraction for the specific task of extraction from an organic aqueous solution such as a simulated pharmaceutical solution consisting of 10 vol.% ethanol in water. The goal was furthermore to investigate the possibility of simultaneously identifying and quantifying the substances in spite of differences in their chemical structures. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. Difficulties appeared due to the ethanol in the solution and the minute amounts of substances present. We have shown that a simultaneous quantification of migrated low molecular weight degradation products of antioxidants using only one fibre is possible if the extraction method and temperature are adjusted in relation to the concentration levels of the analytes. Comparions were made with solid-phase extraction.

Compact Solid-State 213 nm Laser Enables Standoff Deep Ultraviolet Raman Spectrometer: Measurements of Nitrate Photochemistry.

PubMed

Bykov, Sergei V; Mao, Michael; Gares, Katie L; Asher, Sanford A

2015-08-01

We describe a new compact acousto-optically Q-switched diode-pumped solid-state (DPSS) intracavity frequency-tripled neodymium-doped yttrium vanadate laser capable of producing ~100 mW of 213 nm power quasi-continuous wave as 15 ns pulses at a 30 kHz repetition rate. We use this new laser in a prototype of a deep ultraviolet (UV) Raman standoff spectrometer. We use a novel high-throughput, high-resolution Echelle Raman spectrograph. We measure the deep UV resonance Raman (UVRR) spectra of solid and solution sodium nitrate (NaNO3) and ammonium nitrate (NH4NO3) at a standoff distance of ~2.2 m. For this 2.2 m standoff distance and a 1 min spectral accumulation time, where we only monitor the symmetric stretching band, we find a solid state NaNO3 detection limit of ~100 μg/cm(2). We easily detect ~20 μM nitrate water solutions in 1 cm path length cells. As expected, the aqueous solutions UVRR spectra of NaNO3 and NH4NO3 are similar, showing selective resonance enhancement of the nitrate (NO3(-)) vibrations. The aqueous solution photochemistry is also similar, showing facile conversion of NO3(-) to nitrite (NO2(-)). In contrast, the observed UVRR spectra of NaNO3 and NH4NO3 powders significantly differ, because their solid-state photochemistries differ. Whereas solid NaNO3 photoconverts with a very low quantum yield to NaNO2, the NH4NO3 degrades with an apparent quantum yield of ~0.2 to gaseous species.

Methods for analysis of cracks in three-dimensional solids

NASA Technical Reports Server (NTRS)

Raju, I. S.; Newman, J. C., Jr.

1984-01-01

Various analytical and numerical methods used to evaluate the stress intensity factors for cracks in three-dimensional (3-D) solids are reviewed. Classical exact solutions and many of the approximate methods used in 3-D analyses of cracks are reviewed. The exact solutions for embedded elliptic cracks in infinite solids are discussed. The approximate methods reviewed are the finite element methods, the boundary integral equation (BIE) method, the mixed methods (superposition of analytical and finite element method, stress difference method, discretization-error method, alternating method, finite element-alternating method), and the line-spring model. The finite element method with singularity elements is the most widely used method. The BIE method only needs modeling of the surfaces of the solid and so is gaining popularity. The line-spring model appears to be the quickest way to obtain good estimates of the stress intensity factors. The finite element-alternating method appears to yield the most accurate solution at the minimum cost.

Luminescent properties under X-ray excitation of Ba(1-x)PbxWO4 disordered solid solution

NASA Astrophysics Data System (ADS)

Bakiz, B.; Hallaoui, A.; Taoufyq, A.; Benlhachemi, A.; Guinneton, F.; Villain, S.; Ezahri, M.; Valmalette, J.-C.; Arab, M.; Gavarri, J.-R.

2018-02-01

A series of polycrystalline barium-lead tungstate Ba1-xPbxWO4 with 0 ≤ x ≤ 1 was synthesized using a classical solid-state method with thermal treatment at 1000 °C. These materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Raman (FT-Raman) spectroscopy. X-ray diffraction profile analyses were performed using Rietveld method. These materials crystallized in the scheelite tetragonal structure and behaved as quasi ideal solid solution. Raman spectroscopy confirmed the formation of the solid solution. Structural distortions were evidenced in X-ray diffraction profiles and in vibration Raman spectra. The scanning electron microscopy experiments showed large and rounded irregular grains. Luminescence experiments were performed under X-ray excitation. The luminescence emission profiles have been interpreted in terms of four Gaussian components, with a major contribution of blue emission. The integrated intensity of luminescence reached a maximum value in the composition range x = 0.3-0.6, in relation with distortions of crystal lattice.

Recovery of uranium from an irradiated solid target after removal of molybdenum-99 produced from the irradiated target

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

Reilly, Sean Douglas; May, Iain; Copping, Roy

A process for minimizing waste and maximizing utilization of uranium involves recovering uranium from an irradiated solid target after separating the medical isotope product, molybdenum-99, produced from the irradiated target. The process includes irradiating a solid target comprising uranium to produce fission products comprising molybdenum-99, and thereafter dissolving the target and conditioning the solution to prepare an aqueous nitric acid solution containing irradiated uranium. The acidic solution is then contacted with a solid sorbent whereby molybdenum-99 remains adsorbed to the sorbent for subsequent recovery. The uranium passes through the sorbent. The concentrations of acid and uranium are then adjusted tomore » concentrations suitable for crystallization of uranyl nitrate hydrates. After inducing the crystallization, the uranyl nitrate hydrates are separated from a supernatant. The process results in the purification of uranyl nitrate hydrates from fission products and other contaminants. The uranium is therefore available for reuse, storage, or disposal.« less

A finite difference method for a coupled model of wave propagation in poroelastic materials.

PubMed

Zhang, Yang; Song, Limin; Deffenbaugh, Max; Toksöz, M Nafi

2010-05-01

A computational method for time-domain multi-physics simulation of wave propagation in a poroelastic medium is presented. The medium is composed of an elastic matrix saturated with a Newtonian fluid, and the method operates on a digital representation of the medium where a distinct material phase and properties are specified at each volume cell. The dynamic response to an acoustic excitation is modeled mathematically with a coupled system of equations: elastic wave equation in the solid matrix and linearized Navier-Stokes equation in the fluid. Implementation of the solution is simplified by introducing a common numerical form for both solid and fluid cells and using a rotated-staggered-grid which allows stable solutions without explicitly handling the fluid-solid boundary conditions. A stability analysis is presented which can be used to select gridding and time step size as a function of material properties. The numerical results are shown to agree with the analytical solution for an idealized porous medium of periodically alternating solid and fluid layers.

An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Method for treating liquid wastes

DOEpatents

Katti, K.V.; Volkert, W.A.; Singh, P.; Ketring, A.R.

1995-12-26

The method of treating liquid waste in a media is accomplished by exposing the media to phosphinimines and sequestering {sup 99}Tc from the media by the phosphinimine (PN) functionalities. The system for treating the liquid waste in the media includes extraction of {sup 99}TcO{sub 4}{sup {minus}} from aqueous solutions into organic solvents or mixed organic/polar media, extraction of {sup 99}Tc from solutions on a solid matrix by using a container containing PN functionalities on solid matrices including an inlet and outlet for allowing flow of media through an immobilized phosphinimine ligand system contained within the container. Also, insoluble suspensions of phosphinimine functionalities on solid matrices in liquid solutions or present on supported liquid membranes (SLM) can be used to sequester {sup 99}Tc from those liquids. 6 figs.

Method for treating liquid wastes

DOEpatents

Katti, Kattesh V.; Volkert, Wynn A.; Singh, Prahlad; Ketring, Alan R.

1995-01-01

The method of treating liquid waste in a media is accomplished by exposing the media to phosphinimines and sequestering .sup.99 Tc from the media by the phosphinimine (PN) functionalities. The system for treating the liquid waste in the media includes extraction of .sup.99 TcO.sub.4.sup.- from aqueous solutions into organic solvents or mixed organic/polar media, extraction of .sup.99 Tc from solutions on a solid matrix by using a container containing PN functionalities on solid matrices including an inlet and outlet for allowing flow of media through an immobilized phosphinimine ligand system contained within the container. Also, insoluble suspensions of phosphinimine functionalities on solid matrices in liquid solutions or present on supported liquid membranes (SLM) can be used to sequester .sup.99 Tc from those liquids.

Salt-assistant combustion synthesis of nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} (0 {<=} x {<=} 1) solid solutions

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

Tong Yuping, E-mail: huabeitong@yahoo.cn; Wang Yanping

2009-11-15

Nanocrystalline Nd{sub 2}(Zr{sub 1-x}Sn{sub x}){sub 2}O{sub 7} series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.

Tunable Porosities and Shapes of Fullerene-Like Spheres

PubMed Central

Dielmann, Fabian; Fleischmann, Matthias; Heindl, Claudia; Peresypkina, Eugenia V; Virovets, Alexander V; Gschwind, Ruth M; Scheer, Manfred

2015-01-01

The formation of reversible switchable nanostructures monitored by solution and solid-state methods is still a challenge in supramolecular chemistry. By a comprehensive solid state and solution study we demonstrate the potential of the fivefold symmetrical building block of pentaphosphaferrocene in combination with CuI halides to switch between spheres of different porosity and shape. With increasing amount of CuX, the structures of the formed supramolecules change from incomplete to complete spherically shaped fullerene-like assemblies possessing an Ih-C80 topology at one side and to a tetrahedral-structured aggregate at the other. In the solid state, the formed nano-sized aggregates reach an outer diameter of 3.14 and 3.56 nm, respectively. This feature is used to reversibly encapsulate and release guest molecules in solution. PMID:25759976

Efficient estimation of diffusion during dendritic solidification

NASA Technical Reports Server (NTRS)

Yeum, K. S.; Poirier, D. R.; Laxmanan, V.

1989-01-01

A very efficient finite difference method has been developed to estimate the solute redistribution during solidification with diffusion in the solid. This method is validated by comparing the computed results with the results of an analytical solution derived by Kobayashi (1988) for the assumptions of a constant diffusion coefficient, a constant equilibrium partition ratio, and a parabolic rate of the advancement of the solid/liquid interface. The flexibility of the method is demonstrated by applying it to the dendritic solidification of a Pb-15 wt pct Sn alloy, for which the equilibrium partition ratio and diffusion coefficient vary substantially during solidification. The fraction eutectic at the end of solidification is also obtained by estimating the fraction solid, in greater resolution, where the concentration of solute in the interdendritic liquid reaches the eutectic composition of the alloy.

Mathematical Analysis of the Solidification Behavior of Plain Steel Based on Solute- and Heat-Transfer Equations in the Liquid-Solid Zone

NASA Astrophysics Data System (ADS)

Fujimura, Toshio; Takeshita, Kunimasa; Suzuki, Ryosuke O.

2018-04-01

An analytical approximate solution to non-linear solute- and heat-transfer equations in the unsteady-state mushy zone of Fe-C plain steel has been obtained, assuming a linear relationship between the solid fraction and the temperature of the mushy zone. The heat transfer equations for both the solid and liquid zone along with the boundary conditions have been linked with the equations to solve the whole equations. The model predictions ( e.g., the solidification constants and the effective partition ratio) agree with the generally accepted values and with a separately performed numerical analysis. The solidus temperature predicted by the model is in the intermediate range of the reported formulas. The model and Neuman's solution are consistent in the low carbon range. A conventional numerical heat analysis ( i.e., an equivalent specific heat method using the solidus temperature predicted by the model) is consistent with the model predictions for Fe-C plain steels. The model presented herein simplifies the computations to solve the solute- and heat-transfer simultaneous equations while searching for a solidus temperature as a part of the solution. Thus, this model can reduce the complexity of analyses considering the heat- and solute-transfer phenomena in the mushy zone.

