Estimation of the outer-sphere contribution to the activation volume for electron exchange reactions using the mean spherical approximation

NASA Astrophysics Data System (ADS)

Takagi, Hideo D.; Swaddle, Thomas W.

1996-01-01

The outer-sphere contribution to the volume of activation of homogeneous electron exchange reactions is estimated for selected solvents on the basis of the mean spherical approximation (MSA), and the calculated values are compared with those estimated by the Strank-Hush-Marcus (SHM) theory and with activation volumes obtained experimentally for the electron exchange reaction between tris(hexafluoroacetylacetonato)ruthenium(III) and -(II) in acetone, acetonitrile, methanol and chloroform. The MSA treatment, which recognizes the molecular nature of the solvent, does not improve significantly upon the continuous-dielectric SHM theory, which represents the experimental data adequately for the more polar solvents.

Excited-state redox properties of ruthenium(II) phthalocyanine from electron-transfer quenching

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

Prasad, D.R.; Ferraudi, G.

1982-09-30

Electron-transfer reactions between the lowest-lying triplet state, /sup 3/..pi pi../sup */, of ruthenium (phthalocyanine)(pyridine)/sub 2/ and various nitroaromatic compounds have been studied by laser and conventional flash photolysis. Quenching rate constants determined for the oxidation of the excited state have been treated according to the Marcus-Hush theory. A self-exchange rate constant K approx. 10/sup 7/ M/sup -1/ x/sup -1/ was determined for the self-exchange reaction between the /sup 3/..pi pi../sup */ and radical cation, Ru(ph)(py)/sub 2//sup +/. Such a value indicates that the major component to the Franck-Condon reorganizational energy is the outer-sphere contribution. The photochemical properties of the phthalocyaninesmore » are discussed in terms of the redox potentials estimate for various excited states.« less

Kinetics and mechanism of electron transfer reaction of single and double chain surfactant cobalt(III) complex by Fe2+ ions in liposome (dipalmitoylphosphotidylcholine) vesicles: effects of phase transition

NASA Astrophysics Data System (ADS)

Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi

2015-05-01

In this study, we report the kinetics of reduction reactions of single and double chain surfactant cobalt(III) complexes of octahedral geometry, cis-[Co(en)2(4AMP)(DA)](ClO4)3 and cis-[Co(dmp)2(C12H25NH2)2](ClO4)3 (en = ethylenediamine, dmp = 1,3-diaminopropane, 4AMP = 4-aminopropane, C12H25NH2 = dodecylamine) by Fe2+ ion in dipalmitoylphosphotidylcholine (DPPC) vesicles at different temperatures under pseudo first-order conditions. The kinetics of these reactions is followed by spectrophotometry method. The reactions are found to be second order and the electron transfer is postulated as outer sphere. The remarkable findings in the present investigation are that, below the phase transition temperature of DPPC, the rate decreases with an increase in the concentration of DPPC, while above the phase transition temperature the rate increases with an increase in the concentration of DPPC. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes. Besides, comparing the values of rate constants of these outer-sphere electron transfer reactions in the absence and in the presence of DPPC, the rate constant values in the presence of DPPC are always found to be greater than in the absence of DPPC. This is ascribed to the double hydrophobic fatty acid chain in the DPPC that gives the molecule an overall tubular shape due to the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes more suitable for vesicle aggregation which facilitates lower activation energy, and consequently higher rate is observed in the presence of DPPC. The activation parameters (ΔS# and ΔH#) of the reactions at different temperatures have been calculated which corroborate the kinetics of the reaction.

Reductive Outer-Sphere Single Electron Transfer Is an Exception Rather than the Rule in Natural and Engineered Chlorinated Ethene Dehalogenation.

PubMed

Heckel, Benjamin; Cretnik, Stefan; Kliegman, Sarah; Shouakar-Stash, Orfan; McNeill, Kristopher; Elsner, Martin

2017-09-05

Chlorinated ethenes (CEs) such as perchloroethylene, trichloroethylene and dichloroethylene are notorious groundwater contaminants. Although reductive dehalogenation is key to their environmental and engineered degradation, underlying reaction mechanisms remain elusive. Outer-sphere reductive single electron transfer (OS-SET) has been proposed for such different processes as Vitamin B 12 -dependent biodegradation and zerovalent metal-mediated dehalogenation. Compound-specific isotope effect ( 13 C/ 12 C, 37 Cl/ 35 Cl) analysis offers a new opportunity to test these hypotheses. Defined OS-SET model reactants (CO 2 radical anions, S 2- -doped graphene oxide in water) caused strong carbon (ε C = -7.9‰ to -11.9‰), but negligible chlorine isotope effects (ε Cl = -0.12‰ to 0.04‰) in CEs. Greater chlorine isotope effects were observed in CHCl 3 (ε C = -7.7‰, ε Cl = -2.6‰), and in CEs when the exergonicity of C-Cl bond cleavage was reduced in an organic solvent (reaction with arene radical anions in glyme). Together, this points to dissociative OS-SET (SET to a σ* orbital concerted with C-Cl breakage) in alkanes compared to stepwise OS-SET (SET to a π* orbital followed by C-Cl cleavage) in ethenes. The nonexistent chlorine isotope effects of chlorinated ethenes in all aqueous OS-SET experiments contrast strongly with pronounced Cl isotope fractionation in all natural and engineered reductive dehalogenations reported to date suggesting that OS-SET is an exception rather than the rule in environmental transformations of chlorinated ethenes.

Electron transfer reactivity of the aqueous iron(IV)–oxo complex. Outer-sphere vs proton-coupled electron transfer

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2016-06-18

Here, the kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, Fe IV(H 2O) 5O 2+ (hereafter Fe IV aqO 2+), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN) 3 2+ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS–/ABTS 2–, phenothiazines, Co II(dmgBF 2) 2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generatedmore » ligand-modified products. Fe IV aqO 2+ oxidizes even Ce(III) (E 0 in 1 M HClO 4 = 1.7 V) with a rate constant greater than 10 4 M –1 s –1. In 0.10 M aqueous HClO 4 at 25 °C, the reactions of Os(phen) 3 2+ (k = 2.5 × 10 5 M –1 s –1), IrCl 6 3– (1.6 × 10 6), ABTS 2– (4.7 × 10 7), and Fe(cp)(C 5H 4CH 2OH) (6.4 × 10 7) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen) 3 2+ and of ferrocenes remained unchanged in the acidity range 0.05 < [H+] < 0.10 M, ruling out prior protonation of Fe IV aqO 2+ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k 22 + E 0 Fe/0.059) = 17.2 ± 0.8, where k 22 and E 0 Fe are the self-exchange rate constant and reduction potential, respectively, for the Fe IV aqO 2+/Fe III aqO + couple. Comparison with literature work suggests k 22 < 10 –5 M –1 s –1 and thus E 0(Fe IV aqO 2+/Fe III aqO +) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E 0 (Fe IV aqO 2+, H +/Fe III aqOH 2+) ≥ 1.95 V.« less

MD studies of electron transfer at ambient and elevated pressures

NASA Astrophysics Data System (ADS)

Giles, Alex; Spooner, Jacob; Weinberg, Noham

2013-06-01

The effect of pressure on the rate constants of outer-sphere electron transfer reactions has often been described using the Marcus-Hush theory. This theory agrees well with experiment when internal reorganization of the ionic system is negligible, however it does not offer a recipe for calculation of the effects that result from significant solute restructuring. We have recently developed a molecular dynamics technique that accurately describes structural dependence of molecular volumes in non-polar and weakly polar systems. We are now extending this approach to the case of highly polar ionic systems where both solvent and solute restructuring components are important. For this purpose we construct pressure-dependent two-dimensional surfaces for electron transfer reactions in coordinate system composed of interionic distance and Marcus-type solvent polarization coordinate, and use these surfaces to describe pressure effects on reaction kinetics. R.A. Marcus. J. Chem. Phys. 24, 966 (1956); 24, 979 (1956); 26, 867 (1957). Discuss. Faraday Soc. 29, 21 (1960). Faraday Discuss. Chem. Soc. 74, 7 (1982); N.S. Hush. Trans. Faraday Soc. 57, 557 (1961).

Terahertz plasmon and surface-plasmon modes in hollow nanospheres

PubMed Central

2012-01-01

We present a theoretical study of the electronic subband structure and collective electronic excitation associated with plasmon and surface plasmon modes in metal-based hollow nanosphere. The dependence of the electronic subband energy on the sample parameters of the hollow nanosphere is examined. We find that the subband states with different quantum numbers l degenerate roughly when the outer radius of the sphere is r2 ≥ 100 nm. In this case, the energy spectrum of a sphere is mainly determined by quantum number n. Moreover, the plasmon and surface plasmon excitations can be achieved mainly via inter-subband transitions from occupied subbands to unoccupied subbands. We examine the dependence of the plasmon and surface-plasmon frequencies on the shell thickness d and the outer radius r2 of the sphere using the standard random-phase approximation. We find that when a four-state model is employed for calculations, four branches of the plasmon and surface plasmon oscillations with terahertz frequencies can be observed, respectively. PMID:23092121

Minimal proton channel enables H2 oxidation and production with a water-soluble nickel-based catalyst.

PubMed

Dutta, Arnab; Lense, Sheri; Hou, Jianbo; Engelhard, Mark H; Roberts, John A S; Shaw, Wendy J

2013-12-11

Hydrogenase enzymes use first-row transition metals to interconvert H2 with protons and electrons, reactions that are important for the storage and recovery of energy from intermittent sources such as solar, hydroelectric, and wind. Here we present Ni(P(Cy)2N(Gly)2)2, a water-soluble molecular electrocatalyst with the amino acid glycine built into the diphosphine ligand framework. Proton transfer between the outer coordination sphere carboxylates and the second coordination sphere pendant amines is rapid, as observed by cyclic voltammetry and FTIR spectroscopy, indicating that the carboxylate groups may participate in proton transfer during catalysis. This complex oxidizes H2 (1-33 s(-1)) at low overpotentials (150-365 mV) over a range of pH values (0.1-9.0) and produces H2 under identical solution conditions (>2400 s(-1) at pH 0.5). Enzymes employ proton channels for the controlled movement of protons over long distances-the results presented here demonstrate the effects of a simple two-component proton channel in a synthetic molecular electrocatalyst.

Solvent dynamics and electron transfer reactions

NASA Astrophysics Data System (ADS)

Rasaiah, Jayendran C.; Zhu, Jianjun

1994-02-01

Recent experimental and theoretical studies of the influence of solvent dynamics on electron transfer (ET) reactions are discussed. It is seen that the survival probabilities of the reactants and products can be obtained as the solution to an integral equation using experimental or simulation data on the solvation dynamics. The theory developed for ET between thermally equilibrated reactants in solution, in which the ligand vibrations were treated classically, is extended to include quantum effects on the inner-shell ligand vibration and electron transfer from a nonequilibrium initial state prepared, for example, by laser excitation. This leads to a slight modification of the integral equation which is easily solved on a personal computer to provide results that can be directly compared with experiment. Analytic approximations to the solutions of the integral equation, ranging from a single exponential to multiexponential time dependence of the survival probabilities are discussed. The rate constant for the single exponential decay of the reactants interpolates between the thermal equilibrium rate constant kie (that is independent of solvent dynamics) and a diffusion controlled rate constant kid (determined by solvent dynamics) and also between the wide (A=0) and narrow (A=1) window limits dominated by inner-sphere ligand vibration and outer-sphere solvent reorganization respectively. The explicit dependence of the integral equation solutions on solvation dynamics S(t), the free energy of reaction ΔG0, the total reorganization energy λ and its partitioning between ligand vibration λq and solvent polarization fluctuations λ0, and the nature of the initial state should be useful in the analysis and design of ET experiments in different solvents.

Ab initio evaluation of the thermodynamic and electrochemical properties of alkyl halides and radicals and their mechanistic implications for atom transfer radical polymerization.