Constitution of the Sr-Ni-O system

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

Zinkevich, M.

2005-09-15

The constitution of the Sr-Ni-O system was studied experimentally for the first time. Samples were prepared either from SrCO{sub 3} and NiO or from Sr(NO{sub 3}){sub 2} and Ni(NO{sub 3}){sub 2}.6H{sub 2}O and characterized by high-temperature X-ray powder diffraction, scanning electron microscopy, thermogravimetric and differential thermal analyses. In the SrO-NiO quasibinary system an eutectic reaction: liquid-bar SrO+NiO was found to occur at 1396+/-5{sup o}C, while the homogeneity range of terminal solid solutions is negligible. Thermodynamic calculations using the regular solution model for the liquid and rocksalt-type phases were employed to predict liquidus and solidus curves. Three ternary compounds, SrNiO{sub 2.5},more » Sr{sub 5}Ni{sub 4}O{sub 11}, and Sr{sub 9}Ni{sub 7}O{sub 21} were observed in the samples prepared from nitrate solutions, but only Sr{sub 9}Ni{sub 7}O{sub 21} was proved to be thermodynamically stable in air up to 1030+/-6{sup o}C. When heating in air, SrNiO{sub 2.5} and Sr{sub 5}Ni{sub 4}O{sub 11} were found to transform irreversibly into a mixture of Sr{sub 9}Ni{sub 7}O{sub 21} and NiO. Isothermal section of the SrO-NiO-O subsystem, which represents phase equilibria at 950-1030{sup o}C as well as an isobaric section of the Sr-Ni-O system in air were constructed.« less

Investigation of Artificial Forced Cooling in the Bridgman Crystal Growth of Cadmium Zinc Telluride

NASA Astrophysics Data System (ADS)

Liu, Juncheng; Li, Jiao; Zhang, Guodong; Li, Changxing; Lennon, Craig; Sivananthan, Siva

2007-08-01

The effects of artificial forced cooling on the solid liquid interface and on solute segregation were investigated by modeling the vertical Bridgman method for the single-crystal growth of CdZnTe, taking into consideration effects such as increasing the axial outward heat flux from the crucible bottom, the radial outward heat flux from the crucible wall, and the carbon film thickness on the crucible inner wall. Axial artificially forced cooling noticeably increases convection and the temperature gradient in the melt next to the solid liquid interface, and substantially reduces interface concavity at the initial solidification stage. Interface concavity increases a little when the solidification proceeds further, however. Axial artificially forced cooling reduces radial solute segregation of the initial segment of the grown crystal and slightly increases the solute iso-concentration segment. Radial artificially forced cooling enhances melt convection substantially, affects solid liquid interface concavity only slightly, and hardly affects solute segregation in the grown crystal. Doubling the carbon film thickness weakens convection of the melt in front of the interface, substantially increases interface concavity, and hardly affects solute segregation in the grown crystal.

An insight into intrinsic interfacial properties between Li metals and Li10GeP2S12 solid electrolytes.

PubMed

Chen, Bingbing; Ju, Jiangwei; Ma, Jun; Zhang, Jianjun; Xiao, Ruijuan; Cui, Guanglei; Chen, Liquan

2017-11-29

Density functional theory simulations and experimental studies were performed to investigate the interfacial properties, including lithium ion migration kinetics, between lithium metal anode and solid electrolyte Li 10 GeP 2 S 12 (LGPS). The LGPS[001] plane was chosen as the studied surface because the easiest Li + migration pathway is along this direction. The electronic structure of the surface states indicated that the electrochemical stability was reduced at both the PS 4 - and GeS 4 -teminated surfaces. For the interface cases, the equilibrium interfacial structures of lithium metal against the PS 4 -terminated LGPS[001] surface (Li/PS 4 -LGPS) and the GeS 4 -terminated LGPS[001] surface (Li/GeS 4 -LGPS) were revealed based on the structural relaxation and adhesion energy analysis. Solid electrolyte interphases were expected to be formed at both Li/PS 4 -LGPS and Li/GeS 4 -LGPS interfaces, resulting in an unstable state of interface and large interfacial resistance, which was verified by the EIS results of the Li/LGPS/Li cell. In addition, the simulations of the migration kinetics show that the energy barriers for Li + crossing the Li/GeS 4 -LGPS interface were relatively low compared with the Li/PS 4 -LGPS interface. This may contribute to the formation of Ge-rich phases at the Li/LGPS interface, which can tune the interfacial structures to improve the ionic conductivity for future all-solid-state batteries. This work will offer a thorough understanding of the Li/LGPS interface, including local structures, electronic states and Li + diffusion behaviors in all-solid-state batteries.

Triclinic-monoclinic-orthorhombic (T-M-O) structural transitions in phase diagram of FeVO4-CrVO4 solid solutions

NASA Astrophysics Data System (ADS)

Bera, Ganesh; Reddy, V. R.; Rambabu, P.; Mal, P.; Das, Pradip; Mohapatra, N.; Padmaja, G.; Turpu, G. R.

2017-09-01

Phase diagram of FeVO4-CrVO4 solid solutions pertinent with structural and magnetic phases is presented with unambiguous experimental evidences. Solid solutions Fe1-xCrxVO4 (0 ≤ x ≤ 1.0) were synthesized through the standard solid state route and studied by X-ray diffraction, scanning electron microscopy, energy dispersive spectra of X-rays, Raman spectroscopy, d.c. magnetization, and 57Fe Mössbauer spectroscopic studies. FeVO4 and CrVO4 were found to be in triclinic (P-1 space group) and orthorhombic structures (Cmcm space group), respectively. Cr incorporation into the FeVO4 lattice leads to the emergence of a new monoclinic phase dissimilar to the both end members of the solid solutions. In Fe1-xCrxVO4 up to x = 0.10, no discernible changes in the triclinic structure were found. A new structural monoclinic phase (C2/m space group) emerges within the triclinic phase at x = 0.125, and with the increase in Cr content, it gets stabilized with clear single phase signatures in the range of x = 0.175-0.25 as evidenced by the Rietveld analysis of the structures. Beyond x = 0.33, orthorhombic phase similar to CrVO4 (Cmcm space group) emerges and coexists with a monoclinic structure up to x = 0.85, which finally tends to stabilize in the range of x = 0.90-1.00. The Raman spectroscopic studies also confirm the structural transition. FeVO4 Raman spectra show the modes related to three nonequivalent V ions in the triclinic structure, where up to 42 Raman modes are observed in the present study. With the stabilization of structures having higher symmetry, the number of Raman modes decreases and the modes related to symmetry inequivalent sites collate into singular modes from the doublet structure. A systematic crossover from two magnetic transitions in FeVO4, at 21.5 K and 15.4 K to single magnetic transition in CrVO4, at 71 K (antiferromagnetic transition), is observed in magnetization studies. The intermediate solid solution with x = 0.15 shows two magnetic transitions, whereas in the compound with x = 0.33 one of the magnetic transitions disappears. 57Fe Mössbauer spectroscopic studies show a finger print evidence for disappearance of non-equivalent sites of Fe as the structure changes from Triclinic-Monoclinic-Orthorhombic phases with the increasing Cr content in Fe1-xCrxVO4. Comprehensive studies related to the structural changes in Fe1-xCrxVO4 solid solutions lead us to detailed phase diagrams which shall be characteristic for room temperature structural and temperature dependent magnetic transitions in these solid solutions, respectively.

Structure and dynamics of micelle-bound neuropeptide Y: comparison with unligated NPY and implications for receptor selection.

PubMed

Bader, R; Bettio, A; Beck-Sickinger, A G; Zerbe, O

2001-01-12

The biological importance of the neuropeptide Y (NPY) has steered a number of investigations about its solution structure over the last 20 years. Here, we focus on the comparison of the structure and dynamics of NPY free in solution to when bound to a membrane mimetic, dodecylphosphocholine (DPC) micelles, as studied by 2D (1)H NMR spectroscopy. Both, free in solution and in the micelle-bound form, the N-terminal segment (Tyr1-Glu15) is shown to extend like a flexible tail in solution. This is not compatible with the PP-fold model for NPY that postulates backfolding of the flexible N terminus onto the C-terminal helix. The correlation time (tau(c)) of NPY in aqueous solution, 5.5 (+/-1.0) ns at 32 degrees C, is only consistent with its existence in a dimeric form. Exchange contributions especially enhancing transverse relaxation rates (R(2)) of residues located on one side of the C-terminal helix of the molecule are supposed to originate from dimerization of the NPY molecule. The dimerization interface was directly probed by looking at (15)N-labeled NPY/spin-labeled [TOAC34]-[(14)N]-NPY heterodimers and revealed both parallel and anti-parallel alignment of the helices. The NMR-derived three-dimensional structure of micelle-bound NPY at 37 degrees C and pH 6.0 is similar but not identical to that free in solution. The final set of 17 lowest-energy DYANA structures is particularly well defined in the region of residues 21-31, with a mean pairwise RMSD of 0.23 A for the backbone heavy atoms and 0.85 A for all heavy atoms. The combination of NMR relaxation data and CD measurements clearly demonstrates that the alpha-helical region Ala18-Thr32 is more stable, and the C-terminal tetrapeptide becomes structured only in the presence of the phosphocholine micelles. The position of NPY relative to the DPC micelle surface was probed by adding micelle integrating spin labels. Together with information from (1)H,(2)H exchange rates, we conclude that the interaction of NPY with the micelle is promoted by the amphiphilic alpha-helical segment of residues Tyr21-Thr32. NPY is located at the lipid-water interface with its C-terminal helix parallel to the membrane surface and penetrates the hydrophobic interior only via insertions of a few long aliphatic or aromatic side-chains. From these data we can demonstrate that the dimer interface of neuropeptide Y is similar to the interface of the monomer binding to DPC-micelles. We speculate that binding of the NPY monomer to the membrane is an essential key step preceeding receptor binding, thereby pre-orientating the C-terminal tetrapeptide and possibly inducing the bio-active conformation. Copyright 2001 Academic Press.

Analysis of the bond-valence method for calculating (29) Si and (31) P magnetic shielding in covalent network solids.

PubMed

Holmes, Sean T; Alkan, Fahri; Iuliucci, Robbie J; Mueller, Karl T; Dybowski, Cecil

2016-07-05

(29) Si and (31) P magnetic-shielding tensors in covalent network solids have been evaluated using periodic and cluster-based calculations. The cluster-based computational methodology employs pseudoatoms to reduce the net charge (resulting from missing co-ordination on the terminal atoms) through valence modification of terminal atoms using bond-valence theory (VMTA/BV). The magnetic-shielding tensors computed with the VMTA/BV method are compared to magnetic-shielding tensors determined with the periodic GIPAW approach. The cluster-based all-electron calculations agree with experiment better than the GIPAW calculations, particularly for predicting absolute magnetic shielding and for predicting chemical shifts. The performance of the DFT functionals CA-PZ, PW91, PBE, rPBE, PBEsol, WC, and PBE0 are assessed for the prediction of (29) Si and (31) P magnetic-shielding constants. Calculations using the hybrid functional PBE0, in combination with the VMTA/BV approach, result in excellent agreement with experiment. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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

Saidov, A. S., E-mail: amin@uzsci.net; Usmonov, Sh. N., E-mail: sh-usmonov@rambler.ru; Saidov, M. S.