PubMed

Lin, Ching Yeh; Coote, Michelle L; Gennaro, Armando; Matyjaszewski, Krzysztof

2008-09-24

High-level ab initio molecular orbital calculations are used to study the thermodynamics and electrochemistry relevant to the mechanism of atom transfer radical polymerization (ATRP). Homolytic bond dissociation energies (BDEs) and standard reduction potentials (SRPs) are reported for a series of alkyl halides (R-X; R = CH 2CN, CH(CH 3)CN, C(CH 3) 2CN, CH 2COOC 2H 5, CH(CH 3)COOCH 3, C(CH 3) 2COOCH 3, C(CH 3) 2COOC 2H 5, CH 2Ph, CH(CH 3)Ph, CH(CH 3)Cl, CH(CH 3)OCOCH 3, CH(Ph)COOCH 3, SO 2Ph, Ph; X = Cl, Br, I) both in the gas phase and in two common organic solvents, acetonitrile and dimethylformamide. The SRPs of the corresponding alkyl radicals, R (*), are also examined. The computational results are in a very good agreement with the experimental data. For all alkyl halides examined, it is found that, in the solution phase, one-electron reduction results in the fragmentation of the R-X bond to the corresponding alkyl radical and halide anion; hence it may be concluded that a hypothetical outer-sphere electron transfer (OSET) in ATRP should occur via concerted dissociative electron transfer rather than a two-step process with radical anion intermediates. Both the homolytic and heterolytic reactions are favored by electron-withdrawing substituents and/or those that stabilize the product alkyl radical, which explains why monomers such as acrylonitrile and styrene require less active ATRP catalysts than vinyl chloride and vinyl acetate. The rate constant of the hypothetical OSET reaction between bromoacetonitrile and Cu (I)/TPMA complex was estimated using Marcus theory for the electron-transfer processes. The estimated rate constant k OSET = approximately 10 (-11) M (-1) s (-1) is significantly smaller than the experimentally measured activation rate constant ( k ISET = approximately 82 M (-1) s (-1) at 25 degrees C in acetonitrile) for the concerted atom transfer mechanism (inner-sphere electron transfer, ISET), implying that the ISET mechanism is preferred. For monomers bearing electron-withdrawing groups, the one-electron reduction of the propagating alkyl radical to the carbanion is thermodynamically and kinetically favored over the one-electron reduction of the corresponding alkyl halide unless the monomer bears strong radical-stabilizing groups. Thus, for monomers such as acrylates, catalysts favoring ISET over OSET are required in order to avoid chain-breaking side reactions.

Characterization of the organic ligand shell of semiconductor quantum dots by fluorescence quenching experiments.

PubMed

Boldt, Klaus; Jander, Sebastian; Hoppe, Kathrin; Weller, Horst

2011-10-25

We present the characterization of the organic ligand shell of CdSe/Cd(x)Zn(1-x)S/ZnS nanoparticles by means of fluorescence quenching experiments. Both electron scavengers and acceptors for resonance energy transfer were employed as probes. Different quenching behavior for short and long chain thiol ligands in water was found. It could be shown that poly(ethylene oxide) (PEO)-capping of the particles comprises a densely packed inner shell and a loosely packed outer shell in which ions and small molecules diffuse unhindered. A quantitative uptake of quencher molecules into the PEO shell was observed, through which the particle volume including the ligand sphere could be determined.

Recent Developments in the Synthesis of Biomacromolecules and their Conjugates by Single Electron Transfer-Living Radical Polymerization.

PubMed

Lligadas, Gerard; Grama, Silvia; Percec, Virgil

2017-04-10

Single electron transfer-living radical polymerization (SET-LRP) represents a robust and versatile tool for the synthesis of vinyl polymers with well-defined topology and chain end functionality. The crucial step in SET-LRP is the disproportionation of the Cu(I)X generated by activation with Cu(0) wire, powder, or nascent Cu(0) generated in situ into nascent, extremely reactive Cu(0) atoms and nanoparticles and Cu(II)X 2 . Nascent Cu(0) activates the initiator and dormant chains via a homogeneous or heterogeneous outer-sphere single-electron transfer mechanism (SET-LRP). SET-LRP provides an ultrafast polymerization of a plethora of monomers (e.g., (meth)-acrylates, (meth)-acrylamides, styrene, and vinyl chloride) including hydrophobic and water insoluble to hydrophilic and water soluble. Some advantageous features of SET-LRP are (i) the use of Cu(0) wire or powder as readily available catalysts under mild reaction conditions, (ii) their excellent control over molecular weight evolution and distribution as well as polymer chain ends, (iii) their high functional group tolerance allowing the polymerization of commercial-grade monomers, and (iv) the limited purification required for the resulting polymers. In this Perspective, we highlight the recent advancements of SET-LRP in the synthesis of biomacromolecules and of their conjugates.

Redox probing study of the potential dependence of charge transport through Li 2O 2

DOE PAGES

Knudsen, Kristian B.; Luntz, Alan C.; Jensen, Søren H.; ...

2015-11-20

In the field of energy storage devices the pursuit for cheap, high energy density, reliable secondary batteries is at the top of the agenda. The Li–O 2 battery is one of the possible technologies that, in theory, should be able to close the gap, which exists between the present state-of-the-art Li-ion technologies and the demand placed on batteries by technologies such as electrical vehicles. Here we present a redox probing study of the charge transfer across the main deposition product lithium peroxide, Li 2O 2, in the Li–O 2 battery using outer-sphere redox shuttles. The change in heterogeneous electron transfermore » exchange rate as a function of the potential and the Li 2O 2 layer thickness (~depth-of-discharge) was determined using electrochemical impedance spectroscopy. In addition, the attenuation of the electron transfer exchange rate with film thickness is dependent on the probing potential, providing evidence that hole transport is the dominant process for charge transfer through Li 2O 2 and showing that the origin of the sudden death observed upon discharge is due to charge transport limitations.« less

Interaction and charge transfer between dielectric spheres: Exact and approximate analytical solutions.

PubMed

Lindén, Fredrik; Cederquist, Henrik; Zettergren, Henning

2016-11-21

We present exact analytical solutions for charge transfer reactions between two arbitrarily charged hard dielectric spheres. These solutions, and the corresponding exact ones for sphere-sphere interaction energies, include sums that describe polarization effects to infinite orders in the inverse of the distance between the sphere centers. In addition, we show that these exact solutions may be approximated by much simpler analytical expressions that are useful for many practical applications. This is exemplified through calculations of Langevin type cross sections for forming a compound system of two colliding spheres and through calculations of electron transfer cross sections. We find that it is important to account for dielectric properties and finite sphere sizes in such calculations, which for example may be useful for describing the evolution, growth, and dynamics of nanometer sized dielectric objects such as molecular clusters or dust grains in different environments including astrophysical ones.

New insights into hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds by rhenium(V)-dioxo complexes.

PubMed

Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan

2015-04-23

The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.

Electron impact cross-sections and cooling rates for methane. [in thermal balance of electrons in atmospheres and ionospheres of planets and satellites in outer solar system

NASA Technical Reports Server (NTRS)

Gan, L.; Cravens, T. E.

1992-01-01

Energy transfer between electrons and methane gas by collisional processes plays an important role in the thermal balance of electrons in the atmospheres and ionospheres of planets and satellites in the outer solar system. The literature is reviewed for electron impact cross-sections for methane in this paper. Energy transfer rates are calculated for elastic and inelastic processes using a Maxwellian electron distribution. Vibrational, rotational, and electronic excitation and ionization are included. Results are presented for a wide range of electron temperatures and neutral temperatures.

The mechanism of enantioselective ketone reduction with Noyori and Noyori–Ikariya bifunctional catalysts

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

Dub, Pavel A.; Gordon, John C.

2016-03-21

The catalytic hydrogenation of prochiral ketones with second and third-row transition metal complexes bearing chelating chiral ligands containing at least one N–H functionality has achieved unparalleled performance, delivering, in the best cases, chiral alcohols with up to 99.9% ee using extremely small catalyst loadings (~10 -5 mol%). Hence the efficacy of this reaction has closely approached that of natural enzymatic systems and the reaction itself has become one of the most efficient artificial catalytic reactions developed to date. This paper describes the current level of understanding of the mechanism of enantioselective hydrogenation and transfer hydrogenation of aromatic ketones with pioneeringmore » prototypes of bifunctional catalysts, the Noyori and Noyori–Ikariya complexes. Finally, analysis presented herein expands the concept of “metal–ligand cooperation”, redefines the term “cooperative ligand” and introduces “H –/H + outer-sphere hydrogenation” as a novel paradigm in outer-sphere hydrogenation.« less

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.

A trans-outer membrane porin-cytochrome protein complex for extracellular electron transfer by Geobacter sulfurreducens PCA

DOE PAGES

Liu, Yimo; Wang, Zheming; Liu, Juan; ...

2014-09-24

The multiheme, outer membrane c-type cytochrome (c-Cyt) OmcB of Geobacter sulfurreducens was previously proposed to mediate electron transfer across the outer membrane. However, the underlying mechanism has remained uncharacterized. In G. sulfurreducens, the omcB gene is part of two tandem four-gene clusters, each is predicted to encode a transcriptional factor (OrfR/OrfS), a porin-like outer membrane protein (OmbB/OmbC), a periplasmic c-type cytochrome (OmaB/OmaC), and an outer membrane c-Cyt (OmcB/OmcC), respectively. Here we showed that OmbB/OmbC, OmaB/OmaC and OmcB/OmcC of G. sulfurreducens PCA formed the porin-cytochrome (Pcc) protein complexes, which were involved in transferring electrons across the outer membrane. The isolated Pccmore » protein complexes reconstituted in proteoliposomes transferred electrons from reduced methyl viologen across the lipid bilayer of liposomes to Fe(III)-citrate and ferrihydrite. The pcc clusters were found in all eight sequenced Geobacter and 11 other bacterial genomes from six different phyla, demonstrating a widespread distribution of Pcc protein complexes in phylogenetically diverse bacteria. Deletion of ombB-omaB-omcB-orfS-ombC-omaC-omcC gene clusters had no impact on the growth of G. sulfurreducens PCA with fumarate, but diminished the ability of G. sulfurreducens PCA to reduce Fe(III)-citrate and ferrihydrite. Finally, complementation with the ombB-omaB-omcB gene cluster restored the ability of G. sulfurreducens PCA to reduce Fe(III)-citrate and ferrihydrite.« less

Electrochemical Measurement of Electron Transfer Kinetics by Shewanella oneidensis MR-1*

PubMed Central

Baron, Daniel; LaBelle, Edward; Coursolle, Dan; Gralnick, Jeffrey A.; Bond, Daniel R.

2009-01-01

Shewanella oneidensis strain MR-1 can respire using carbon electrodes and metal oxyhydroxides as electron acceptors, requiring mechanisms for transferring electrons from the cell interior to surfaces located beyond the cell. Although purified outer membrane cytochromes will reduce both electrodes and metals, S. oneidensis also secretes flavins, which accelerate electron transfer to metals and electrodes. We developed techniques for detecting direct electron transfer by intact cells, using turnover and single turnover voltammetry. Metabolically active cells attached to graphite electrodes produced thin (submonolayer) films that demonstrated both catalytic and reversible electron transfer in the presence and absence of flavins. In the absence of soluble flavins, electron transfer occurred in a broad potential window centered at ∼0 V (versus standard hydrogen electrode), and was altered in single (ΔomcA, ΔmtrC) and double deletion (ΔomcA/ΔmtrC) mutants of outer membrane cytochromes. The addition of soluble flavins at physiological concentrations significantly accelerated electron transfer and allowed catalytic electron transfer to occur at lower applied potentials (−0.2 V). Scan rate analysis indicated that rate constants for direct electron transfer were slower than those reported for pure cytochromes (∼1 s−1). These observations indicated that anodic current in the higher (>0 V) window is due to activation of a direct transfer mechanism, whereas electron transfer at lower potentials is enabled by flavins. The electrochemical dissection of these activities in living cells into two systems with characteristic midpoint potentials and kinetic behaviors explains prior observations and demonstrates the complementary nature of S. oneidensis electron transfer strategies. PMID:19661057

Experimental and Theoretical Demonstrations for the Mechanism behind Enhanced Microbial Electron Transfer by CNT Network

NASA Astrophysics Data System (ADS)

Liu, Xian-Wei; Chen, Jie-Jie; Huang, Yu-Xi; Sun, Xue-Fei; Sheng, Guo-Ping; Li, Dao-Bo; Xiong, Lu; Zhang, Yuan-Yuan; Zhao, Feng; Yu, Han-Qing

2014-01-01

Bioelectrochemical systems (BESs) share the principle of the microbially catalyzed anodic substrate oxidation. Creating an electrode interface to promote extracellular electron transfer from microbes to electrode and understanding such mechanisms are crucial for engineering BESs. In this study, significantly promoted electron transfer and a 10-times increase in current generation in a BES were achieved by the utilization of carbon nanotube (CNT) network, compared with carbon paper. The mechanisms for the enhanced current generation with the CNT network were elucidated with both experimental approach and molecular dynamic simulations. The fabricated CNT network was found to be able to substantially enhance the interaction between the c-type cytochromes and solid electron acceptor, indicating that the direct electron transfer from outer-membrane decaheme c-type cytochromes to electrode might occur. The results obtained in this study will benefit for the optimized design of new materials to target the outer membrane proteins for enhanced electron exchanges.