(Si{sub 2}){sub 1−x−y}(Ge{sub 2}){sub x}(GaAs){sub y} substitutional solid solutions (0 ≤ x ≤ 0.91, 0 ≤ y ≤ 0.94) are grown by liquid-phase epitaxy from a Pb-based solution-melt on Si substrates with the (111) crystallographic orientation. The chemical composition of the epitaxial films is studied by X-rays probe microanalysis, and the distribution profile of solid solution components is determined. Spectral dependences of the photosensitivity and photoluminescence of the n-Si-p(Si{sub 2}){sub 1−x−y}(Ge{sub 2}){sub x}(GaAs){sub y} heterostructures are studied at room and liquid-nitrogen temperatures. Two maxima are found in the photoluminescence spectra of the (Si{sub 2}){sub 1−x−y}(Ge{sub 2}){sub x}(GaAs){sub y} films (0more » ≤ x ≤ 0.91, 0 ≤ y ≤ 0.94) against the background of a broad emission spectrum. The fundamental maximum with an energy of 1.45 eV is caused by the band-to-band recombination of solid solution carriers, and an additional maximum with an energy of 1.33 eV is caused by the recombination of carriers with the participation of impurity levels of the Si-Si bond (Si{sub 2} is covalently coupled with the tetrahedral lattice of the solid solution host)« less

Heat sterilizable solid-propellant development

NASA Technical Reports Server (NTRS)

Kalfayan, S. H.

1981-01-01

The binders tested were polyurethanes made from two hydroxy-terminated polybutadienes, R-45 and Butarez HT, one hydroxy-terminated butadiene-acrylonitrile copolymer, Hycar 1300X 17, and a hydroxy-terminated prepolymer, Esterdiol 560, made from the dimerized fatty acid Empol 1010. The isocyanates used most extensively were isophorone diisocyanate (IPDI) and a polymeric diisocyanate, DDI. Stress relaxation was used to examine the chemical changes that took place in the binder when subjected to the sterilization temperatures. The thermal stability of the oxidizer, ammonium perchlorate (AP), was tested by thermogravimetry in the isothermal and nonisothermal modes. The effect of particle size, recrystallization, moisture content, and doping on the heat stability of AP could be evaluated by this method. The volatile degradation products, obtained when AP samples were aged at 135 C for prolonged periods, were analyzed by mass spectroscopy.

Thermal properties of spinel based solid solutions

NASA Astrophysics Data System (ADS)

O'Hara, Kelley Rae

Solid solution formation in spinel based systems proved to be a viable approach to decreasing thermal conductivity. Samples with systematically varied additions of MgGa2O4 to MgAl2O 4 were prepared and thermal diffusivity was measured using the laser flash technique. Additionally, heat capacity was measured using differential scanning calorimetry and modeled for the MgAl2O4-MgGa 2O4 system. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa2O4 to the system. The solid solution continued to decrease the thermal conductivity by 13% up to 1000°C with 5 mol% addition. The decrease in thermal conductivity ultimately resulted in a decrease in heat flux when applied to a theoretical furnace lining, which could lead to energy savings in industrial settings. The MgAl2O4-Al2O3 phase equilibria was investigated to fully understand the system and the thermal properties at elevated temperatures. The solvus line between MgAl2O4 and Al2O3 has been defined at 79.6 wt% Al 2O3 at 1500°C, 83.0 wt% Al2O4 at 1600°C, and 86.5 wt% Al2O3 at 1700°C. A metastable region has been identified at temperatures up to 1700°C which could have significant implications for material processing and properties. The spinel solid solution region has been extended to form an infinite solid solution with Al2O3 at elevated temperatures. A minimum in melting at 1975°C and a chemistry of 96 wt% Al2O3 rather than a eutectic is present. Thermal properties in the MgAl2O4-Al2O 3 system were investigated in both the single phase solid solution region and the two phase region. The thermal diffusivity decreased through the MgAl 2O4 solid solution region and was at a minimum through the entire metastable (nucleation and growth) region. As Al2O 3 became present as a second phase the thermal diffusivity increased with Al2O3 content. There was an 11.7% increase in thermal diffusivity with a change in overall chemistry of 85.20 wt% Al2O 3 to 87.71 wt% Al2O3, due to the drastic change in final chemistry (38.3 wt% Al20 3) caused by the nucleation and growth region in the system.

Neural Network Assisted Inverse Dynamic Guidance for Terminally Constrained Entry Flight

PubMed Central

Chen, Wanchun

2014-01-01

This paper presents a neural network assisted entry guidance law that is designed by applying Bézier approximation. It is shown that a fully constrained approximation of a reference trajectory can be made by using the Bézier curve. Applying this approximation, an inverse dynamic system for an entry flight is solved to generate guidance command. The guidance solution thus gotten ensures terminal constraints for position, flight path, and azimuth angle. In order to ensure terminal velocity constraint, a prediction of the terminal velocity is required, based on which, the approximated Bézier curve is adjusted. An artificial neural network is used for this prediction of the terminal velocity. The method enables faster implementation in achieving fully constrained entry flight. Results from simulations indicate improved performance of the neural network assisted method. The scheme is expected to have prospect for further research on automated onboard control of terminal velocity for both reentry and terminal guidance laws. PMID:24723821

Single Protein Structural Analysis with a Solid-state Nanopore Sensor

NASA Astrophysics Data System (ADS)

Li, Jiali; Golovchenko, Jene; McNabb, David

2005-03-01

We report on the use of solid-state nanopore sensors to detect single polypeptides. These solid-state nanopores are fabricated in thin membranes of silicon nitride by ion beam sculpting...[1]. When an electrically biased nanopore is exposed to denatured proteins in ionic solution, discrete transient electronic signals: current blockages are observed. We demonstrate examples of such transient electronic signals for Bovine Serum Albumin (BSA) and human placental laminin M proteins in Guanidine hydrochloride solution, which suggest that these polypeptides are individually translocating through the nanopore during the detecting process. The amplitude of the current blockages is proportional to the bias voltage. No transient current blockages are observed when proteins are not present in the solution. To probe protein-folding state, pH and temperature dependence experiments are performed. The results demonstrate a solid-state nanopore sensor can be used to detect and analyze single polypeptide chains. Similarities and differences with signals obtained from double stranded DNA in a solid-state nanopore and single stranded DNA in a biological nanopore are discussed. [.1] Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169.

Aromatic hydrazones derived from nicotinic acid hydrazide as fluorimetric pH sensing molecules: Structural analysis by computational and spectroscopic methods in solid phase and in solution

NASA Astrophysics Data System (ADS)

Benković, T.; Kenđel, A.; Parlov-Vuković, J.; Kontrec, D.; Chiş, V.; Miljanić, S.; Galić, N.

2018-02-01

Structural analyses of aroylhydrazones were performed by computational and spectroscopic methods (solid state NMR, 1 and 2D NMR spectroscopy, FT-IR (ATR) spectroscopy, Raman spectroscopy, UV-Vis spectrometry and spectrofluorimetry) in solid state and in solution. The studied compounds were N‧-(2,3-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (1), N‧-(2,5-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N‧-(3-chloro-2-hydroxy-phenylmethylidene)-3-pyridinecarbohydrazide (3), and N‧-(2-hydroxy-4-methoxyphenyl-methylidene)-3-pyridinecarbohydrazide (4). Both in solid state and in solution, all compounds were in ketoamine form (form I, sbnd COsbnd NHsbnd Ndbnd Csbnd), stabilized by intramolecular H-bond between hydroxyl proton and nitrogen atom of the Cdbnd N group. In solid state, the Cdbnd O group of 1-4 were involved in additional intermolecular H-bond between closely packed molecules. Among hydrazones studied, the chloro- and methoxy-derivatives have shown pH dependent and reversible fluorescence emission connected to deprotonation/protonation of salicylidene part of the molecules. All findings acquired by experimental methods (NMR, IR, Raman, and UV-Vis spectra) were in excellent agreement with those obtained by computational methods.

Solid aerosol generator

DOEpatents

Prescott, D.S.; Schober, R.K.; Beller, J.

1992-03-17

An improved solid aerosol generator used to produce a gas borne stream of dry, solid particles of predetermined size and concentration is disclosed. The improved solid aerosol generator nebulizes a feed solution of known concentration with a flow of preheated gas and dries the resultant wet heated aerosol in a grounded, conical heating chamber, achieving high recovery and flow rates. 2 figs.

Improved solid aerosol generator

DOEpatents

Prescott, D.S.; Schober, R.K.; Beller, J.

1988-07-19

An improved solid aerosol generator used to produce a gas borne stream of dry, solid particles of predetermined size and concentration. The improved solid aerosol generator nebulizes a feed solution of known concentration with a flow of preheated gas and dries the resultant wet heated aerosol in a grounded, conical heating chamber, achieving high recovery and flow rates. 2 figs.

Fabrication of Hierarchical Layer-by-Layer Assembled Diamond-based Core-Shell Nanocomposites as Highly Efficient Dye Absorbents for Wastewater Treatment

NASA Astrophysics Data System (ADS)

Zhao, Xinna; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Ma, Xilong; Hu, Jie; Huang, Hao; Zhang, Lexin; Yan, Xuehai

2017-03-01

The effective chemical modification and self-assembly of diamond-based hierarchical composite materials are of key importance for a broad range of diamond applications. Herein, we report the preparation of novel core-shell diamond-based nanocomposites for dye adsorption toward wastewater treatment through a layer-by-layer (LbL) assembled strategy. The synthesis of the reported composites began with the carboxyl functionalization of microdiamond by the chemical modification of diamond@graphene oxide composite through the oxidation of diamond@graphite. The carboxyl-terminated microdiamond was then alternatively immersed in the aqueous solution of amine-containing polyethylenimine and carboxyl-containing poly acrylic acid, which led to the formation of adsorption layer on diamond surface. Alternating (self-limiting) immersions in the solutions of the amine-containing and carboxyl-containing polymers were continued until the desired number of shell layers were formed around the microdiamond. The obtained core-shell nanocomposites were successfully synthesized and characterized by morphological and spectral techniques, demonstrating higher surface areas and mesoporous structures for good dye adsorption capacities than nonporous solid diamond particles. The LbL-assembled core-shell nanocomposites thus obtained demonstrated great adsorption capacity by using two model dyes as pollutants for wastewater treatment. Therefore, the present work on LbL-assembled diamond-based composites provides new alternatives for developing diamond hybrids as well as nanomaterials towards wastewater treatment applications.

Preparation and Structural Properties of InIII–H Complexes

PubMed Central

Sickerman, Nathaniel S.; Henry, Renée M.; Ziller, Joseph W.

2013-01-01

The use of the tripodal ligands tris[(N'-tert-butylureaylato)-N-ethyl]aminato ([H3buea]3−) and the sulfonamide-based N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzene-sulfonamidato) ([MST]3−) has led to the synthesis of two structurally distinct In(III)–OH complexes. The first example of a five-coordinate indium(III) complex with a terminal hydroxide ligand, K[InIIIH3buea(OH)], was prepared by addition of In(OAc)3 and water to a deprotonated solution of H6buea. X-ray diffraction analysis, as well as FTIR and 1H NMR spectroscopic methods, provided evidence for the formation of a monomeric In(III)–OH complex. The complex contains an intramolecular hydrogen bonding (H-bonding) network involving the In(III)–OH unit and [H3buea]3− ligand, which aided in isolation of the complex. Isotope labeling studies verified the source of the hydroxo ligand as water. Treatment of the [InIIIMST] complex with a mixture of 15-crown-5 ether and NaOH led to isolation of the complex [15-crown-5⊃NaI-(μ-OH)-InIIIMST], whose solid-state structure was confirmed using X-ray diffraction methods. Nuclear magnetic resonance studies on this complex suggest it retains its heterobimetallic structure in solution. PMID:25309019

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1998-01-13

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

Closed-form recursive formula for an optimal tracker with terminal constraints

NASA Technical Reports Server (NTRS)

Juang, J.-N.; Turner, J. D.; Chun, H. M.

1984-01-01

Feedback control laws are derived for a class of optimal finite time tracking problems with terminal constraints. Analytical solutions are obtained for the feedback gain and the closed-loop response trajectory. Such formulations are expressed in recursive forms so that a real-time computer implementation becomes feasible. Two examples are given to illustrate the validity and usefulness of the formulations.

Phased Arrays of Ground and Airborne Mobile Terminals for Satellite Communications

NASA Technical Reports Server (NTRS)

Huang, John

1996-01-01

Phased array antenna is beginning to play an important in the arena of mobile/satellite communications. Two examples of mobile terminal phased arrays will be shown. Their technical background, challenges, and cost drivers will be discussed. A possible solution to combat some of the deficiencies of the conventional phased array by exploiting the phased reflectarray technology will be briefly presented.

An approximate, maximum terminal velocity descent to a point

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

Eisler, G.R.; Hull, D.G.

1987-01-01

No closed form control solution exists for maximizing the terminal velocity of a hypersonic glider at an arbitrary point. As an alternative, this study uses neighboring extremal theory to provide a sampled data feedback law to guide the vehicle to a constrained ground range and altitude. The guidance algorithm is divided into two parts: 1) computation of a nominal, approximate, maximum terminal velocity trajectory to a constrained final altitude and computation of the resulting unconstrained groundrange, and 2) computation of the neighboring extremal control perturbation at the sample value of flight path angle to compensate for changes in the approximatemore » physical model and enable the vehicle to reach the on-board computed groundrange. The trajectories are characterized by glide and dive flight to the target to minimize the time spent in the denser parts of the atmosphere. The proposed on-line scheme successfully brings the final altitude and range constraints together, as well as compensates for differences in flight model, atmosphere, and aerodynamics at the expense of guidance update computation time. Comparison with an independent, parameter optimization solution for the terminal velocity is excellent. 6 refs., 3 figs.« less

Alkali metal nitrate purification

DOEpatents

Fiorucci, Louis C.; Morgan, Michael J.

1986-02-04

A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

Solid state RF power: The route to 1W per euro cent

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

Heid, Oliver

2013-04-19

In most particle accelerators RF power is a decisive design constraint due to high costs and relative inflexibility of current electron beam based RF sources, i.e. Klystrons, Magnetrons, Tetrodes etc. At VHF/UHF frequencies the transition to solid state devices promises to fundamentally change the situation. Recent progress brings 1 Watt per Euro cent installed cost within reach. We present a Silicon Carbide semiconductor solution utilising the Solid State Direct Drive technology at unprecedented efficiency, power levels and power densities. The proposed solution allows retrofitting of existing RF accelerators and opens the route to novel particle accelerator concepts.

Results of Copper-Silver Rail Materials Tests

DTIC Science & Technology

2006-05-01

dislocation-dense grain structure. An annealing, recrystallization , and re-straining model is proposed to predict the bandwidth within which the...darker phase is the copper-rich solid solution, while the lighter regions are the eutectic structure consisting of both copper-rich and silver-rich solid...solutions. The eutectic phase ribbons consist of finer copper and silver filaments [1], [5]. The two phases are inhomogeneously deformed during the

Community Solutions to Solid Waste Pollution. Operation Waste Watch: The New Three Rs for Elementary School. Grade 6. [Second Edition.

ERIC Educational Resources Information Center

Virginia State Dept. of Waste Management, Richmond. Div. of Litter & Recycling.

This publication, the last in a series of seven for elementary schools, is an environmental education curriculum guide with a focus on waste management issues. It contains a unit of exercises selected for sixth grade students focusing on community solutions to solid waste pollution. Waste management activities included in this unit seek to…

Phase Relations in Ternary Systems in the Subsolidus Region: Methods to Formulate Solid Solution Equations and to Find Particular Compositions

ERIC Educational Resources Information Center

Alvarez-Montan~o, Victor E.; Farías, Mario H.; Brown, Francisco; Mun~oz-Palma, Iliana C.; Cubillas, Fernando; Castillon-Barraza, Felipe F.

2017-01-01

A good understanding of ternary phase diagrams is required to advance and/or to reproduce experimental research in solid-state and materials chemistry. The aim of this paper is to describe the solutions to problems that appear when studying or determining ternary phase diagrams. A brief description of the principal features shown in phase diagrams…

Destruction of Navy Hazardous Wastes by Supercritical Water Oxidation

DTIC Science & Technology

1994-08-01

cleaning and derusting (nitrite and citric acid solutions), electroplating ( acids and metal bearing solutions), electronics and refrigeration... acid forming chemical species or that contain a large amount of dissolved solids present a challenge to current SCWO •-chnology. Approved for public...Waste streams that contain a large amount of mineral- acid forming chemical species or that contain a large amount of dissolved solids present a challenge

Performance evaluation of Space Shuttle SRB parachutes from air drop and scaled model wind tunnel tests. [Solid Rocket Booster recovery system

NASA Technical Reports Server (NTRS)

Moog, R. D.; Bacchus, D. L.; Utreja, L. R.

1979-01-01

The aerodynamic performance characteristics have been determined for the Space Shuttle Solid Rocket Booster drogue, main, and pilot parachutes. The performance evaluation on the 20-degree conical ribbon parachutes is based primarily on air drop tests of full scale prototype parachutes. In addition, parametric wind tunnel tests were performed and used in parachute configuration development and preliminary performance assessments. The wind tunnel test data are compared to the drop test results and both sets of data are used to determine the predicted performance of the Solid Rocket Booster flight parachutes. Data from other drop tests of large ribbon parachutes are also compared with the Solid Rocket Booster parachute performance characteristics. Parameters assessed include full open terminal drag coefficients, reefed drag area, opening characteristics, clustering effects, and forebody interference.

Microwave spectroscopic observation of multiple phase transitions in the bilayer electron solid in wide quantum wells

NASA Astrophysics Data System (ADS)

Hatke, Anthony; Engel, Lloyd; Liu, Yang; Shayegan, Mansour; Pfeiffer, Loren; West, Ken; Baldwin, Kirk

2015-03-01

The termination of the low Landau filling factor (ν) fractional quantum Hall series for a single layer two dimensional system results in the formation of a pinned Wigner solid for ν < 1 / 5. In a wide quantum well the system can support a bilayer state in which interlayer and intralayer interactions become comparable, which is measured in traditional transport as an insulating state for ν < 1 / 2. We perform microwave spectroscopic studies of this bilayer state and observe that this insulator exhibits a resonance, a signature of a solid phase. Additionally, we find that as we increase the density of the well at fixed ν this bilayer solid exhibits multiple sharp reductions in the resonance amplitude vs ν. This behavior is characteristic of multiple phase transitions, which remain hidden from dc transport measurements.

Chemical effects induced by gamma-irradiation in solid and in aqueous methanol solutions of 4-iodophenol

NASA Astrophysics Data System (ADS)

Mahfouz, R. M.; Siddiqui, M. R. H.; Al-Wassil, A. I.; Al-Resayes, S. I.; Al-Otaibi, A. M.

2005-05-01

The present work is a study on radiolyses of 4-iodophenol in aqueous methanol solutions. The radiolysis products are separated and identified using spectrophotometric and chromatographic techniques. The radiolytic products (I-2, I- and IO3-) formed in aerated solutions at room temperature were identified and the yields are investigated as a function of absorbed gamma-ray dose. The formation of I-2 is mainly dependent on the acidity of solution and produced via the pathway of secondary free radical reactions. Aromatic products of lower and higher molecular weight than the corresponding investigated compound were analysed and separated by HPLC. The results have been discussed in view of mechanisms based on free radicals and ion-molecule interactions. The chemical effects induced by gamma-irradiation in solid 4-iodophenol have also been investigated and the degradation products were identified in solid state by NMR, GC/MS experiments and HPLC after dissolution in aqueous methanol. The results were evaluated and compared with radiolysis data.

Influence of an americium solid phase on americium concentrations in solutions

NASA Astrophysics Data System (ADS)

Rai, Dhanpat; Strickert, R. G.; Moore, D. A.; Serne, R. J.

1981-11-01

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex)+] was found to be -4.12. The predictions based upon thermodynamic data suggest that Am (aq complex)+ is likely to be Am(OH) 2+. Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3(a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

Fluorous tagging strategy for solution-phase synthesis of small molecules, peptides and oligosaccharides

PubMed Central

Zhang, Wei

2005-01-01

The purification of reaction mixtures is a slow process in organic synthesis, especially during the production of large numbers of analogs and compound libraries. Phase-tag methods such as solid-phase synthesis and fluorous synthesis, provide efficient ways of addressing the separation issue. Fluorous synthesis employs functionalized perfluoroalkyl groups attached to substrates or reagents. The separation of the resulting fluorous molecules can be achieved using strong and selective fluorous liquid-liquid extraction, fluorous silica gel-based solid-phase extraction or high-performance liquid chromatography. Fluorous technology is a novel solution-phase method, which has the advantages of fast reaction times in homogeneous environments, being readily adaptable to literature conditions, having easy intermediate analysis, and having flexibility in reaction scale and scope. In principle, any synthetic methods that use a solid-support could be conducted in solution-phase by replacing the polymer linker with a corresponding fluorous tag. This review summarizes the progress of fluorous tags in solution-phase synthesis of small molecules, peptides and oligosaccharides. PMID:15595439

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

Nucleation-controlled microstructures and anomalous eutectic formation in undercooled Co-Sn and Ni-Si eutectic melts

NASA Astrophysics Data System (ADS)

Li, Mingjun; Kuribayashi, Kazuhiko

2003-12-01

Co-20.5 at. pct Sn and Ni-21.4 at. pct Si eutectic alloys have been levitated and undercooled in an electromagnetic levitator (EML) and then solidified spontaneously at different undercoolings. The original surface and cross-sectional morphologies of these solidified samples consist of separate eutectic colonies regardless of melt undercooling, indicating that microstructures in the free solidification of the eutectic systems are nucleation controlled. Regular lamellae always grow from the periphery of an independent anomalous eutectic grain in each eutectic colony. This typical morphology shows that the basic unit should be a single eutectic colony, when discussing the solidification behavior. Special emphasis is focused on the anomalous eutectic formation after a significant difference in linear kinetic coefficients is recognized for terminal eutectic phases, in particular when a eutectic reaction contains a nonfaceted disordered solid solution and a faceted ordered intermetallic compound as the terminal eutectic phases. It is this remarkable difference in the linear kinetic coefficients that leads to a pronounced difference in kinetic undercoolings. The sluggish kinetics in the interface atomic attachment of the intermetallic compound originates the occurrence of the decoupled growth of two eutectic phases. Hence, the current eutectic models are modified to incorporate kinetic undercooling, in order to account for the competitive growth behavior of eutectic phases in a single eutectic colony. The critical condition for generating the decoupled growth of eutectic phases is proposed. Further analysis reveals that a dimensionless critical undercooling may be appropriate to show the tendency for the anomalous eutectic-forming ability when considering the difference in linear kinetic coefficients of terminal eutectic phases. This qualitative criterion, albeit crude with several approximations and assumptions, can elucidate most of the published experimental results with the correct order of magnitude. Solidification modes in some eutectic alloys are predicted on the basis of the present criterion. Future work that may result in some probable errors is briefly directed to improve the model.

Ab initio molecular dynamics simulations of the initial stages of solid-electrolyte interphase formation on lithium ion battery graphitic anodes.