In situ spectroscopic evidence for neptunium(V)-carbonate inner-sphere and outer-sphere ternary surface complexes on hematite surfaces.

PubMed

Arai, Yuji; Moran, P B; Honeyman, B D; Davis, J A

2007-06-01

Np(V) surface speciation on hematite surfaces at pH 7-9 under pC2 = 10(-3.45) atm was investigated using X-ray absorption spectroscopy (XAS). In situ XAS analyses suggest that bis-carbonato inner-sphere and tris-carbonato outer-sphere ternary surface species coexist at the hematite-water interface at pH 7-8.8, and the fraction of outer-sphere species gradually increases from 27 to 54% with increasing pH from 7 to 8.8. The results suggest that the heretofore unknown Np(V)-carbonato ternary surface species may be important in predicting the fate and transport of Np(V) in the subsurface environment down gradient of high-level nuclear waste respositories.

Introducing Students to Inner Sphere Electron Transfer Concepts through Electrochemistry Studies in Diferrocene Mixed-Valence Systems

ERIC Educational Resources Information Center

Ventura, Karen; Smith, Mark B.; Prat, Jacob R.; Echegoyen, Lourdes E.; Villagran´, Dino

2017-01-01

We have designed a 4 h physical chemistry laboratory to introduce upper division students to electrochemistry concepts, including mixed valency and electron transfer (ET), using cyclic and differential pulse voltammetries. In this laboratory practice, students use a ferrocene dimer consisting of two ferrocene centers covalently bonded through a…

The Shadow Knows: Using Shadows to Investigate the Structure of the Pretransitional Disk of HD 100453

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

Long, Zachary C.; Fernandes, Rachel B.; Sitko, Michael

2017-03-20

We present Gemini Planet Imager polarized intensity imagery of HD 100453 in Y , J , and K 1 bands that reveals an inner gap (9–18 au), an outer disk (18–39 au) with two prominent spiral arms, and two azimuthally localized dark features that are also present in Spectro-Polarimetric High-contrast Exoplanet REsearch (SPHERE) total intensity images. Spectral energy distribution fitting further suggests that the radial gap extends to 1 au. The narrow, wedge-like shape of the dark features appears similar to predictions of shadows cast by an inner disk that is misaligned with respect to the outer disk. Using themore » Monte Carlo radiative transfer code HOCHUNCK3D, we construct a model of the disk that allows us to determine its physical properties in more detail. From the angular separation of the features, we measure the difference in inclination between the disks (45°) and their major axes, PA = 140° east of north for the outer disk, and 100° for the inner disk. We find an outer-disk inclination of 25° ± 10° from face-on, in broad agreement with the Wagner et al. measurement of 34°. SPHERE data in J and H bands indicate a reddish disk, which indicates that HD 100453 is evolving into a young debris disk.« less

The Shadow Knows: Using Shadows to Investigate the Structure of the Pretransitional Disk of HD 100453

NASA Astrophysics Data System (ADS)

Long, Zachary C.; Fernandes, Rachel B.; Sitko, Michael; Wagner, Kevin; Muto, Takayuki; Hashimoto, Jun; Follette, Katherine; Grady, Carol A.; Fukagawa, Misato; Hasegawa, Yasuhiro; Kluska, Jacques; Kraus, Stefan; Mayama, Satoshi; McElwain, Michael W.; Oh, Daehyon; Tamura, Motohide; Uyama, Taichi; Wisniewski, John P.; Yang, Yi

2017-03-01

We present Gemini Planet Imager polarized intensity imagery of HD 100453 in Y, J, and K1 bands that reveals an inner gap (9-18 au), an outer disk (18-39 au) with two prominent spiral arms, and two azimuthally localized dark features that are also present in Spectro-Polarimetric High-contrast Exoplanet REsearch (SPHERE) total intensity images. Spectral energy distribution fitting further suggests that the radial gap extends to 1 au. The narrow, wedge-like shape of the dark features appears similar to predictions of shadows cast by an inner disk that is misaligned with respect to the outer disk. Using the Monte Carlo radiative transfer code HOCHUNCK3D, we construct a model of the disk that allows us to determine its physical properties in more detail. From the angular separation of the features, we measure the difference in inclination between the disks (45°) and their major axes, PA = 140° east of north for the outer disk, and 100° for the inner disk. We find an outer-disk inclination of 25° ± 10° from face-on, in broad agreement with the Wagner et al. measurement of 34°. SPHERE data in J and H bands indicate a reddish disk, which indicates that HD 100453 is evolving into a young debris disk.

The Shadow Knows: Using Shadows to Investigate the Structure of the Pretransitional Disk of HD 100453

NASA Technical Reports Server (NTRS)

Long, Zachary C.; Fernandes, Rachel B.; Sitko, Michael; Wagner, Kevin; Muto, Takayuki; Hashimoto, Jun; Follette, Katherine; Grady, Carol A.; Fukagawa, Misato; Hasegawa, Yasuhiro;

Self-assembled clusters of spheres related to spherical codes.

PubMed

Phillips, Carolyn L; Jankowski, Eric; Marval, Michelle; Glotzer, Sharon C

2012-10-01

We consider the thermodynamically driven self-assembly of spheres onto the surface of a central sphere. This assembly process forms self-limiting, or terminal, anisotropic clusters (N-clusters) with well-defined structures. We use Brownian dynamics to model the assembly of N-clusters varying in size from two to twelve outer spheres and free energy calculations to predict the expected cluster sizes and shapes as a function of temperature and inner particle diameter. We show that the arrangements of outer spheres at finite temperatures are related to spherical codes, an ideal mathematical sequence of points corresponding to the densest possible sphere packings. We demonstrate that temperature and the ratio of the diameters of the inner and outer spheres dictate cluster morphology. We present a surprising result for the equilibrium structure of a 5-cluster, for which the square pyramid arrangement is preferred over a more symmetric structure. We show this result using Brownian dynamics, a Monte Carlo simulation, and a free energy approximation. Our results suggest a promising way to assemble anisotropic building blocks from constituent colloidal spheres.

Charge-transfer-to-solvent reactions from I{sup −} to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

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

Okuyama, Haruki; Karashima, Shutaro; Suzuki, Toshinori, E-mail: suzuki@kuchem.kyoto-u.ac.jp

The charge-transfer-to-solvent (CTTS) reactions from iodide (I{sup −}) to H{sub 2}O, D{sub 2}O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H{sub 2}O and D{sub 2}O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field createdmore » for I{sup −}. The photoelectron spectra for CTTS in H{sub 2}O and D{sub 2}O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I{sup −*} (CTTS) state are less than 10%, while alcohols provide 2–3 times greater yields of internal conversion from I{sup −*}. The overall geminate recombination yields are found to be in the order of H{sub 2}O > D{sub 2}O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.« less

Toward simulating complex systems with quantum effects

NASA Astrophysics Data System (ADS)

Kenion-Hanrath, Rachel Lynn

Quantum effects like tunneling, coherence, and zero point energy often play a significant role in phenomena on the scales of atoms and molecules. However, the exact quantum treatment of a system scales exponentially with dimensionality, making it impractical for characterizing reaction rates and mechanisms in complex systems. An ongoing effort in the field of theoretical chemistry and physics is extending scalable, classical trajectory-based simulation methods capable of capturing quantum effects to describe dynamic processes in many-body systems; in the work presented here we explore two such techniques. First, we detail an explicit electron, path integral (PI)-based simulation protocol for predicting the rate of electron transfer in condensed-phase transition metal complex systems. Using a PI representation of the transferring electron and a classical representation of the transition metal complex and solvent atoms, we compute the outer sphere free energy barrier and dynamical recrossing factor of the electron transfer rate while accounting for quantum tunneling and zero point energy effects. We are able to achieve this employing only a single set of force field parameters to describe the system rather than parameterizing along the reaction coordinate. Following our success in describing a simple model system, we discuss our next steps in extending our protocol to technologically relevant materials systems. The latter half focuses on the Mixed Quantum-Classical Initial Value Representation (MQC-IVR) of real-time correlation functions, a semiclassical method which has demonstrated its ability to "tune'' between quantum- and classical-limit correlation functions while maintaining dynamic consistency. Specifically, this is achieved through a parameter that determines the quantumness of individual degrees of freedom. Here, we derive a semiclassical correction term for the MQC-IVR to systematically characterize the error introduced by different choices of simulation parameters, and demonstrate the ability of this approach to optimize MQC-IVR simulations.

Interactions of solvent with the heme region of methemoglobin and fluoro-methemoglobin.

PubMed

Koenig, S H; Brown, R D; Lindstrom, T R

1981-06-01

It is now more than 20 years since Davidson and collaborators (1957, Biochim. Biophys, Acta. 26:370-373; J. Mol. Biol. 1:190-191) applied the theoretical ideas of Bloembergen et al. (1948. Phys. Rev. 73:679-712) on outer sphere magnetic relaxation of solvent protons to studies of solutions of methemoglobin. From then on, there has been debate regarding the relative contributions to paramagnetic solvent proton relaxation by inner sphere (ligand-exchange) effects and by outer sphere (diffusional) effects in methemoglobin solutions. Gupta and Mildvan (1975. J. Biol. Chem 250:146-253) extended the early measurements, attributed the relatively small paramagnetic effects to exchange with solvent of the water ligand of the heme-Fe3+ ion, and interpreted their data to indicate cooperativity and an alkaline Bohr effect in the presence of inositol hexaphosphate. They neglected the earlier discussions entirely, and made no reference to outer sphere effects. We have measured the relaxation rate of solvent protons as a function of magnetic field for solutions of methemoglobin, under a variety of conditions of pH and temperature, and have given careful consideration to the relatively large diamagnetic corrections that are necessary by making analogous measurements on oxyhemoglobin, carbonmonoxyhemoglobin, and cyano- and azide-methemoglobin. (The latter two, because of their short electronic relaxation times, behave as though diamagnetic). We show that the paramagnetic contribution to solvent relaxation can be dominated by outer sphere effects, a result implying that many conclusions, including those of Gupta and Mildvan, require reexamination. Finally, we present data for fluoro-methemoglobin, which relaxes solvent protons an order of magnitude better than does methemoglobin. Here one has a startling breakdown of the dogma that has been the basis for interpreting many ligand-replacement studies; in contrast to the prevailing view that replacement of a water ligand of a protein-bound paramagnetic ion by another ligand should decrease relaxation rates, replacement of H2O by F- increases the relaxation rate drastically. The data can all be reconciled, however, with what is anticipated from knowledge of ligand interactions in the heme region.

Reaction of ferrate (VI)/ferrate (V) with hydrogen peroxide and superoxide anion--a stopped-flow and premix pulse radiolysis study.

PubMed

Rush, J D; Zhao, Z; Bielski, B H

1996-03-01

The reduction of ferrate(VI) to ferrate(V) by superoxide ions was studied over the pH range 2.6-13.0 using the premix pulse radiolysis technique. The pH dependence indicates that only the unstable protonated forms of ferrate, H2FeO4 (pKa3.5) and HFeO4- (pKa7.3) are reactive, k(HFeO4(-) + O2) = (1.7 +/- 0.2) x 10(7) M-1 s-1. The stable ferrate ion, FeO4(2-), showed no significant reactivity towards either hydrogen peroxide or superoxide anion. The rate constants for the spontaneous dimerization and decomposition of the protonated ferrates, e.g. k(HFeO4(-) + HFe04) approximately 250 M-1s-1, are orders of magnitude slower than their corresponding reduction reduction by superoxide indicating an outer-sphere mode of electron transfer for the latter process. In contrast the ferrate(VI) species H3FeO4+ (pKa = 1.6 +/- 0.2), H2FeO4, and HFeO4- oxidize hydrogen peroxide, e.g. k(HFeO4(-) + H2O2) = 170 M-1 s-1), at rates which correspond closely to their dimerization rates suggesting an inner-sphere controlled mechanism.

Respiration of metal (hydr)oxides by Shewanella and Geobacter: a key role for multihaem c-type cytochromes

PubMed Central

Shi, Liang; Squier, Thomas C; Zachara, John M; Fredrickson, James K

2007-01-01

Dissimilatory reduction of metal (e.g. Fe, Mn) (hydr)oxides represents a challenge for microorganisms, as their cell envelopes are impermeable to metal (hydr)oxides that are poorly soluble in water. To overcome this physical barrier, the Gram-negative bacteria Shewanella oneidensis MR-1 and Geobacter sulfurreducens have developed electron transfer (ET) strategies that require multihaem c-type cytochromes (c-Cyts). In S. oneidensis MR-1, multihaem c-Cyts CymA and MtrA are believed to transfer electrons from the inner membrane quinone/quinol pool through the periplasm to the outer membrane. The type II secretion system of S. oneidensis MR-1 has been implicated in the reduction of metal (hydr)oxides, most likely by translocating decahaem c-Cyts MtrC and OmcA across outer membrane to the surface of bacterial cells where they form a protein complex. The extracellular MtrC and OmcA can directly reduce solid metal (hydr)oxides. Likewise, outer membrane multihaem c-Cyts OmcE and OmcS of G. sulfurreducens are suggested to transfer electrons from outer membrane to type IV pili that are hypothesized to relay the electrons to solid metal (hydr)oxides. Thus, multihaem c-Cyts play critical roles in S. oneidensis MR-1- and G. sulfurreducens-mediated dissimilatory reduction of solid metal (hydr)oxides by facilitating ET across the bacterial cell envelope. PMID:17581116

Dissimilatory Reduction of Extracellular Electron Acceptors in Anaerobic Respiration

PubMed Central

Richter, Katrin; Schicklberger, Marcus

2012-01-01

An extension of the respiratory chain to the cell surface is necessary to reduce extracellular electron acceptors like ferric iron or manganese oxides. In the past few years, more and more compounds were revealed to be reduced at the surface of the outer membrane of Gram-negative bacteria, and the list does not seem to have an end so far. Shewanella as well as Geobacter strains are model organisms to discover the biochemistry that enables the dissimilatory reduction of extracellular electron acceptors. In both cases, c-type cytochromes are essential electron-transferring proteins. They make the journey of respiratory electrons from the cytoplasmic membrane through periplasm and over the outer membrane possible. Outer membrane cytochromes have the ability to catalyze the last step of the respiratory chains. Still, recent discoveries provided evidence that they are accompanied by further factors that allow or at least facilitate extracellular reduction. This review gives a condensed overview of our current knowledge of extracellular respiration, highlights recent discoveries, and discusses critically the influence of different strategies for terminal electron transfer reactions. PMID:22179232

Neutron dose equivalent meter

DOEpatents

Olsher, Richard H.; Hsu, Hsiao-Hua; Casson, William H.; Vasilik, Dennis G.; Kleck, Jeffrey H.; Beverding, Anthony

1996-01-01

A neutron dose equivalent detector for measuring neutron dose capable of accurately responding to neutron energies according to published fluence to dose curves. The neutron dose equivalent meter has an inner sphere of polyethylene, with a middle shell overlying the inner sphere, the middle shell comprising RTV.RTM. silicone (organosiloxane) loaded with boron. An outer shell overlies the middle shell and comprises polyethylene loaded with tungsten. The neutron dose equivalent meter defines a channel through the outer shell, the middle shell, and the inner sphere for accepting a neutron counter tube. The outer shell is loaded with tungsten to provide neutron generation, increasing the neutron dose equivalent meter's response sensitivity above 8 MeV.

Adsorption mechanisms of selenium oxyanions at the aluminum oxide/water interface

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

Peak, Derek

2008-06-09

Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO{sub 4}{sup 2-}) and selenite (SeO{sub 3}{sup 2-}) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum ({alpha}-Al{sub 2}O{sub 3}) was studied to determine if adsorption mechanisms change as the aluminum oxide surfacemore » structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and {alpha}-Me{sub 2}O{sub 3}.« less

Outer-Sphere Direction in Iridium C-H Borylation

PubMed Central

Roosen, Philipp C.; Kallepalli, Venkata A.; Chattopadhyay, Buddhadeb; Singleton, Daniel A.; Maleczka, Robert E.; Smith, Milton R.

2013-01-01

The NHBoc group affords ortho selective C–H borylations in arenes and alkenes. Experimental and computational studies support an outer sphere mechanism where the N–H proton hydrogen bonds to a boryl ligand oxygen. The regioselectivities are unique and complement those of directed ortho metalations. PMID:22703452

Fenton chemistry at aqueous interfaces

PubMed Central

Enami, Shinichi; Sakamoto, Yosuke; Colussi, Agustín J.

2014-01-01

In a fundamental process throughout nature, reduced iron unleashes the oxidative power of hydrogen peroxide into reactive intermediates. However, notwithstanding much work, the mechanism by which Fe2+ catalyzes H2O2 oxidations and the identity of the participating intermediates remain controversial. Here we report the prompt formation of O=FeIVCl3− and chloride-bridged di-iron O=FeIV·Cl·FeIICl4− and O=FeIV·Cl·FeIIICl5− ferryl species, in addition to FeIIICl4−, on the surface of aqueous FeCl2 microjets exposed to gaseous H2O2 or O3 beams for <50 μs. The unambiguous identification of such species in situ via online electrospray mass spectrometry let us investigate their individual dependences on Fe2+, H2O2, O3, and H+ concentrations, and their responses to tert-butanol (an ·OH scavenger) and DMSO (an O-atom acceptor) cosolutes. We found that (i) mass spectra are not affected by excess tert-butanol, i.e., the detected species are primary products whose formation does not involve ·OH radicals, and (ii) the di-iron ferryls, but not O=FeIVCl3−, can be fully quenched by DMSO under present conditions. We infer that interfacial Fe(H2O)n2+ ions react with H2O2 and O3 >103 times faster than Fe(H2O)62+ in bulk water via a process that favors inner-sphere two-electron O-atom over outer-sphere one-electron transfers. The higher reactivity of di-iron ferryls vs. O=FeIVCl3− as O-atom donors implicates the electronic coupling of mixed-valence iron centers in the weakening of the FeIV–O bond in poly-iron ferryl species. PMID:24379389

Inner- and outer-wall sorting of double-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Li, Han; Gordeev, Georgy; Wasserroth, Sören; Chakravadhanula, Venkata Sai Kiran; Neelakandhan, Shyam Kumar Chethala; Hennrich, Frank; Jorio, Ado; Reich, Stephanie; Krupke, Ralph; Flavel, Benjamin Scott

2017-12-01

Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.

Inner- and outer-wall sorting of double-walled carbon nanotubes.

PubMed

Li, Han; Gordeev, Georgy; Wasserroth, Sören; Chakravadhanula, Venkata Sai Kiran; Neelakandhan, Shyam Kumar Chethala; Hennrich, Frank; Jorio, Ado; Reich, Stephanie; Krupke, Ralph; Flavel, Benjamin Scott

2017-12-01

Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.

Increasing the rate of hydrogen oxidation without increasing the overpotential: A bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay

DOE PAGES

Darmon, Jonathan M.; Kumar, Neeraj; Hulley, Elliott B.; ...

2015-03-05

Oxidation of hydrogen (H₂) to protons and electrons for energy production in fuel cells is catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton delivery and removal is critical in hydrogenase enzymes in nature that catalyze H₂ oxidation using earth-abundant metals (iron and nickel). Here we report a synthetic iron complex, (Cp C5F4N)Fe(P EtN (CH2)3NMe2PEt)(Cl), that serves as a precatalyst for the oxidation of H₂, with turnover frequencies of 290 s⁻¹ in fluorobenzene, under 1 atm of H₂ using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the exogenous base. The cooperative effect of the primary,more » secondary and outer coordination spheres for moving protons in this remarkably fast catalyst emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.« less

Preparation of Geophysical Fluid Flow Experiments With The Rotating Spherical Gap Flow Model In Space

NASA Astrophysics Data System (ADS)

Egbers, C.

The'GeoFlow' is an ESA experiment planned for the Fluid Science Laboratory on ISS under the scientific coordination (PI) of the Department of Aerodynamics and Fluid Mechanics (LAS) at the Brandenburg Technical University (BTU) of Cottbus, Germany. The objective of the experiment is to study thermal convection in the gap between two concentric rotating (full) spheres. A central symmetric force field simi- lar to the gravity field acting on planets can be produced by applying a high voltage between inner and outer sphere using the dielectrophoretic effect (rotating capacitor). To counter the unidirectional gravity under terrestrial conditions, this experiment re- quires a microgravity environment. The parameters of the experiment are chosen in analogy to the thermal convective motions in the outer core of the Earth. In analogy to geophysical motions in the Earth`s liquid core the experiment can rotate as solid body as well as differential (inner to outer). Thermal convection is produced by heat- ing the inner sphere and cooling the outer ones. Furtheron, the variation of radius ratio between inner and outer sphere is foreseen as a parameter variation. The flows to be investigated will strongly depend on the gap width and on the Prandtl number.

Electrohydrodynamics of a compound vesicle under an AC electric field

NASA Astrophysics Data System (ADS)

Priti Sinha, Kumari; Thaokar, Rochish M.

2017-07-01

Compound vesicles are relevant as simplified models for biological cells as well as in technological applications such as drug delivery. Characterization of these compound vesicles, especially the inner vesicle, remains a challenge. Similarly their response to electric field assumes importance in light of biomedical applications such as electroporation. Fields lower than that required for electroporation cause electrodeformation in vesicles and can be used to characterize their mechanical and electrical properties. A theoretical analysis of the electrohydrodynamics of a compound vesicle with outer vesicle of radius R o and an inner vesicle of radius λ {{R}o} , is presented. A phase diagram for the compound vesicle is presented and elucidated using detailed plots of electric fields, free charges and electric stresses. The electrohydrodynamics of the outer vesicle in a compound vesicle shows a prolate-sphere and prolate-oblate-sphere shape transitions when the conductivity of the annular fluid is greater than the outer fluid, and vice-versa respectively, akin to single vesicle electrohydrodynamics reported in the literature. The inner vesicle in contrast shows sphere-prolate-sphere and sphere-prolate-oblate-sphere transitions when the inner fluid conductivity is greater and smaller than the annular fluid, respectively. Equations and methodology are provided to determine the bending modulus and capacitance of the outer as well as the inner membrane, thereby providing an easy way to characterize compound vesicles and possibly biological cells.

Porous Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, Fred

2005-01-01

This document is a slide presentation that examines the use of a simple templating process to produce hollow ceramic spheres with a pore size of 1 to 10 microns. Using ion exchange process it was determined that the method produces porous ceramic spheres with a unique structure: (i.e., inner sphere surrounded by an outer sphere.)

Equatorial symmetry of Boussinesq convective solutions in a rotating spherical shell allowing rotation of the inner and outer spheres

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

Kimura, Keiji; Takehiro, Shin-ichi; Yamada, Michio

2014-08-15

We investigate properties of convective solutions of the Boussinesq thermal convection in a moderately rotating spherical shell allowing the respective rotation of the inner and outer spheres due to the viscous torque of the fluid. The ratio of the inner and outer radii of the spheres, the Prandtl number, and the Taylor number are fixed to 0.4, 1, and 500{sup 2}, respectively. The Rayleigh number is varied from 2.6 × 10{sup 4} to 3.4 × 10{sup 4}. In this parameter range, the behaviours of obtained asymptotic convective solutions are almost similar to those in the system whose inner and outermore » spheres are restricted to rotate with the same constant angular velocity, although the difference is found in the transition process to chaotic solutions. The convective solution changes from an equatorially symmetric quasi-periodic one to an equatorially symmetric chaotic one, and further to an equatorially asymmetric chaotic one, as the Rayleigh number is increased. This is in contrast to the transition in the system whose inner and outer spheres are assumed to rotate with the same constant angular velocity, where the convective solution changes from an equatorially symmetric quasi-periodic one, to an equatorially asymmetric quasi-periodic one, and to equatorially asymmetric chaotic one. The inner sphere rotates in the retrograde direction on average in the parameter range; however, it sometimes undergoes the prograde rotation when the convective solution becomes chaotic.« less

Electron and Oxygen Atom Transfer Chemistry of Co(II) in a Proton Responsive, Redox Active Ligand Environment.