PubMed

Leung, Kevin; Budzien, Joanne L

2010-07-07

The decomposition of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase (SEI) films at the solvent-graphitic anode interface is critical to lithium ion battery operations. Ab initio molecular dynamics simulations of explicit liquid EC/graphite interfaces are conducted to study these electrochemical reactions. We show that carbon edge terminations are crucial at this stage, and that achievable experimental conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decomposition products seen in experiments but not previously predicted.

Raman effect in multiferroic Bi5Fe1+xTi3-xO15 solid solutions: A temperature study

NASA Astrophysics Data System (ADS)

Rodríguez Aranda, Ma. Del Carmen; Rodríguez-Vázquez, Ángel G.; Salazar-Kuri, Ulises; Mendoza, María Eugenia; Navarro-Contreras, Hugo R.

2018-02-01

In this work, a Raman study of powder samples of multiferroic Bi5Fe1+xTi3-xO15 solid solutions and Bi6Fe2Ti3O18 as a function of temperature from 27 °C (room temperature) to 850 °C is presented. The values of x (i.e., the Fe composition) for the solid solutions were 1.0, 1.1, 1.3, and 1.4. The temperature coefficients of eight phonon frequencies were determined for all the samples. The large observed phonon broadenings with increasing temperature precluded the observation of several of the phonon bands above defined temperatures in the range of 200-700 °C depending on the sample. These phonon broadenings were explained on the basis of the Klemens model, which considers that the broadenings are due to the thermal expansion of the lattice with a major contribution in terms of magnitude from anharmonic phonon-phonon interactions. However, some evidence for the presence of several of the phonons persisted up to 800-850 °C. These solid solutions are expected to exhibit a ferroelectric-paraelectric phase transition at 742 to 750 °C and a ferromagnetic-antiferromagnetic transition at 426 °C. We also observed changes in the slopes of the temperature dependence of the phonon frequencies for the lines at 228 cm-1 for Bi5FeTi3O15 and 330 cm-1 for Bi6Fe2Ti3O18 at temperatures of 247 °C and 347 °C, respectively. No similar temperature-frequency slope changes indicative of possible phase transitions were observed for any of the phonon lines of the other three Bi5Fe1+xTi3-xO15 solid solutions examined.

In situ polymerization of monomers for polyphenylquinoxaline/graphite fiber composites

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1974-01-01

Methods currently used to prepare fiber reinforced, high temperature resistant polyphenylquinoxaline (PPQ) composites employ extremely viscous, low solids content solutions of high molecular weight PPQ polymers. An improved approach, described in this report, consists of impregnating the fiber with a solution of the appropriate monomers instead of a solution of previously synthesized high molecular weight polymer. Polymerization of the monomers occurs in situ on the fiber during the solvent removal and curing stages. The in situ polymerization approach greatly simplifies the fabrication of PPQ graphite fiber composites. The use of low viscosity monomeric type solutions facilitates fiber wetting, permits a high solids content, and eliminates the need for prior polymer synthesis.

Providing solid angle formalism for skyshine calculations.

PubMed

Gossman, Michael S; Pahikkala, A Jussi; Rising, Mary B; McGinley, Patton H

2010-08-17

We detail, derive and correct the technical use of the solid angle variable identified in formal guidance that relates skyshine calculations to dose-equivalent rate. We further recommend it for use with all National Council on Radiation Protection and Measurements (NCRP), Institute of Physics and Engineering in Medicine (IPEM) and similar reports documented. In general, for beams of identical width which have different resulting areas, within ± 1.0 % maximum deviation the analytical pyramidal solution is 1.27 times greater than a misapplied analytical conical solution through all field sizes up to 40 × 40 cm². Therefore, we recommend determining the exact results with the analytical pyramidal solution for square beams and the analytical conical solution for circular beams.

Task reports on developing techniques for scattering by 3D composite structures and to generate new solutions in diffraction theory using higher order boundary conditions

NASA Technical Reports Server (NTRS)

Volakis, John L.

1991-01-01

There are two tasks described in this report. First, an extension of a two dimensional formulation is presented for a three dimensional body of revolution. A Fourier series expansion of the vector electric and magnetic fields is employed to reduce the dimensionality of the system, and an exact boundary condition is employed to terminate the mesh. The mesh termination boundary is chosen such that it leads to convolutional boundary operators for low O(n) memory demand. Second, rigorous uniform geometrical theory of diffraction (UTD) diffraction coefficients are presented for a coated convex cylinder simulated with generalized impedance boundary conditions. Ray solutions are obtained which remain valid in the transition region and reduce uniformly those in the deep lit and shadow regions. A uniform asymptotic solution is also presented for observations in the close vicinity of the cylinder.

Sequential N-Terminal Pro-B-Type Natriuretic Peptide and High-Sensitivity Cardiac Troponin Measurements During Albumin Replacement in Patients With Severe Sepsis or Septic Shock.

PubMed

Masson, Serge; Caironi, Pietro; Fanizza, Caterina; Carrer, Sara; Caricato, Anselmo; Fassini, Paola; Vago, Tarcisio; Romero, Marilena; Tognoni, Gianni; Gattinoni, Luciano; Latini, Roberto

2016-04-01

Myocardial dysfunction is a frequent complication in patients with severe sepsis and can worsen the prognosis. We investigated whether circulating biomarkers related to myocardial function and injury predicted outcome and were associated with albumin replacement. A multicenter, randomized clinical trial about albumin replacement in severe sepsis or septic shock (the Albumin Italian Outcome Sepsis trial). Forty ICUs in Italy. Nine hundred and ninety-five patients with severe sepsis or septic shock. Randomization to albumin and crystalloid solutions or crystalloid solutions alone. Plasma concentrations of N- terminal pro-B-type natriuretic peptide and high-sensitivity cardiac troponin T were measured 1, 2, and 7 days after enrollment. We tested the relationship of single marker measurements or changes over time with clinical events, organ dysfunctions, albumin replacement, and ICU or 90-day mortality in the overall population and after stratification by shock. N-terminal pro-B-type natriuretic peptide levels were abnormal in 97.4% of the patients and high-sensitivity cardiac troponin T in 84.5%, with higher concentrations in those with shock. After extensive adjustments, N-terminal pro-B-type natriuretic peptide concentrations predicted ICU or 90-day mortality, better than high-sensitivity cardiac troponin T. Early changes in N-terminal pro-B-type natriuretic peptide or high-sensitivity cardiac troponin T concentrations were independently associated with subsequent mortality in patients with shock. Patients given albumin had significantly higher N-terminal pro-B-type natriuretic peptide levels; in addition, early rise in N-terminal pro-B-type natriuretic peptide was associated with a better outcome in this subgroup. Circulating N-terminal pro-B-type natriuretic peptide and high-sensitivity cardiac troponin T are frequently elevated in severe sepsis or septic shock and have relevant prognostic value, which may be important in monitoring the clinical efficacy of supporting therapy.

Experimental study of the Ca-Mg-Zn system using diffusion couples and key alloys

NASA Astrophysics Data System (ADS)

Zhang, Yi-Nan; Kevorkov, Dmytro; Bridier, Florent; Medraj, Mamoun

2011-03-01

Nine diffusion couples and 32 key samples were prepared to map the phase diagram of the Ca-Mg-Zn system. Phase relations and solubility limits were determined for binary and ternary compounds using scanning electron microscopy, electron probe microanalysis and x-ray diffraction (XRD). The crystal structure of the ternary compounds was studied by XRD and electron backscatter diffraction. Four ternary intermetallic (IM) compounds were identified in this system: Ca3MgxZn15-x (4.6<=x<=12 at 335 °C, IM1), Ca14.5Mg15.8Zn69.7 (IM2), Ca2Mg5Zn13 (IM3) and Ca1.5Mg55.3Zn43.2 (IM4). Three binary compounds were found to have extended solid solubility into ternary systems: CaZn11, CaZn13 and Mg2Ca form substitutional solid solutions where Mg substitutes for Zn atoms in the first two compounds, and Zn substitutes for both Ca and Mg atoms in Mg2Ca. The isothermal section of the Ca-Mg-Zn phase diagram at 335 °C was constructed on the basis of the obtained experimental results. The morphologies of the diffusion couples in the Ca-Mg-Zn phase diagram at 335 °C were studied. Depending on the terminal compositions of the diffusion couples, the two-phase regions in the diffusion zone have either a tooth-like morphology or contain a matrix phase with isolated and/or dendritic precipitates.

Determination of Aromatic Amines Using Solid-Phase Microextraction Based on an Ionic Liquid-Mediated Sol–Gel Technique

PubMed Central

Abbasi, Vajihe; Sarafraz-Yazdi, Ali; Amiri, Amirhassan; Vatani, Hossein

2016-01-01

A headspace solid-phase microextraction (HS-SPME) method was developed for isolation of monocyclic aromatic amines from water samples followed by gas chromatography–flame ionization detector (GC–FID). In this work, the effect of the presence of ionic liquid (namely, 1-hexyl-3-methyl-imidazolium hexafluorophosphate [C6MIM][PF6]) was investigated in the sol–gel coating solutions on the morphology and extraction behavior of the resulting hybrid organic–inorganic sol–gel sorbents utilized in SPME. Hydroxy-terminated poly(dimethylsiloxane) (PDMS) was used as the sol–gel active organic component for sol–gel hybrid coatings. Two different coated fibers that were prepared are PDMS and PDMS-IL ([C6MIM][PF6]) fibers. Under the optimal conditions, the method detection limits (S/N = 3) with PDMS-IL were in the range of 0.001–0.1 ng/mL and the limits of quantification (S/N = 10) between 0.005 and 0.5 ng/mL. The relative standard deviations for one fiber (n = 5) were obtained from 3.1 up to 8.5% and between fibers or batch to batch (n = 3) in the range of 5.3–10.1%. The developed method was successfully applied to real water and juice fruits samples while the relative recovery percentages obtained for the spiked water samples at 0.1 ng/mL were from 83.3 to 95.0%. PMID:26759488

Synthesis and structure analysis of ferrocene-containing pseudopeptides.

PubMed

Angelici, Gaetano; Górecki, Marcin; Pescitelli, Gennaro; Zanna, Nicola; Monari, Magda; Tomasini, Claudia

2017-10-23

Ferrocene with its aromaticity and facile redox properties is an attractive moiety to be incorporated into functional moieties. Medicinal applications of ferrocene are well known and ferrocene itself shows cytotoxic and antianemic properties. In this article, we will describe the synthesis and the structure analysis of two pseudopeptides containing a ferrocene moiety as N-terminal group. After purification, Fc-l-Phe-d-Oxd-OBn [l-Phel-phenylalanine; d-Oxd(4R,5S)-4-Methyl-5-carboxy-oxazolidin-2-one] appears as bright brown solid that spontaneously forms brown needles. The X-ray diffraction of the crystals shows the presence of strong π interactions between the ferrocenyl moiety and the phenyl rings, while no NH•••OC hydrogen bonds are formed. This result is confirmed by FT-IR and 1 H NMR analysis. In contrast, both FT-IR and 1 H NMR analysis suggest that Fc-(l-Phe-d-Oxd) 2 -OBn forms a turn conformation stabilized by intramolecular NH•••OC hydrogen bonds in solution. Chiroptical spectroscopies (ECD and VCD) substantially confirmed the absence of a well-defined folded structure. The presence of the Fc moiety is responsible for specific ECD signals, one of which displayed pronounced temperature dependence and is directly related with the helicity assumed by the Fc core. Solid-state ECD spectra were recorded and rationalized on the basis of the X-ray geometry and quantum-mechanical calculations. © 2017 Wiley Periodicals, Inc.