PubMed

Cook, Brian J; Pink, Maren; Pal, Kuntal; Caulton, Kenneth G

2018-05-21

The bis-pyrazolato pyridine complex LCo(PEt 3 ) 2 serves as a masked form of three-coordinate Co II and shows diverse reactivity in its reaction with several potential outer sphere oxidants and oxygen atom transfer reagents. N-Methylmorpholine N-oxide (NMO) oxidizes coordinated PEt 3 from LCo(PEt 3 ) 2 , but the final cobalt product is still divalent cobalt, in LCo(NMO) 2 . The thermodynamics of a variety of oxygen atom transfer reagents, including NMO, are calculated by density functional theory, to rank their oxidizing power. Oxidation of LCo(PEt 3 ) 2 with AgOTf in the presence of LiCl as a trapping nucleophile forms the unusual aggregate [LCo(PEt 3 ) 2 Cl(LiOTf) 2 ] 2 held together by Li + binding to very nucleophilic chloride on Co(III) and triflate binding to those Li + . In contrast, Cp 2 Fe + effects oxidation to trivalent cobalt, to form (HL)Co(PEt 3 ) 2 Cl + ; proton and the chloride originate from solvent in a rare example of CH 2 Cl 2 dehydrochlorination. An unexpected noncomplementary redox reaction is reported involving attack by 2e reductant PEt 3 nucleophile on carbon of the 1e oxidant radical Cp 2 Fe + , forming a P-C bond and H + ; this reaction competes in the reaction of LCo(PEt 3 ) 2 with Cp 2 Fe + .

Design and Synthesis of Hierarchical SiO2@C/TiO2 Hollow Spheres for High-Performance Supercapacitors.

PubMed

Zhang, Ying; Zhao, Yan; Cao, Shunsheng; Yin, Zhengliang; Cheng, Li; Wu, Limin

2017-09-06

TiO 2 has been widely investigated as an electrode material because of its long cycle life and good durability, but the relatively low theoretical capacity restricts its practical application. Herein, we design and synthesize novel hierarchical SiO 2 @C/TiO 2 (HSCT) hollow spheres via a template-directed method. These unique HSCT hollow spheres combine advantages from both TiO 2 such as cycle stability and SiO 2 with a high accessible area and ionic transport. In particular, the existence of a C layer is able to enhance the electrical conductivity. The SiO 2 layer with a porous structure can increase the ion diffusion channels and accelerate the ion transfer from the outer to the inner layers. The electrochemical measurements demonstrate that the HSCT-hollow-sphere-based electrode manifests a high specific capacitance of 1018 F g -1 at 1 A g -1 which is higher than those for hollow TiO 2 (113 F g -1 ) and SiO 2 /TiO 2 (252 F g -1 ) electrodes, and substantially higher than those of all the previously reported TiO 2 -based electrodes.

Stabilizing photoassociated Cs2 molecules by optimal control

NASA Astrophysics Data System (ADS)

Zhang, Wei; Xie, Ting; Huang, Yin; Wang, Gao-Ren; Cong, Shu-Lin

2013-01-01

We demonstrate theoretically that photoassociated molecules can be stabilized to deeply bound states. This process is achieved by transferring the population from the outer well to the inner well using the optimal control theory, the Cs2 molecule is taken as an example. Numerical calculations show that weakly bound molecules formed in the outer well by a pump pulse can be compressed to the inner well via a vibrational level of the ground electronic state as an intermediary by an additionally optimized laser pulse. The positively chirped pulse can enhance the population of the target state. With a transform-limited dump pulse, nearly all the photoassociated molecules in the inner well of the excited electronic state can be transferred to the deeply vibrational level of the ground electronic state.

Preparation of Geophysical Fluid Flow Experiments ( GeoFlow ) in the Fluid Science Laboratory on ISS

NASA Astrophysics Data System (ADS)

Egbers, C.

The ,,GeoFlow" is an ESA experiment planned for the Fluid Science Laboratory on ISS under the scientific coordination (PI) of the Department of Aerodynamics and Fluidmechanics (LAS) at the Brandenburg Technical University (BTU) of Cottbus, Germany. The objective of the experiment is to study thermal convection in the gap between two concentric rotating (full) spheres. A central symmetric force field similar to the gravity field acting on planets can be produced by applying a high voltage between inner and outer sphere using the dielectrophoretic effect (rotating capacitor). To counter the unidirectional gravity under terrestrial conditions, this experiment requires a microgravity environment. The parameters of the experiment are chosen in analogy to the thermal convective motions in the outer core of the Earth. In analogy to geophysical motions in the Earth's liquid core the exp eriment can rotate as solid body as well as differential (inner to outer). Thermal convection is produced by heating the inner sphere and cooling the outer ones. Furtheron, the variation of radius ratio between inner and outer sphere is foreseen as a parameter variation. The flows to be investigated will strongly depend on the gap width and on the Prandtl number. Results of preparatory experiments and numerical simulation of the space experiment will be presented. Funding from DLR under grant 50 WM 0122 is greatfully ackwnoledged.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1}). A much higher energy band was observed in the UV/Vis region, at 520 nm (19,230 cm^{-1}) in acetonitrile for the corresponding bis(hydrazine) radical cation. The width of this band was estimated to be 240 nm (7211 cm^{-1}). The difference in the energies of these absorbance bands, E _{rm op}, reflects the different inner-sphere reorganization energies of the hydrazyl and hydrazine systems. Using Hush analysis, the electron coupling, H_{rm AB} , was calculated to be ca. 3.5 kcal/mol for the bis(hydrazyl) radical cation systems; a smaller value of H_{rm AB} of 1 kcal/mol was obtained for the bis(hydrazine) radical cations. This difference in electronic coupling is consistent with the faster rate of electron transfer, as well as the smaller inner-sphere reorganization energy in the bis(hydrazyl) systems.

Spectroscopic Characterization of YedY: The Role of Sulfur Coordination in a Mo(V) Sulfite Oxidase Family Enzyme Form

PubMed Central

Yang, Jing; Rothery, Richard; Sempombe, Joseph

2011-01-01

Electronic paramagnetic resonance, electronic absorption, and magnetic circular dichroism spectroscopies have been performed on YedY, a SUOX fold protein with a Mo domain that is remarkably similar to that found in chicken sulfite oxidase, A. thaliana plant sulfite oxidase, and the bacterial sulfite dehydrogenase from S. novella. Low-energy dithiolene→Mo and cysteine thiolate→Mo charge transfer bands have been assigned for the first time in a Mo(V) form of a SUOX fold protein, and the spectroscopic data have been used to interpret the results of bonding calculations. The analysis shows that second coordination sphere effects modulate dithiolene and cysteine sulfur covalency contributions to the Mo bonding scheme. Namely, a more acute Ooxo-Mo-SCys-C dihedral angle results in increased cysteine thiolate S→Mo charge transfer and a high g1 in the EPR spectrum. The spectrosocopic results, coupled with the available structural data, indicate that these second coordination sphere effects may play key roles in modulating the active site redox potential, facilitating hole superexchange pathways for electron transfer regeneration, and affecting the type of reactions catalyzed by sulfite oxidase family enzymes. PMID:19860477

Structure of a bacterial cell surface decaheme electron conduit

USDA-ARS?s Scientific Manuscript database

Some bacterial species are able to utilize extracellular mineral forms of iron and manganese as respiratory electron acceptors. In Shewanella oneidensis this involves decaheme cytochromes that are located on the bacterial cell surface at the termini of trans-outer-membrane electron transfer conduits...

NiO/NiWO4 Composite Yolk-Shell Spheres with Nanoscale NiO Outer Layer for Ultrasensitive and Selective Detection of Subppm-level p-Xylene.

PubMed

Kim, Tae-Hyung; Kwak, Chang-Hoon; Lee, Jong-Heun

2017-09-20

NiO/NiWO 4 composite yolk-shell spheres with a nanoscale NiO outer layer were prepared using one-pot ultrasonic spray pyrolysis and their gas sensing characteristics were studied. The NiO/NiWO 4 yolk-shell spheres exhibited an extremely high response to 5 ppm p-xylene (ratio of resistance to gas and air = 343.5) and negligible cross-responses to 5 ppm ethanol, ammonia, carbon monoxide, hydrogen, and benzene, whereas pure NiO yolk-shell spheres showed very low responses and selectivity to all the analyte gases. The detection limit for p-xylene was as low as 22.7 ppb. This ultrasensitive and selective detection of p-xylene is attributed to a synergistic catalytic effect between NiO and NiWO 4 , high gas accessibility with large specific surface area, and increased chemiresistive variation due to the formation of a heterojunction. The NiO/NiWO 4 yolk-shell spheres with a thin NiO outer layer can be used to detect subppm-level p-xylene in a highly sensitive and selective manner for monitoring indoor air pollution.

Mechanism of Electrophilic Fluorination with Pd(IV): Fluoride Capture and Subsequent Oxidative Fluoride Transfer†, ‡

PubMed Central

Brandt, Jochen R.; Lee, Eunsung; Boursalian, Gregory B.

2013-01-01

Electrophilic fluorinating reagents derived from fluoride are desirable for the synthesis of 18F-labeled molecules for positron emission tomography (PET). Here, we study the mechanism by which a Pd(IV)-complex captures fluoride and subsequently transfers it to nucleophiles. The intermediate Pd(IV)-F is formed with high rates even at the nano- to micromolar fluoride concentrations typical for radiosyntheses with 18F due to fast formation of an outer-sphere complex between fluoride and Pd(IV). The subsequent fluorine transfer from the Pd(IV)-F complex is proposed to proceed through an unusual SET/fluoride transfer/SET mechanism. The findings detailed in this manuscript provide a theoretical foundation suitable for addressing a more general approach for electrophilic fluorination with high specific activity 18F PET imaging. PMID:24376910

Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

PubMed

Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

2013-12-18

Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

Can direct extracellular electron transfer occur in the absence of outer membrane cytochromes in Desulfovibrio vulgaris?

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

Elias, Dwayne A; Zane, Mr. Grant M.; Auer, Dr. Manfred

2010-01-01

Extracellular electron transfer has been investigated over several decades via forms of soluble electron transfer proteins that are exported for extracellular reoxidation. More recently, several organisms have been shown to reduce extracellular metals via the direct transfer of electron through appendages; also known as nanowires. They have been reported most predominantly in Shewanella and Geobacter. While the relevancy and composition of these structures in each genus has been debated, both possess outer membrane cytochrome complexes that could theoretically come into direct contact with solid phase oxidized metals. Members of the genus Desulfovibrio apparently have no such cytochromes although similar appendagesmore » are present, are electrically conductive, and are different from flagella. Upon U(VI)-reduction, the structures in Desulfovibrio become coated with U(IV). Deletion of flagellar genes did not alter soluble or amorphous Fe(III) or U(VI) reduction, or appendage appearance. Removal of the chromosomal pilA gene hampered amorphous Fe(III)-reduction by ca. 25%, but cells lacking the native plasmid, pDV1, reduced soluble Fe(III) and U(VI) at ca. 50% of the wild type rate while amorphous Fe(III)-reduction slowed to ca. 20% of the wild type rate. Appendages were present in all deletions as well as pDV1, except pilA. Gene complementation restored all activities and morphologies to wild type levels. This suggests that pilA encodes the structural component, whereas genes within pDV1 may provide the reactive members. How such appendages function without outer membrane cytochromes is under investigation.« less

NASA Technology Transfer - Human Robot Teaming

NASA Image and Video Library

2016-12-23

Produced for Intelligent Robotics Group to show at January 2017 Consumer Electronics Show (CES). Highlights development of VERVE (Visual Environment for Remote Virtual Exploration) software used on K-10, K-REX, SPHERES and AstroBee projects for 3D awareness. Also mentions transfer of software to Nissan for their development in their Autonomous Vehicle project. Video includes Nissan's self-driving car around NASA Ames.

Exploring the biochemistry at the extracellular redox frontier of bacterial mineral Fe(III) respiration

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

Richardson, David J.; Edwards, Marcus; White, Gaye F.

2012-06-01

Many species of the bacterial Shewanella genus are notable for their ability to respire in anoxic environments utilizing insoluble minerals of Fe(III) and Mn(IV) as extracellular electron acceptors. In Shewanella oneidensis, the process is dependent on the decahaem electron-transport proteins that lie at the extracellular face of the outer membrane where they can contact the insoluble mineral substrates. These extracellular proteins are charged with electrons provided by an inter-membrane electron-transfer pathway that links the extracellular face of the outer membrane with the inner cytoplasmic membrane and thereby intracellular electron sources. In the present paper, we consider the common structural featuresmore » of two of these outermembrane decahaem cytochromes, MtrC and MtrF, and bring this together with biochemical, spectroscopic and voltammetric data to identify common and distinct properties of these prototypical members of different clades of the outer-membrane decahaem cytochrome superfamily.« less

Spherical EUV and Plasma Spectrometer (seps) -a Monitor to Measure the Plasma and EUV Environment in Space

NASA Astrophysics Data System (ADS)

Brunner, Raimund; Schmidtke, Gerhard; Konz, Werner; Pfeffer, Wilfried

A low-cost monitor to measure the EUV and plasma environment in space is presented. The device consists of three (or more) isolated spheres, a metallic sphere, one or more highly trans-parent Inner Grids and Outer Grids. Each one is being connected to a sensitive floating elec-trometer. By setting different potentials to the grids as well as to the sphere and varying one or more of their voltages, measurements of spectral solar EUV irradiance (15-200 nm), of local plasma parameters such as electron and ion densities, electron energies and temperatures as well as ion compositions and debris events can be derived from the current recordings. This detector does not require any (solar) pointing device. The primary goal is to study the impact of solar activity events (e.g. CMEs) as well as subsequent reactions of the ionospheric/thermospheric systems (including space weather occurences). The capability of SEPS for measuring EUV pho-ton fluxes as well as plasma parameters in the energy range from 0 to +/-70 eV is demonstrated by laboratory measurements as performed in the IPM laboratory, at BESSY-PTB electron syn-chrotron in Berlin and at ESA/ESTEC plasma chamber. Based on the laboratory recording of plasma recombination EUV emission the sensor is suitable to detect also auroral and airglow radiations. -The state of the art in the development of this device is reported.

Peroxydisulfate activation by [RuII(tpy)(pic)(H2O)]+. Kinetic, mechanistic and anti-microbial activity studies.

PubMed

Chatterjee, Debabrata; Banerjee, Priyabrata; Bose, Jagadeesh C K; Mukhopadhyay, Sudit

2012-03-07

The oxidation of [Ru(II)(tpy)(pic)H(2)O](+) (tpy = 2,2',6',2''-terpyridine; pic(-) = picolinate) by peroxidisulfate (S(2)O(8)(2-)) as precursor oxidant has been investigated kinetically by UV-VIS, IR and EPR spectroscopy. The overall oxidation of Ru(II)- to Ru(IV)-species takes place in a consecutive manner involving oxidation of [Ru(II)(tpy)(pic)H(2)O](+) to [Ru(III)(tpy)(pic)(OH)](+), and its further oxidation of to the ultimate product [Ru(IV)(tpy)(pic)(O)](+) complex. The time course of the reaction was followed as a function of [S(2)O(8)(2-)], ionic strength (I) and temperature. Kinetic data and activation parameters are interpreted in terms of an outer-sphere electron transfer mechanism. Anti-microbial activity of Ru(II)(tpy)(pic)H(2)O](+) complex by inhibiting the growth of Escherichia coli DH5α in presence of peroxydisulfate has been explored, and the results of the biological studies have been discussed in terms of the [Ru(IV)(tpy)(pic)(O)](+) mediated cleavage of chromosomal DNA of the bacteria.

Grid-Sphere Electrodes for Contact with Ionospheric Plasma

NASA Technical Reports Server (NTRS)

Stone, Nobie H.; Poe, Garrett D.

2010-01-01

Grid-sphere electrodes have been proposed for use on the positively biased end of electrodynamic space tethers. A grid-sphere electrode is fabricated by embedding a wire mesh in a thin film from which a spherical balloon is formed. The grid-sphere electrode would be deployed from compact stowage by inflating the balloon in space. The thin-film material used to inflate the balloon is formulated to vaporize when exposed to the space environment. This would leave the bare metallic spherical grid electrode attached to the tether, which would present a small cross-sectional area (essentially, the geometric wire shadow area only) to incident neutral atoms and molecules. Most of the neutral particles, which produce dynamic drag when they impact a surface, would pass unimpeded through the open grid spaces. However, partly as a result of buildup of a space charge inside the grid-sphere, and partially, the result of magnetic field effects, the electrode would act almost like a solid surface with respect to the flux of electrons. The net result would be that grid-sphere electrodes would introduce minimal aerodynamic drag, yet have effective electrical-contact surface areas large enough to collect multiampere currents from the ionospheric plasma that are needed for operation of electrodynamic tethers. The vaporizable-balloon concept could also be applied to the deployment of large radio antennas in outer space.

Visualization of natural convection heat transfer on a sphere

NASA Astrophysics Data System (ADS)

Lee, Dong-Young; Chung, Bum-Jin

2017-12-01

Natural convection heat transfer phenomena on spheres were investigated by adopting mass transfer experiments based on analogy concept. The diameters of spheres were varied from 0.01 m to 0.12 m, which correspond to the Rayleigh numbers of 1.69×108-2.91×1011. The measured mass transfer coefficients agreed well with the existing correlations. The copper electroplating patterns on the spheres visualized the local heat transfer depending on angular distance. The streak plating patterns were observed on the upper part of the sphere, resulting from the wavy flow patterns caused by the instability.

The unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

PubMed

Wang, Jiandi; Wang, Wenmin; Huang, Liangfang; Yang, Xiaodi; Wei, Haiyan

2015-04-07

In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

PubMed

Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

2011-09-15

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

Scalable synthesis of Na3V2(PO4)(3)/C porous hollow spheres as a cathode for Na-ion batteries

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

Mao, JF; Luo, C; Gao, T

2015-01-01

Na3V2(PO4)(3) (NVP) has been considered as a very promising cathode material for sodium-ion batteries (SIBs) due to its typical NASICON structure, which provides an open and three dimensional (3D) framework for Na+ migration. However, the low electronic conductivity of NVP limits its rate capability and cycling ability. In this study, carbon coated hollow structured NVP/C composites are synthesized via a template-free and scalable ultrasonic spray pyrolysis process, where the carbon coated NVP particles are uniformly decorated on the inner and outer surfaces of the porous hollow carbon spheres. When evaluated as a cathode material for SIBs, the unique NVP/C porousmore » hollow sphere cathode delivers an initial discharge capacity of 99.2 mA h g(-1) and retains 89.3 mA h g(-1) after 300 charge/discharge cycles with a very low degradation rate of 0.035% per cycle. For comparison, the NVP/C composite, prepared by the traditional sol-gel method, delivers a lower initial discharge capacity of 97.4 mA h g(-1) and decreases significantly to 71.5 mA h g(-1) after 300 cycles. The superior electrochemical performance of NVP/C porous hollow spheres is attributed to their unique porous, hollow and spherical structures, as well as the carbon-coating layer, which provides a high contact area between electrode/electrolyte, high electronic conductivity, and high mechanical strength.« less

Outer-sphere Pb(II) adsorbed at specific surface sites on single crystal α-alumina

USGS Publications Warehouse

Bargar, John R.; Towle, Steven N.; Brown, Gordon E.; Parks, George A.

1996-01-01

Solvated Pb(II) ions were found to adsorb as structurally well-defined outer-sphere complexes at specific sites on the α-Al2O3 (0001) single crystal surface, as determined by grazing-incidence X-ray absorption fine structure (GI-XAFS) measurements. The XAFS results suggest that the distance between Pb(II) adions and the alumina surface is approximately 4.2 Å. In contrast, Pb(II) adsorbs as more strongly bound inner-sphere complexes on α-Al2O3 (102). The difference in reactivities of the two alumina surfaces has implications for modeling surface complexation reactions of contaminants in natural environments, catalysis, and compositional sector zoning of oxide crystals.

Bacterial decolorization of textile dyes is an extracellular process requiring a multicomponent electron transfer pathway

PubMed Central

Brigé, Ann; Motte, Bart; Borloo, Jimmy; Buysschaert, Géraldine; Devreese, Bart; Van Beeumen, Jozef J.

2008-01-01

Summary Many studies have reported microorganisms as efficient biocatalysts for colour removal of dye‐containing industrial wastewaters. We present the first comprehensive study to identify all molecular components involved in decolorization by bacterial cells. Mutants from the model organism Shewanella oneidensis MR‐1, generated by random transposon and targeted insertional mutagenesis, were screened for defects in decolorization of an oxazine and diazo dye. We demonstrate that decolorization is an extracellular reduction process requiring a multicomponent electron transfer pathway that consists of cytoplasmic membrane, periplasmic and outer membrane components. The presence of melanin, a redox‐active molecule excreted by S. oneidensis, was shown to enhance the dye reduction rates. Menaquinones and the cytochrome CymA are the crucial cytoplasmic membrane components of the pathway, which then branches off via a network of periplasmic cytochromes to three outer membrane cytochromes. The key proteins of this network are MtrA and OmcB in the periplasm and outer membrane respectively. A model of the complete dye reduction pathway is proposed in which the dye molecules are reduced by the outer membrane cytochromes either directly or indirectly via melanin. PMID:21261820

Kinetic Monte Carlo Simulations and Molecular Conductance Measurements of the Bacterial Decaheme Cytochrome MtrF

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

Byun, H. S.; Pirbadian, S.; Nakano, Aiichiro

2014-09-05

Microorganisms overcome the considerable hurdle of respiring extracellular solid substrates by deploying large multiheme cytochrome complexes that form 20 nanometer conduits to traffic electrons through the periplasm and across the cellular outer membrane. Here we report the first kinetic Monte Carlo simulations and single-molecule scanning tunneling microscopy (STM) measurements of the Shewanella oneidensis MR-1 outer membrane decaheme cytochrome MtrF, which can perform the final electron transfer step from cells to minerals and microbial fuel cell anodes. We find that the calculated electron transport rate through MtrF is consistent with previously reported in vitro measurements of the Shewanella Mtr complex, asmore » well as in vivo respiration rates on electrode surfaces assuming a reasonable (experimentally verified) coverage of cytochromes on the cell surface. The simulations also reveal a rich phase diagram in the overall electron occupation density of the hemes as a function of electron injection and ejection rates. Single molecule tunneling spectroscopy confirms MtrF's ability to mediate electron transport between an STM tip and an underlying Au(111) surface, but at rates higher than expected from previously calculated heme-heme electron transfer rates for solvated molecules.« less

Electron Flow in Multiheme Bacterial Cytochromes is a Balancing Act Between Heme Electronic Interaction and Redox Potentials

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

Breuer, Marian; Rosso, Kevin M.; Blumberger, Jochen

The naturally widespread process of electron transfer from metal reducing bacteria to extracellular solid metal oxides entails unique biomolecular machinery optimized for long-range electron transport. To perform this function efficiently microorganisms have adapted multi-heme c-type cytochromes to arrange heme cofactors into wires that cooperatively span the cellular envelope, transmitting electrons along distances greater than 100 Angstroms. Implications and opportunities for bionanotechnological device design are self-evident. However, at the molecular level how these proteins shuttle electrons along their heme wires, navigating intraprotein intersections and interprotein interfaces effciently, remains a mystery so far inaccessible to experiment. To shed light on this criticalmore » topic, we carried out extensive computer simulations to calculate Marcus theory quantities for electron transfer along the ten heme cofactors in the recently crystallized outer membrane cytochrome MtrF. The combination of electronic coupling matrix elements with free energy calculations of heme redox potentials and reorganization energies for heme-to-heme electron transfer allows the step-wise and overall electron transfer rate to be estimated and understood in terms of structural and dynamical characteristics of the protein. By solving a master equation for electron hopping, we estimate an intrinsic, maximum possible electron flux through solvated MtrF of 104-105 s-1, consistent with recently measured rates for the related MtrCAB protein complex. Intriguingly, this flux must navigate thermodynamically uphill steps past low potential hemes. Our calculations show that the rapid electron transport through MtrF is the result of a clear correlation between heme redox potential and the strength of electronic coupling along the wire: Thermodynamically uphill steps occur only between electronically well connected stacked heme pairs. This suggests that the protein evolved to harbor low potential hemes, presumably necessary for reduction of certain soluble substrates, without slowing down electron ow. These findings are particularly profound in light of the apparently well conserved staggered cross heme wire structural motif in functionally related outer-membrane proteins.« less

Rotational Splittings of Acoustic Modes in an Experimental Model of a Planetary Core

NASA Astrophysics Data System (ADS)

Adams, M. M.; Stone, D.; Lathrop, D. P.