Thiolated graphene - a new platform for anchoring CdSe quantum dots for hybrid heterostructures

NASA Astrophysics Data System (ADS)

Debgupta, Joyashish; Pillai, Vijayamohanan K.

2013-04-01

Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe QD attachment to any graphene surface has remarkable implications in designing hybrid heterostructures.Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe QD attachment to any graphene surface has remarkable implications in designing hybrid heterostructures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00363a

Planet Patrol. An Environmental Unit on Solid Waste Solutions for Grades 4-6.

ERIC Educational Resources Information Center

Procter and Gamble Educational Services, Cincinnati, OH.

This classroom unit was developed for use in grades 4-6 to help teach the concept of solid waste management. The teacher's guide provides an overview of the issue of solid waste disposal, a description of government, industry, and consumer roles in resolving the solid waste issue, and four lessons involving sanitary landfills, the reduction of…

Evaluation of Heavy-Chain C-Terminal Deletion on Product Quality and Pharmacokinetics of Monoclonal Antibodies.

PubMed

Jiang, Guoying; Yu, Christopher; Yadav, Daniela B; Hu, Zhilan; Amurao, Annamarie; Duenas, Eileen; Wong, Marc; Iverson, Mark; Zheng, Kai; Lam, Xanthe; Chen, Jia; Vega, Roxanne; Ulufatu, Sheila; Leddy, Cecilia; Davis, Helen; Shen, Amy; Wong, Pin Y; Harris, Reed; Wang, Y John; Li, Dongwei

2016-07-01

Due to their potential influence on stability, pharmacokinetics, and product consistency, antibody charge variants have attracted considerable attention in the biotechnology industry. Subtle to significant differences in the level of charge variants and new charge variants under various cell culture conditions are often observed during routine manufacturing or process changes and pose a challenge when demonstrating product comparability. To explore potential solutions to control charge heterogeneity, monoclonal antibodies (mAbs) with native, wild-type C-termini, and mutants with C-terminal deletions of either lysine or lysine and glycine were constructed, expressed, purified, and characterized in vitro and in vivo. Analytical and physiological characterization demonstrated that the mAb mutants had greatly reduced levels of basic variants without decreasing antibody biologic activity, structural stability, pharmacokinetics, or subcutaneous bioavailability in rats. This study provides a possible solution to mitigate mAb heterogeneity in C-terminal processing, improve batch-to-batch consistency, and facilitate the comparability study during process changes. Published by Elsevier Inc.

Solution Structure of Enterocin HF, an Antilisterial Bacteriocin Produced by Enterococcus faecium M3K31.

PubMed

Arbulu, Sara; Lohans, Christopher T; van Belkum, Marco J; Cintas, Luis M; Herranz, Carmen; Vederas, John C; Hernández, Pablo E

2015-12-16

The solution structure of enterocin HF (EntHF), a class IIa bacteriocin of 43 amino acids produced by Enterococcus faecium M3K31, was evaluated by CD and NMR spectroscopy. Purified EntHF was unstructured in water, but CD analysis supports that EntHF adopts an α-helical conformation when exposed to increasing concentrations of trifluoroethanol. Furthermore, NMR spectroscopy indicates that this bacteriocin adopts an antiparallel β-sheet structure in the N-terminal region (residues 1-17), followed by a well-defined central α-helix (residues 19-30) and a more disordered C-terminal end (residues 31-43). EntHF could be structurally organized into three flexible regions that might act in a coordinated manner. This is in agreement with the absence of long-range nuclear Overhauser effect signals between the β-sheet domain and the C-terminal end of the bacteriocin. The 3D structure recorded for EntHF fits emerging facts regarding target recognition and mode of action of class IIa bacteriocins.

The structure of neuronal calcium sensor-1 in solution revealed by molecular dynamics simulations.

PubMed

Bellucci, Luca; Corni, Stefano; Di Felice, Rosa; Paci, Emanuele

2013-01-01

Neuronal calcium sensor-1 (NCS-1) is a protein able to trigger signal transduction processes by binding a large number of substrates and re-shaping its structure depending on the environmental conditions. The X-ray crystal structure of the unmyristoilated NCS-1 shows a large solvent-exposed hydrophobic crevice (HC); this HC is partially occupied by the C-terminal tail and thus elusive to the surrounding solvent. We studied the native state of NCS-1 by performing room temperature molecular dynamics (MD) simulations starting from the crystal and the solution structures. We observe relaxation to a state independent of the initial structure, in which the C-terminal tail occupies the HC. We suggest that the C-terminal tail shields the HC binding pocket and modulates the affinity of NCS-1 for its natural targets. By analyzing the topology and nature of the inter-residue potential energy, we provide a compelling description of the interaction network that determines the three-dimensional organization of NCS-1.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1993-07-27

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1991-12-10

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

Activities of the components in a spinel solid solution of the Fe-Al-O system

NASA Astrophysics Data System (ADS)

Lykasov, A. A.; Kimyashev, A. A.

2011-09-01

The conditions of the equilibrium between the Fe3O4-FeAl2O4 solution and wustite are determined by measuring the EMF of galvanic cells containing a solid electrolyte, and the activities of the components in the Fe3O4-FeAl2O4 solution are calculated by treating the results of the experiment on the equilibrium between the spinel solution and wustite. Their properties are found to be different from those of ideal solutions at temperatures of 1000-1300 K. A significant positive deviation from the Raoult's law is believed to indicate the tendency of the solution to decompose. The experimental data are treated in terms of the theory of regular solutions, assuming the energy of mixing to be a function of temperature only. The critical temperature of decomposition for the Fe3O4-FeAl2O4 solution is found to be 1084 K.

Solution-processed ultrathin chemically derived graphene films as soft top contacts for solid-state molecular electronic junctions.

PubMed

Li, Tao; Hauptmann, Jonas Rahlf; Wei, Zhongming; Petersen, Søren; Bovet, Nicolas; Vosch, Tom; Nygård, Jesper; Hu, Wenping; Liu, Yunqi; Bjørnholm, Thomas; Nørgaard, Kasper; Laursen, Bo W

2012-03-08

A novel method using solution-processed ultrathin chemically derived graphene films as soft top contacts for the non-destructive fabrication of molecular junctions is demonstrated. We believe this protocol will greatly enrich the solid-state test beds for molecular electronics due to its low-cost, easy-processing and flexible nature. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lunar Rotation and the Lunar Interior

NASA Technical Reports Server (NTRS)

Williams, J. G.; Boggs, D. H.; Ratcliff, J. T.; Dickey, J. O.

2003-01-01

Variations in rotation and orientation of the Moon are sensitive to solid-body tidal dissipation, dissipation due to relative motion at the fluid-core/ solid-mantle boundary, and tidal Love number k2. There is weaker sensitivity to flattening of the core-mantle boundary (CMB) and fluid core moment of inertia. Accurate Lunar Laser Ranging (LLR) measurements of the distance from observatories on the Earth to four retroreflector arrays on the Moon are sensitive to lunar rotation and orientation variations and tidal displacements. Past solutions using the LLR data have given results for dissipation due to solid-body tides and fluid core plus Love number. Past detection of CMB flattening has been marginal but is improving, while direct detection of the core moment has not yet been achieved. Three decades of Lunar Laser Ranging (LLR) data are analyzed using a weighted least-squares approach. The lunar solution parameters include dissipation at the fluid-core/solid-mantle boundary, tidal dissipation, dissipation-related coefficients for rotation and orientation terms, potential Love number k2, a correction to the constant term in the tilt of the equator to the ecliptic which is meant to approximate the influence of core-mantle boundary flattening, and displacement Love numbers h2 and l2. Several solutions, with different combinations of solution parameters and constraints, are considered.

Fe–Ni solid solutions in nano-size dimensions: Effect of hydrogen annealing

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

Kumar, Asheesh, E-mail: asheeshk@barc.gov.in; Meena, S.S.; Banerjee, S.

Highlights: • Fe–Ni solid solution with nano-size dimensions were prepared and characterized. • Both as prepared and hydrogenated solid solutions have FCC structure of Ni. • Paramagnetic and ferromagnetic domains coexist in these samples. - Abstract: Nanoparticles of Ni{sub 0.50}Fe{sub 0.50} and Ni{sub 0.75}Fe{sub 0.25} alloys were prepared by chemical reduction in ethylene glycol medium. XRD and {sup 57}Fe Mössbauer studies have confirmed the formation of Fe–Ni solid solution in nano-size dimensions with FCC structure. These samples consist of both ferromagnetic and paramagnetic domains which have been attributed to the coexistence of large and small particles as confirmed by atomicmore » force microscopic (AFM) and {sup 57}Fe Mössbauer spectroscopic studies. Improved extent of Fe–Fe exchange interaction existing in Ni{sub 0.50}Fe{sub 0.50} alloy compared to Ni{sub 0.75}Fe{sub 0.25} alloy explains the observed increase in the relative extent of ferromagnetic domains compared to paramagnetic domains in the former sample. Increase in the relative extent of ferromagnetic domains for hydrogenated alloys is due to increase in particle size brought about by the high temperature activation prior to hydrogenation.« less

Bi2MoxW1-xO6 solid solutions with tunable band structure and enhanced visible-light photocatalytic activities

NASA Astrophysics Data System (ADS)

Li, Wenqi; Ding, Xingeng; Wu, Huating; Yang, Hui

2018-07-01

Semiconductor photocatalysis is an effective green way to combat water pollution. For the first time, this study reports a novel method to develop Bi2MoxW1-xO6 solid solution with microsphere structure through anion-exchange method. All Bi2MoxW1-xO6 samples exhibit an Aurivillius-type crystal structure without any secondary phase, confirming that in complete solid solutions as the value of x increases, the band gap energy of Bi2MoxW1-xO6 solid solutions decreases, while the optical absorption edge moves to longer wavelength. The Raman spectra research shows an increase in orthorhombic distortion with progressive replacement of W sites in Bi2WO6 with Mo6+ ions. Compared to Bi2MoO6 and Bi2WO6 samples, Bi2Mo0.4W0.6O6 sample displayed best photocatalytic activity and cycling stability for degradation of RhB dye. The enhanced photocatalytic activity of Bi2Mo0.4W0.6O6 sample can be synergetically linked to hierarchical hollow structure, enhanced light absorbance, and high carrier-separation efficiency. Additionally, the hollow Bi2MoxW1-xO6 microspheres formation can be attributed to the Kirkendall effect.

Theoretical prediction of morphotropic compositions in Na1/2Bi1/2TiO3-based solid solutions from transition pressures

NASA Astrophysics Data System (ADS)

Gröting, Melanie; Albe, Karsten

2014-02-01

In this article we present a method based on ab initio calculations to predict compositions at morphotropic phase boundaries in lead-free perovskite solid solutions. This method utilizes the concept of flat free energy surfaces and involves the monitoring of pressure-induced phase transitions as a function of composition. As model systems, solid solutions of Na1/2Bi1/2TiO3 with the alkali substituted Li1/2Bi1/2TiO3 and K1/2Bi1/2TiO3 and the alkaline earth substituted CaTiO3 and BaTiO3 are chosen. The morphotropic compositions are identified by determining the composition at which the phase transition pressure equals zero. In addition, we discuss the different effects of hydrostatic pressure (compression and tension) and chemical substitution on the antiphase tilts about the [111] axis (a-a-a-) present in pure Na1/2Bi1/2TiO3 and how they develop in the two solid solutions Na1/2Bi1/2TiO3-CaTiO3 and Na1/2Bi1/2TiO3-BaTiO3. Finally, we discuss the advantages and shortcomings of this simple computational approach.