2014-12-01

Planetary zonal flows can be probed in principle using the tools of helioseismology. We explore this technique using laboratory experiments where the measurement of zonal flows is also of geophysical relevance. The experiments are carried out in a device with a geometry similar to that of Earth's core. It consists of a 60 cm diameter outer spherical shell concentric with a 20 cm diameter inner sphere. Air between the inner sphere and outer shell is used as the working fluid. A turbulent shear flow is driven in the air by independently rotating the inner sphere and outer shell. Acoustic modes are excited in the vessel with a speaker, and microphones are used to measure the rotational splittings of these modes. The radial profile of azimuthal velocities is inferred from these splittings, in an approach analogous to that used in helioseismology to determine solar velocity profiles. By varying the inner and outer rotation rates, different turbulent states can be investigated. Comparison is made to previous experimental investigations of turbulent spherical Couette flow. These experiments also serve as a test of this diagnostic, which may be used in the future in liquid sodium experiments, providing information on zonal flows in hydromagnetic experiments.

Acoustic scattering by arbitrary distributions of disjoint, homogeneous cylinders or spheres.

PubMed

Hesford, Andrew J; Astheimer, Jeffrey P; Waag, Robert C

2010-05-01

A T-matrix formulation is presented to compute acoustic scattering from arbitrary, disjoint distributions of cylinders or spheres, each with arbitrary, uniform acoustic properties. The generalized approach exploits the similarities in these scattering problems to present a single system of equations that is easily specialized to cylindrical or spherical scatterers. By employing field expansions based on orthogonal harmonic functions, continuity of pressure and normal particle velocity are directly enforced at each scatterer using diagonal, analytic expressions to eliminate the need for integral equations. The effect of a cylinder or sphere that encloses all other scatterers is simulated with an outer iterative procedure that decouples the inner-object solution from the effect of the enclosing object to improve computational efficiency when interactions among the interior objects are significant. Numerical results establish the validity and efficiency of the outer iteration procedure for nested objects. Two- and three-dimensional methods that employ this outer iteration are used to measure and characterize the accuracy of two-dimensional approximations to three-dimensional scattering of elevation-focused beams.

Long distance electron-transfer mechanism in peptidylglycine alpha-hydroxylating monooxygenase: a perfect fitting for a water bridge.

PubMed

de la Lande, Aurélien; Martí, Sergio; Parisel, Olivier; Moliner, Vicent

2007-09-26

The active sites of copper enzymes have been the subject of many theoretical and experimental investigations from a number of years. Such studies have embraced topics devoted to the modeling of the first coordination sphere at the metallic cations up to the development of biomimetic, or bioinspired, catalytic systems. At least from the theoretical viewpoint, fewer efforts have been dedicated to elucidate how the two copper cations act concertedly in noncoupled dicopper enzymes such as peptidylglycine alpha-hydroxylating monooxygenase (PHM) and dopamine beta-monooxygenase (DbetaM). In these metalloenzymes, an electronic transfer is assumed between the two distant copper cations (11 A). Recent experimental results suggest that this transfer occurs through water molecules, a phenomenon which has been theoretically evidenced to be of high efficiency in the case of cytochrome b5 (Science, 2005, 310, 1311). In the present contribution dedicated to PHM, we overpass the common theoretical approaches dedicated to the electronic and geometrical structures of sites CuM or CuH restricted to their first coordination spheres and aim at directly comparing theoretical results to the experimentally measured activity of the PHM enzyme. To achieve this goal, molecular dynamics simulations were performed on wild-type and various mutants of PHM. More precisely, we provide an estimate of the electron-transfer efficiency between the CuM and CuH sites by means of such molecular dynamics simulations coupled to Marcus theory joined to the Beratan model to approximate the required coupling matrix elements. The theoretical results are compared to the kinetics measurements performed on wild and mutated PHM. The present work, the dynamic aspects of which are essential, accounts for the experimental results issued from mutagenesis. It supports the conclusion that an electronic transfer can occur between two copper(I) sites along a bridge involving a set of hydrogen and chemical bonds. Residue Gln170 is evidenced to be the keystone of this water-mediated pathway.

Fabrication of sub-micrometer-sized jingle bell-shaped hollow spheres from multilayered core-shell particles.

PubMed

Gu, Shunchao; Kondo, Tomohiro; Mine, Eiichi; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

2004-11-01

Jingle bell-shaped hollow spheres were fabricated starting from multilayered particles composed of a silica core, a polystyrene inner shell, and a titania outer shell. Composite particles of silica core-polystyrene shell, synthesized by coating a 339-nm-sized silica core with a polystyrene shell of thickness 238 nm in emulsion polymerization, were used as core particles for a succeeding titania-coating. A sol-gel method was employed to form the titania outer shell with a thickness of 37 nm. The inner polystyrene shell in the multilayered particles was removed by immersing them in tetrahydrofuran. These successive procedures could produce jingle bell-shaped hollow spheres that contained a silica core in the titania shell.

Comparison of cation adsorption by isostructural rutile and cassiterite.

PubMed

Machesky, Michael; Wesolowski, David; Rosenqvist, Jörgen; Předota, Milan; Vlcek, Lukas; Ridley, Moira; Kohli, Vaibhav; Zhang, Zhan; Fenter, Paul; Cummings, Peter; Lvov, Serguei; Fedkin, Mark; Rodriguez-Santiago, Victor; Kubicki, James; Bandura, Andrei

2011-04-19

Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner-sphere cation binding is relatively more favorable. © 2011 American Chemical Society

Colloidal Material Box: In-situ Observations of Colloidal Self-Assembly and Liquid Crystal Phase Transitions in Microgravity

NASA Astrophysics Data System (ADS)

Li, WeiBin; Lan, Ding; Sun, ZhiBin; Geng, BaoMing; Wang, XiaoQing; Tian, WeiQian; Zhai, GuangJie; Wang, YuRen

2016-05-01

To study the self-assembly behavior of colloidal spheres in the solid/liquid interface and elucidate the mechanism of liquid crystal phase transition under microgravity, a Colloidal Material Box (CMB) was designed which consists of three modules: (i) colloidal evaporation experimental module, made up of a sample management unit, an injection management unit and an optical observation unit; (ii) liquid crystal phase transition experimental module, including a sample management unit and an optical observation unit; (iii) electronic control module. The following two experimental plans will be performed inside the CMB aboard the SJ-10 satellite in space. (i) Self-assembly of colloidal spheres (with and without Au shell) induced by droplet evaporation, allowing observation of the dynamic process of the colloidal spheres within the droplet and the change of the droplet outer profile during evaporation; (ii) Phase behavior of Mg2Al LDHs suspensions in microgravity. The experimental results will be the first experimental observations of depositing ordered colloidal crystals and their self-assembly behavior under microgravity, and will illustrate the influence of gravity on liquid crystal phase transition.

Dust modeling of the combined ALMA and SPHERE datasets of HD 163296. Is HD 163296 really a Meeus group II disk?

NASA Astrophysics Data System (ADS)

Muro-Arena, G. A.; Dominik, C.; Waters, L. B. F. M.; Min, M.; Klarmann, L.; Ginski, C.; Isella, A.; Benisty, M.; Pohl, A.; Garufi, A.; Hagelberg, J.; Langlois, M.; Menard, F.; Pinte, C.; Sezestre, E.; van der Plas, G.; Villenave, M.; Delboulbé, A.; Magnard, Y.; Möller-Nilsson, O.; Pragt, J.; Rabou, P.; Roelfsema, R.

2018-06-01

Context. Multiwavelength observations are indispensable in studying disk geometry and dust evolution processes in protoplanetary disks. Aims: We aim to construct a three-dimensional model of HD 163296 that is capable of reproducing simultaneously new observations of the disk surface in scattered light with the SPHERE instrument and thermal emission continuum observations of the disk midplane with ALMA. We want to determine why the spectral energy distribution of HD 163296 is intermediary between the otherwise well-separated group I and group II Herbig stars. Methods: The disk was modeled using the Monte Carlo radiative transfer code MCMax3D. The radial dust surface density profile was modeled after the ALMA observations, while the polarized scattered light observations were used to constrain the inclination of the inner disk component and turbulence and grain growth in the outer disk. Results: While three rings are observed in the disk midplane in millimeter thermal emission at 80, 124, and 200 AU, only the innermost of these is observed in polarized scattered light, indicating a lack of small dust grains on the surface of the outer disk. We provide two models that are capable of explaining this difference. The first model uses increased settling in the outer disk as a mechanism to bring the small dust grains on the surface of the disk closer to the midplane and into the shadow cast by the first ring. The second model uses depletion of the smallest dust grains in the outer disk as a mechanism for decreasing the optical depth at optical and near-infrared wavelengths. In the region outside the fragmentation-dominated regime, such depletion is expected from state-of-the-art dust evolution models. We studied the effect of creating an artificial inner cavity in our models, and conclude that HD 163296 might be a precursor to typical group I sources.

Kinetic Effects Of Increased Proton Transfer Distance On Proton-Coupled Oxidations Of Phenol-Amines

PubMed Central

Rhile, Ian J.

2011-01-01

To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh2NH2 substituent (1). Spectroscopic, structural, thermochemical and computational studies show that the two amino-phenols are very similar, except that the O⋯N distance (dON) is >0.1 Å longer in 2 than in 1. The difference in dON is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations •OAr–NH3+ by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. two orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C6H4OMe)3•+ (3a+) occurs at (1.4 ± 0.1) × 104 M-1 s-1, only a factor of two slower than the closely related reaction of 1 with N(C6H4OMe)2(C6H4Br)•+ (3b+). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ΔG°(2 + 3a+) = +0.078 V vs. ΔG°(1 + 3b+) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted α, Δln(k)/Δln(Keq)). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly anharmonic O⋯H⋯N potential energy surface and the influence of proton vibrational excited states. PMID:21919508

Analysis for Heat Transfer in a High Current-Passing Carbon Nanosphere Using Nontraditional Thermal Transport Model.

PubMed

Hol C Y; Chen, B C; Tsai, Y H; Ma, C; Wen, M Y

2015-11-01

This paper investigates the thermal transport in hollow microscale and nanoscale spheres subject to electrical heat source using nontraditional thermal transport model. Working as supercapacitor electrodes, carbon hollow micrometer- and nanometer-sized spheres needs excellent heat transfer characteristics to maintain high specific capacitance, long cycle life, and high power density. In the nanoscale regime, the prediction of heat transfer from the traditional heat conduction equation based on Fourier's law deviates from the measured data. Consequently, the electrical heat source-induced heat transfer characteristics in hollow micrometer- and nanometer-sized spheres are studied using nontraditional thermal transport model. The effects of parameters on heat transfer in the hollow micrometer- and nanometer-sized spheres are discussed in this study. The results reveal that the heat transferred into the spherical interior, temperature and heat flux in the hollow sphere decrease with the increasing Knudsen number when the radius of sphere is comparable to the mean free path of heat carriers.

Using Combinations of Oxidants and Bases as PCET Reactants: Thermochemical and Practical Considerations

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

Waidmann, Christopher R.; Miller, Alexander J.; Ng, Cheuk-Wa A.