A study of room-temperature LixMn1.5Ni0.5O4 solid solutions

PubMed Central

Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; Chen, Guoying

2015-01-01

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature LixMn1.5Ni0.5O4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of LixMn1.5Ni0.5O4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn1.5Ni0.5O4 (Phase I), Li0.5Mn1.5Ni0.5O4 (Phase II) and Mn1.5Ni0.5O4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. The work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance. PMID:25619504

A study of room-temperature Li xMn 1.5Ni 0.5O 4 solid solutions

DOE PAGES

Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert; ...

2015-01-26

Understanding the kinetic implication of solid-solution vs. biphasic reaction pathways is critical for the development of advanced intercalation electrode materials. Yet this has been a long-standing challenge in materials science due to the elusive metastable nature of solid solution phases. The present study reports the synthesis, isolation, and characterization of room-temperature Li xMn 1.5Ni 0.5O 4 solid solutions. In situ XRD studies performed on pristine and chemically-delithiated, micron-sized single crystals reveal the thermal behavior of Li xMn 1.5Ni 0.5O 4 (0 ≤ x ≤ 1) cathode material consisting of three cubic phases: LiMn 1.5Ni 0.5O 4 (Phase I), Li 0.5Mnmore » 1.5Ni 0.5O 4 (Phase II) and Mn 1.5Ni 0.5O 4 (Phase III). A phase diagram capturing the structural changes as functions of both temperature and Li content was established. In conclusion, the work not only demonstrates the possibility of synthesizing alternative electrode materials that are metastable in nature, but also enables in-depth evaluation on the physical, electrochemical and kinetic properties of transient intermediate phases and their role in battery electrode performance.« less

High-throughput 96-well solvent mediated sonic blending synthesis and on-plate solid/solution stability characterization of pharmaceutical cocrystals.

PubMed

Luu, Van; Jona, Janan; Stanton, Mary K; Peterson, Matthew L; Morrison, Henry G; Nagapudi, Karthik; Tan, Helming

2013-01-30

A 96-well high-throughput cocrystal screening workflow has been developed consisting of solvent-mediated sonic blending synthesis and on-plate solid/solution stability characterization by XRPD. A strategy of cocrystallization screening in selected blend solvents including water mixtures is proposed to not only manipulate solubility of the cocrystal components but also differentiate physical stability of the cocrystal products. Caffeine-oxalic acid and theophylline-oxalic acid cocrystals were prepared and evaluated in relation to saturation levels of the cocrystal components and stability of the cocrystal products in anhydrous and hydrous solvents. AMG 517 was screened with a number of coformers, and solid/solution stability of the resulting cocrystals on the 96-well plate was investigated. A stability trend was observed and confirmed that cocrystals comprised of lower aqueous solubility coformers tended to be more stable in water. Furthermore, cocrystals which could be isolated under hydrous solvent blending condition exhibited superior physical stability to those which could only be obtained under anhydrous condition. This integrated HTS workflow provides an efficient route in an API-sparing approach to screen and identify cocrystal candidates with proper solubility and solid/solution stability properties. Copyright © 2012 Elsevier B.V. All rights reserved.

Application of a thiourea-containing task-specific ionic liquid for the solid-phase extraction cleanup of lead ions from red lipstick, pine leaves, and water samples.

PubMed

Saljooqi, Asma; Shamspur, Tayebeh; Mohamadi, Maryam; Mostafavi, Ali

2014-07-01

Here, task-specific ionic liquid solid-phase extraction is proposed for the first time. In this approach, a thiourea-functionalized ionic liquid is immobilized on the solid sorbent, multiwalled carbon nanotubes. These modified nanotubes packed into a solid-phase extraction column are used for the selective extraction and preconcentration of ultra-trace amounts of lead(II) from aqueous samples prior to electrothermal atomic absorption spectroscopy determination. The thiourea functional groups act as chelating agents for lead ions retaining them and so, give the selectivity to the sorbent. Elution of the retained ions can be performed using an acidic thiourea solution. The effects of experimental parameters including pH of the aqueous solution, type and amount of eluent, and the flow rates of sample and eluent solutions on the separation efficiency are investigated. The linear dependence of absorbance of lead on its concentration in the initial solution is in the range of 0.5-40.0 ng/mL with the detection limit of 0.13 ng/mL (3(Sb)/m, n = 10). The proposed method is applicable to the analysis of red lipstick, pine leaves, and water samples for their lead contents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CSBB-ConeExclusion, adapting structure based solution virtual screening to libraries on solid support.

PubMed

Shave, Steven; Auer, Manfred

2013-12-23

Combinatorial chemical libraries produced on solid support offer fast and cost-effective access to a large number of unique compounds. If such libraries are screened directly on-bead, the speed at which chemical space can be explored by chemists is much greater than that addressable using solution based synthesis and screening methods. Solution based screening has a large supporting body of software such as structure-based virtual screening tools which enable the prediction of protein-ligand complexes. Use of these techniques to predict the protein bound complexes of compounds synthesized on solid support neglects to take into account the conjugation site on the small molecule ligand. This may invalidate predicted binding modes, the linker may be clashing with protein atoms. We present CSBB-ConeExclusion, a methodology and computer program which provides a measure of the applicability of solution dockings to solid support. Output is given in the form of statistics for each docking pose, a unique 2D visualization method which can be used to determine applicability at a glance, and automatically generated PyMol scripts allowing visualization of protein atom incursion into a defined exclusion volume. CSBB-ConeExclusion is then exemplarically used to determine the optimum attachment point for a purine library targeting cyclin-dependent kinase 2 CDK2.

Structural and ferroelectric phase evolution in [KNbO3]1-x[BaNi1/2Nb1/2O3 -δ] x (x =0 ,0.1 )

NASA Astrophysics Data System (ADS)

Hawley, Christopher J.; Wu, Liyan; Xiao, Geoffrey; Grinberg, Ilya; Rappe, Andrew M.; Davies, Peter K.; Spanier, Jonathan E.

2017-08-01

The phase transition evolution for [KNbO3]1-x[BaNi1/2Nb1/2O3 -δ] x(x =0 ,0.1 ) is determined via complementary dielectric permittivity and Raman-scattering measurements. Raman scattering by optical phonons over the range of 100-1000 cm-1 for 83 K

Short-range order in the Ca sub 1-x La sub x F sub 2+x solid solution: 1:0:3 or 1:0:4 clusters

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

Laval, J.P.; Abaouz, A.; Frit, B.

1989-08-01

The defect structure of the Ca{sub 1-x}La{sub x}F{sub 2+x} solid solution (0 {le} x {le} 0.38) has been examined at room temperature by powder neutron diffraction. Two kinds of (xxx) interstitial anions, whose respective numbers increase linearly with increasing dopant cation concentration, have been found: one labeled F{sup 0} (x {approx} 0.41) is a true interstitial; the other labeled F{sup {prime}{double prime}} (x {approx} 0.31) can be considered a relaxed normal anion. Two 1:0:n defect clusters are compatible, within the experimental errors, with these results: the 1:0:3 (1V{sub F}, OF{prime}, 3F{sup {double prime}}, 2 La{sup 3+}) and the 1:0:4 (1V{submore » F}, OF{prime}, 4F{sup {double prime}}, 3La{sup 3+}) clusters. Charge balance considerations and comparisons with the homologous Ca{sub 1-x}M{sub x}{sup IV}F{sub 2+2x} solid solutions (M{sup IV} = Th, U) allow us to think that the less dense 1:0:3 cluster is present for the whole domain of both kinds of solid solutions.« less

High Hydrogen Content Graphene Hydride Compounds & High Cross-­ Section Cladding Coatings for Fast Neutron Detection

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

Chandrashekhar, MVS

The objective is to develop and implement a superior low-cost, large area (potentially >32in), easily deployable, close proximity, harsh environment innovative neutron sensor needed for next generation fuel cycle monitoring. We will exploit recent breakthroughs at the PI’s lab on the electrochemistry of epitaxial graphene (EG) formed on commercial SiC wafers, a transformative nanomaterial system with superior radiation detection and durability properties to develop a new paradigm in detection for fast neutrons, a by-product of fission reactors. There are currently few effective detection/monitoring schemes, especially solid-state ones at present. This is essential for monitoring and control of future fuel cyclesmore » to make them more efficient and reliable. By exploiting these novel materials, as well as innovative hybrid SiC/EG/Cladding device architectures conceived by the team, will develop low-cost, high performance solutions to fast-neutron detection. Finally, we will also explore 3-terminal device implementations for neutron detectors with built-in electronic gain to further shrink these devices and improve their sensitivity.« less

Phase Equilibria of Sn-Co-Cu Ternary System

NASA Astrophysics Data System (ADS)

Chen, Yu-Kai; Hsu, Chia-Ming; Chen, Sinn-Wen; Chen, Chih-Ming; Huang, Yu-Chih

2012-10-01

Sn-Co-Cu ternary alloys are promising lead-free solders, and isothermal sections of Sn-Co-Cu phase equilibria are fundamentally important for the alloys' development and applications. Sn-Co-Cu ternary alloys were prepared and equilibrated at 523 K, 1073 K, and 1273 K (250 °C, 800 °C, and 1000 °C), and the equilibrium phases were experimentally determined. In addition to the terminal solid solutions and binary intermetallic compounds, a new ternary compound, Sn3Co2Cu8, was found. The solubilities of Cu in the α-CoSn3 and CoSn2 phases at 523 K (250 °C) are 4.2 and 1.6 at. pct, respectively, while the Cu solubility in the α-Co3Sn2 phase is as high as 20.0 at. pct. The Cu solubility increases with temperature and is around 30.0 at. pct in the β-Co3Sn2 at 1073 K (800 °C). The Co solubility in the η-Cu6Sn5 phase is also significant and is 15.5 at. pct at 523 K (250 °C).

Charge transport and intrinsic fluorescence in amyloid-like fibrils

PubMed Central

del Mercato, Loretta Laureana; Pompa, Pier Paolo; Maruccio, Giuseppe; Torre, Antonio Della; Sabella, Stefania; Tamburro, Antonio Mario; Cingolani, Roberto; Rinaldi, Ross

2007-01-01

The self-assembly of polypeptides into stable, conductive, and intrinsically fluorescent biomolecular nanowires is reported. We have studied the morphology and electrical conduction of fibrils made of an elastin-related polypeptide, poly(ValGlyGlyLeuGly). These amyloid-like nanofibrils, with a diameter ranging from 20 to 250 nm, result from self-assembly in aqueous solution at neutral pH. Their morphological properties and conductivity have been investigated by atomic force microscopy, scanning tunneling microscopy, and two-terminal transport experiments at the micro- and nanoscales. We demonstrate that the nanofibrils can sustain significant electrical conduction in the solid state at ambient conditions and have remarkable stability. We also show intrinsic blue-green fluorescence of the nanofibrils by confocal microscopy analyses. These results indicate that direct (label-free) excitation can be used to investigate the aggregation state or the polymorphism of amyloid-like fibrils (and possibly of other proteinaceous material) and open up interesting perspectives for the use of peptide-based nanowire structures, with tunable physical and chemical properties, for a wide range of nanobiotechnological and bioelectronic applications. PMID:17984067

Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes.

PubMed

Xu, Chao; Hedin, Niklas; Shi, Hua-Tian; Xin, ZhiFeng; Zhang, Qian-Feng

2015-04-14

Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

Bioavailable cadmium during the bioremediation of phenanthrene-contaminated soils using the diffusive gradients in thin-film technique.

PubMed

Amezcua-Allieri, M A; Rodríguez-Vázquez, R

2006-03-01

To study the impact of fungal bioremediation of phenanthrene on trace cadmium solid-solution fluxes and solution phase concentration. The bioremediation of phenanthrene in soils was performed using the fungus Penicillium frequentans. Metal behaviour was evaluated by the techniques of diffusive gradient in thin-films (DGT) and filtration. Fluxes of cadmium (Cd) show a significant (P < 0.002) increase after the start of bioremediation, indicating that the bioremediation process itself releases significant amount of Cd into solution from the soil solid-phase. Unlike DGT devices, the solution concentration from filtration shows a clear bimodal distribution. We postulate that the initial action of the fungi is most likely to breakdown the surface of the solid phase to smaller, 'solution-phase' material (<0.45 microm) leading to a peak in Cd concentration in solution. Phenanthrene removal from soils by bioremediation ironically results in the mobilization of another toxic pollutant (Cd). Bioremediation of organic pollutants in contaminated soil will likely lead to large increases in the mobilization of toxic metals, increasing metal bio-uptake and incorporation into the wider food chain. Bioremediation strategies need to account for this behaviour and further research is required both to understand the generality of this behaviour and the operative mechanisms.

The dominant role of side chains in supramolecular double helical organisation in synthetic tripeptides

NASA Astrophysics Data System (ADS)

Sharma, Ankita; Tiwari, Priyanka; Dutt Konar, Anita

2018-06-01

Peptide self-assembled nanostructures have attracted attention recently owing to their promising applications in diversified avenues. To validate the importance of sidechains in supramolecular architectural stabilization, herein this report describes the self-assembly propensities involving weak interactions in a series of model tripeptides Boc-Xaa-Aib-Yaa-OMe I-IV, (where Xaa = 4-F-Phe/NMeSer/Ile & Yaa = Tyr in peptide I-III respectively and Xaa = 4-F-Phe & Yaa = Ile in peptide IV) differing in terminal side chains. The solid state structural analysis reveals that tripeptide (I) displays supramolecular preference for double helical architecture. However, when slight modification has been introduced in the N-terminal side chains disfavour the double helical organisation (Peptide II and III). Indeed the peptides display sheet like ensemble within the framework. Besides replacement of C-terminal Tyr by Ile in peptide I even do not promote the architecture, emphasizing the dominant role of balance of side chains in stabilizing double helical organisation. The CD measurements, concentration dependant studies, NMR titrations and ROESY spectra are well in agreement with the solid state conformational investigation. Moreover the morphological experiments utilizing FE-SEM, support the heterogeneity present in the peptides. Thus this work may not only hold future promise in understanding the structure and function of neurodegenerative diseases but also assist in rational design of protein modification in biologically active peptides.

Ion conducting fluoropolymer carbonates for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

2017-09-05

Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

40 CFR 264.280 - Closure and post-closure care.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 25 2010-07-01 2010-07-01 false Closure and post-closure care. 264.280 Section 264.280 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES... § 264.278, except that soil-pore liquid monitoring may be terminated 90 days after the last application...

New microwave spectrometer/imager has possible applications for pollution monitoring

NASA Technical Reports Server (NTRS)

Tooley, R. D.

1970-01-01

Microwave imager forms thermal-emissivity image of solid portion of planet Venus and provides data on the planet's atmosphere, surface, terminator, and temperature changes. These thermally produced multifrequency microwaves for image production of temperature profiles can be applied to water pollution monitoring, agriculture, and forestry survey.

Cellular interface morphologies in directional solidification. III - The effects of heat transfer and solid diffusivity

NASA Technical Reports Server (NTRS)

Ungar, Lyle H.; Bennett, Mark J.; Brown, Robert A.

1985-01-01

The shape and stability of two-dimensional finite-amplitude cellular interfaces arising during directional solidification are compared for several solidification models that account differently for latent heat released at the interface, unequal thermal conductivities of melt and solid, and solute diffusivity in the solid. Finite-element analysis and computer-implemented perturbation methods are used to analyze the families of steadily growing cellular forms that evolve from the planar state. In all models a secondary bifurcation between different families of finite-amplitude cells exists that halves the spatial wavelength of the stable interface. The quantitative location of this transition is very dependent on the details of the model. Large amounts of solute diffusion in the solid retard the growth of large-amplitude cells.

Location-allocation models and new solution methodologies in telecommunication networks

NASA Astrophysics Data System (ADS)

Dinu, S.; Ciucur, V.

2016-08-01

When designing a telecommunications network topology, three types of interdependent decisions are combined: location, allocation and routing, which are expressed by the following design considerations: how many interconnection devices - consolidation points/concentrators should be used and where should they be located; how to allocate terminal nodes to concentrators; how should the voice, video or data traffic be routed and what transmission links (capacitated or not) should be built into the network. Including these three components of the decision into a single model generates a problem whose complexity makes it difficult to solve. A first method to address the overall problem is the sequential one, whereby the first step deals with the location-allocation problem and based on this solution the subsequent sub-problem (routing the network traffic) shall be solved. The issue of location and allocation in a telecommunications network, called "The capacitated concentrator location- allocation - CCLA problem" is based on one of the general location models on a network in which clients/demand nodes are the terminals and facilities are the concentrators. Like in a location model, each client node has a demand traffic, which must be served, and the facilities can serve these demands within their capacity limit. In this study, the CCLA problem is modeled as a single-source capacitated location-allocation model whose optimization objective is to determine the minimum network cost consisting of fixed costs for establishing the locations of concentrators, costs for operating concentrators and costs for allocating terminals to concentrators. The problem is known as a difficult combinatorial optimization problem for which powerful algorithms are required. Our approach proposes a Fuzzy Genetic Algorithm combined with a local search procedure to calculate the optimal values of the location and allocation variables. To confirm the efficiency of the proposed algorithm with respect to the quality of solutions, significant size test problems were considered: up to 100 terminal nodes and 50 concentrators on a 100 × 100 square grid. The performance of this hybrid intelligent algorithm was evaluated by measuring the quality of its solutions with respect to the following statistics: the standard deviation and the ratio of the best solution obtained.

C-Terminal Protein Characterization by Mass Spectrometry: Isolation of C-Terminal Fragments from Cyanogen Bromide-Cleaved Protein

PubMed Central

Nika, Heinz; Hawke, David H.; Angeletti, Ruth Hogue

2014-01-01

A sample preparation method for protein C-terminal peptide isolation from cyanogen bromide (CNBr) digests has been developed. In this strategy, the analyte was reduced and carboxyamidomethylated, followed by CNBr cleavage in a one-pot reaction scheme. The digest was then adsorbed on ZipTipC18 pipette tips for conjugation of the homoserine lactone-terminated peptides with 2,2′-dithiobis (ethylamine) dihydrochloride, followed by reductive release of 2-aminoethanethiol from the derivatives. The thiol-functionalized internal and N-terminal peptides were scavenged on activated thiol sepharose, leaving the C-terminal peptide in the flow-through fraction. The use of reversed-phase supports as a venue for peptide derivatization enabled facile optimization of the individual reaction steps for throughput and completeness of reaction. Reagents were replaced directly on the support, allowing the reactions to proceed at minimal sample loss. By this sequence of solid-phase reactions, the C-terminal peptide could be recognized uniquely in mass spectra of unfractionated digests by its unaltered mass signature. The use of the sample preparation method was demonstrated with low-level amounts of a whole, intact model protein. The C-terminal fragments were retrieved selectively and efficiently from the affinity support. The use of covalent chromatography for C-terminal peptide purification enabled recovery of the depleted material for further chemical and/or enzymatic manipulation. The sample preparation method provides for robustness and simplicity of operation and is anticipated to be expanded to gel-separated proteins and in a scaled-up format to high-throughput protein profiling in complex biological mixtures. PMID:24688319

Pseudomorphic Semiconducting Heterostructures from Combinations of AlN, GaN and Selected SiC Polytypes: Theoretical Advancement and its Coordination with Experimental Studies of Nucleation, Growth, Characterization and Device Development

DTIC Science & Technology

1994-06-01

simultaneously expluiting the favorable characteristics of these materials include the thin film deposition of both pseudomorphic beterostructure and alloys ...diagram proposed by Zangvil and Ruh [10] shows a flat miscibility gap at =1900*C between -20 and 80 wt % AIN. Above this temperature, a 2H solid solution...was reported from >20 wt % AIN. For .20 wt % AIN, 8 I I solutions and two phase mixtures of 6H, 4H, and 2H were observed. Thin film solid solutions

Metal/Metal Oxide Differential Electrode pH Sensors

NASA Technical Reports Server (NTRS)

West, William; Buehler, Martin; Keymeulen, Didier

2007-01-01

Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

Targeting BET bromodomain proteins in solid tumors

PubMed Central

Sahai, Vaibhav; Redig, Amanda J.; Collier, Katharine A.; Eckerdt, Frank D.; Munshi, Hidayatullah G.

2016-01-01

There is increasing interest in inhibitors targeting BET (bromodomain and extra-terminal) proteins because of the association between this family of proteins and cancer progression. BET inhibitors were initially shown to have efficacy in hematologic malignancies; however, a number of studies have now shown that BET inhibitors can also block progression of non-hematologic malignancies. In this Review, we summarize the efficacy of BET inhibitors in select solid tumors; evaluate the role of BET proteins in mediating resistance to current targeted therapies; and consider potential toxicities of BET inhibitors. We also evaluate recently characterized mechanisms of resistance to BET inhibitors; summarize ongoing clinical trials with these inhibitors; and discuss potential future roles of BET inhibitors in patients with solid tumors. PMID:27283767

Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles.

PubMed

Giuliani, J R; Harley, S J; Carter, R S; Power, P P; Augustine, M P

2007-08-01

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.

The Use of Aryl Hydrazide Linkers for the Solid Phase Synthesis of Chemically Modified Peptides

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

Woo, Y; Mitchell, A R; Camarero, J A

2006-11-03

Since Merrifield introduced the concept of solid phase synthesis in 1963 for the rapid preparation of peptides, a large variety of different supports and resin-linkers have been developed that improve the efficiency of peptide assembly and expand the myriad of synthetically feasible peptides. The aryl hydrazide is one of the most useful resin-linkers for the synthesis of chemically modified peptides. This linker is completely stable during Boc- and Fmoc-based solid phase synthesis and yet it can be cleaved under very mild oxidative conditions. The present article reviews the use of this valuable linker for the rapid and efficient synthesis ofmore » C-terminal modified peptides, head-to-tail cyclic peptides and lipidated peptides.« less

Compatibility and stability of tramadol and dexamethasone in solution and its use in terminally ill patients.

PubMed

Negro, S; Salama, A; Sánchez, Y; Azuara, M L; Barcia, E

2007-10-01

Delivery of drug admixtures by continuous subcutaneous infusion is common practice in palliative medicine, but analytical confirmation of their compatibility and stability is not always available. To study the compatibility and stability of tramadol hydrochloride and dexamethasone sodium phosphate combined in solution and to report on its use in terminally ill patients. Twelve different solutions containing tramadol hydrochloride (8.33-33.33 mg/mL) and dexamethasone sodium phosphate (0.33-3.33 mg/mL) were prepared in saline and stored in polypropylene syringes for 5 days (25 degrees C). Analysis was performed on days 1, 3 and 5 days with simultaneous determination by HPLC. pH was measured at 0 and 5 days. Clinical performance was assessed retrospectively in six terminal-ill oncology patients. Maximum losses of 7% and 6% were observed for tramadol and dexamethasone. Pain was completely controlled in four patients. Local tolerance resulted in haematoma in three patients, which resolved by switching to a butterfly insertion site. Tramadol hydrochloride (100-400 mg/day) and dexamethasone sodium phosphate (4-40 mg/day) are stable for at least 5 days when combined in saline and stored at 25 degrees C. These results are only valid for the type of syringes and the specific commercial preparations tested.