Studies in proton-coupled electron transfer (PCET) often require the combination of an outer-sphere oxidant and a base, to remove an electron and a proton. A common problem is the incompatibility of the oxidant and the base, because the former is electron deficient and the latter electron rich. We have tested a variety of reagents and report a number of oxidant/base combinations that are compatible and therefore potentially useful as PCET reagents. A formal bond dissociation free energy (BDFE) for a reagent combination is defined by the redox potential of the oxidant and pKa of the base. This is a formalmore » BDFE because no X-H bond is homolytically cleaved, but it is a very useful way to categorize the H• accepting ability of an oxidant/base PCET pair. Formal BDFEs of stable oxidant/base combinations range from 71 to at least 100 kcal mol-1. Effects of solvent, concentration, temperature, and counterions on the stability of the oxidant/base combinations are discussed. Possible extensions to related reductant/acid combinations are mentioned. We gratefully acknowledge the financial support of the U.S. National Science Foundation Center for Enabling New Technologies through Catalysis, the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry (for a fellowship to A.J.M.M.), the U.S. National Institutes of Health (grant GM-50422), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Retuning the Catalytic Bias and Overpotential of a [NiFe]-Hydrogenase via a Single Amino Acid Exchange at the Electron Entry/Exit Site

PubMed Central

2017-01-01

The redox chemistry of the electron entry/exit site in Escherichia coli hydrogenase-1 is shown to play a vital role in tuning biocatalysis. Inspired by nature, we generate a HyaA-R193L variant to disrupt a proposed Arg–His cation−π interaction in the secondary coordination sphere of the outermost, “distal”, iron–sulfur cluster. This rewires the enzyme, enhancing the relative rate of H2 production and the thermodynamic efficiency of H2 oxidation catalysis. On the basis of Fourier transformed alternating current voltammetry measurements, we relate these changes in catalysis to a shift in the distal [Fe4S4]2+/1+ redox potential, a previously experimentally inaccessible parameter. Thus, metalloenzyme chemistry is shown to be tuned by the second coordination sphere of an electron transfer site distant from the catalytic center. PMID:28697596

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

The microbe electric: conversion of organic matter to electricity.

PubMed

Lovley, Derek R

2008-12-01

Broad application of microbial fuel cells will require substantial increases in current density. A better understanding of the microbiology of these systems may help. Recent studies have greatly expanded the range of microorganisms known to function either as electrode-reducing microorganisms at the anode or as electrode-oxidizing microorganisms at the cathode. Microorganisms that can completely oxidize organic compounds with an electrode serving as the sole electron acceptor are expected to be the primary contributors to power production. Several mechanisms for electron transfer to anodes have been proposed including: direct electron transfer via outer-surface c-type cytochromes, long-range electron transfer via microbial nanowires, electron flow through a conductive biofilm matrix containing cytochromes, and soluble electron shuttles. Which mechanisms are most important depend on the microorganisms and the thickness of the anode biofilm. Emerging systems biology approaches to the study, design, and evolution of microorganisms interacting with electrodes are expected to contribute to improved microbial fuel cells.

p-Aminophenylacetic acid-mediated synthesis of monodispersed titanium oxide hybrid microspheres in ethanol solution.

PubMed

Zhang, Hongye; Xie, Yun; Liu, Zhimin; Tao, Ranting; Sun, Zhenyu; Ding, Kunlun; An, Guimin

2009-10-15

Monodispersed TiO2 hybrid microspheres were prepared via the hydrolysis of titanium isopropoxide (TTIP) in ethanol solution containing p-aminophenylacetic acid (APA). The effects of the APA:TTIP molar ratio, water content, reaction time and reaction temperature on the morphology of the resultant spheres were investigated. The products were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. It was demonstrated that the diameters of the resultant TiO2 spheres could be tuned in the range of 380-800 nm by changing the APA:TTIP molar ratio (1:3 to 3:1) and water content (1-3 v/v%) in the reaction medium, and that increasing the APA:TTIP molar ratio led to larger TiO2 hybrid spheres while increasing the water content decreased their size. The loading content of APA in the hybrid spheres could reach 20 wt.% as they were prepared with the APA:TTIP ratio of 3:1. The possible formation mechanism of the hybrid spheres was also investigated. It was found that APA slowed down the hydrolysis rate of the titanium precursor so that resulted in the formation of the TiO2 spheres. In addition, the APA present in TiO2 spheres acted as a reducing agent to in situ convert HAuCl4 into metallic Au on the surface of the TiO2 spheres. The catalytic activity of the resultant Au/APA-TiO2 composite was examined using transfer hydrogenation of phenylacetone with 2-propanol, and it was indicated that the catalyst displayed high efficiency for this reaction.

An experimental study of laminar film condensation with Stefan number greater than unity

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

Mahajan, R.L.; Dickinson, D.A.; Chu, T.Y.

1991-05-01

Experimental laminar condensation heat transfer data are reported for fluids with Stefan number up to 3.5. The fluid is a member of a family of fluorinated fluids, which have been used extensively in the electronics industry for soldering, cooling, and testing applications. Experiments were performed by suddenly immersing cold copper spheres in the saturated vapor of this fluid, and heat transfer rates were calculated using the quasi-steady temperature response of the spheres. In these experiments, the difference between saturation and wall temperature varied from 0.5C to 190C. Over this range of temperature difference, the condensate properties vary significantly; viscosity ofmore » the condensate varies by a factor of nearly 50. Corrections for the temperature-dependent properties of the condensate therefore were incorporated in calculating the Nusselt number based on the average heat transfer coefficient. The results are discussed in light of past experimental data and theory for Stefan number less than unity. To the knowledge of the authors, this is the first reported study of condensation heat transfer examining the effects of Stefan number greater than unity.« less

Implications of Marcus-Hush theory for steady-state heterogeneous electron transfer at an inlaid disk electrode.

PubMed

Feldberg, Stephen W

2010-06-15

For an outer-sphere heterogeneous electron transfer, Ox + e = Red, between an electrode and a redox couple, the Butler-Volmer formalism predicts that the operative heterogeneous rate constant, k(red) (cm s(-1)) for reduction (or k(ox) for oxidation) increases without limit as an exponential function of -alpha (E - E(0)) for reduction (or (1 - alpha)(E - E(0)) for oxidation), where E is the applied electrode potential, alpha (~1/2) is the transfer coefficient and E(0) is the formal potential. The Marcus-Hush formalism, as exposited by Chidsey (Chidsey, C. E. D. Science 1991, 215, 919), predicts that the value of k(red) or k(ox) limits at sufficiently large values of -(E - E(0)) or (E - E(0)). The steady-state currents at an inlaid disk electrode obtained for a redox species in solution were computed using both formalisms with the Oldham-Zoski approximation (Oldham, K. B.; Zoski, C. G. J. Electroanal. Chem. 1988, 256, 11). Significant differences are noted for the two formalisms. When k(0)r(0)/D is sufficiently small (k(0) is the standard rate constant, r(0) is the radius of the disk electrode, and D is the diffusion coefficient of the redox species), the Marcus-Hush formalism effects a limiting current that can be significantly smaller than the mass transport limited current. This is easily explained in terms of the limiting values of k(red) and k(ox) predicted by the Marcus-Hush formalism. The experimental conditions that must be met to effect significant differences in behavior are discussed; experimental conditions that effect virtually identical behavior are also discussed. As a caveat for experimentalists, applications of the Butler-Volmer formalism to systems that are more properly described using the Marcus-Hush formalism are shown to yield incorrect values of k(0) and meaningless values of alpha, which serves only as a fitting parameter.

Microbial Biofilm Voltammetry: Direct Electrochemical Characterization of Catalytic Electrode-Attached Biofilms▿ †

PubMed Central

Marsili, Enrico; Rollefson, Janet B.; Baron, Daniel B.; Hozalski, Raymond M.; Bond, Daniel R.

2008-01-01

While electrochemical characterization of enzymes immobilized on electrodes has become common, there is still a need for reliable quantitative methods for study of electron transfer between living cells and conductive surfaces. This work describes growth of thin (<20 μm) Geobacter sulfurreducens biofilms on polished glassy carbon electrodes, using stirred three-electrode anaerobic bioreactors controlled by potentiostats and nondestructive voltammetry techniques for characterization of viable biofilms. Routine in vivo analysis of electron transfer between bacterial cells and electrodes was performed, providing insight into the main redox-active species participating in electron transfer to electrodes. At low scan rates, cyclic voltammetry revealed catalytic electron transfer between cells and the electrode, similar to what has been observed for pure enzymes attached to electrodes under continuous turnover conditions. Differential pulse voltammetry and electrochemical impedance spectroscopy also revealed features that were consistent with electron transfer being mediated by an adsorbed catalyst. Multiple redox-active species were detected, revealing complexity at the outer surfaces of this bacterium. These techniques provide the basis for cataloging quantifiable, defined electron transfer phenotypes as a function of potential, electrode material, growth phase, and culture conditions and provide a framework for comparisons with other species or communities. PMID:18849456

Genomic analyses of bacterial porin-cytochrome gene clusters

DOE PAGES

Shi, Liang; Fredrickson, James K.; Zachara, John M.

2014-11-26

In this study, the porin-cytochrome (Pcc) protein complex is responsible for trans-outer membrane electron transfer during extracellular reduction of Fe(III) by the dissimilatory metal-reducing bacterium Geobacter sulfurreducens PCA. The identified and characterized Pcc complex of G. sulfurreducens PCA consists of a porin-like outer-membrane protein, a periplasmic 8-heme c type cytochrome (c-Cyt) and an outer-membrane 12-heme c-Cyt, and the genes encoding the Pcc proteins are clustered in the same regions of genome (i.e., the pcc gene clusters) of G. sulfurreducens PCA. A survey of additionally microbial genomes has identified the pcc gene clusters in all sequenced Geobacter spp. and other bacteriamore » from six different phyla, including Anaeromyxobacter dehalogenans 2CP-1, A. dehalogenans 2CP-C, Anaeromyxobacter sp. K, Candidatus Kuenenia stuttgartiensis, Denitrovibrio acetiphilus DSM 12809, Desulfurispirillum indicum S5, Desulfurivibrio alkaliphilus AHT2, Desulfurobacterium thermolithotrophum DSM 11699, Desulfuromonas acetoxidans DSM 684, Ignavibacterium album JCM 16511, and Thermovibrio ammonificans HB-1. The numbers of genes in the pcc gene clusters vary, ranging from two to nine. Similar to the metal-reducing (Mtr) gene clusters of other Fe(III)-reducing bacteria, such as Shewanella spp., additional genes that encode putative c-Cyts with predicted cellular localizations at the cytoplasmic membrane, periplasm and outer membrane often associate with the pcc gene clusters. This suggests that the Pcc-associated c-Cyts may be part of the pathways for extracellular electron transfer reactions. The presence of pcc gene clusters in the microorganisms that do not reduce solid-phase Fe(III) and Mn(IV) oxides, such as D. alkaliphilus AHT2 and I. album JCM 16511, also suggests that some of the pcc gene clusters may be involved in extracellular electron transfer reactions with the substrates other than Fe(III) and Mn(IV) oxides.« less

Characterisation of FAP-1 expression and CD95 mediated apoptosis in the A818-6 pancreatic adenocarcinoma differentiation system.

PubMed

Winterhoff, Boris J N; Arlt, Alexander; Duttmann, Angelika; Ungefroren, Hendrik; Schäfer, Heiner; Kalthoff, Holger; Kruse, Marie-Luise

2012-03-01

The present study investigated the expression and localisation of FAP-1 (Fas associated phosphatase-1) and CD95 in a 3D differentiation model in comparison to 2D monolayers of the pancreatic adenocarcinoma cell line A818-6. Under non-adherent growth conditions, A818-6 cells differentiate into 3D highly organised polarised epithelial hollow spheres, resembling duct-like structures. A818-6 cells showed a differentiation-dependent FAP-1 localisation. Cells grown as 2D monolayers revealed FAP-1 staining in a juxtanuclear cisternal position, as well as localisation in the nucleus. After differentiation into hollow spheres, FAP-1 was relocated towards the actin cytoskeleton beneath the outer plasma membrane of polarised cells and no further nuclear localisation was observed. CD95 surface staining was found only in a subset of A818-6 monolayer cells, while differentiated hollow spheres appeared to express CD95 in all cells of a given sphere. We rarely observed co-localisation of CD95 and FAP-1 in A818-6 monolayer cells, but strong co-localisation beneath the outer plasma membrane in polarised cells. Analysis of surface expression by flow cytometry revealed that only a subset (36%) of monolayer cells showed CD95 surface expression, and after induction of hollow spheres, CD95 presentation at the outer plasma membrane was reduced to 13% of hollow spheres. Induction of apoptosis by stimulation with agonistic anti-CD95 antibodies, resulted in increased caspase activity in both, monolayer cells and hollow spheres. Knock down of FAP-1 mRNA in A818-6 monolayer cells did not alter resposiveness to CD95 agonistic antibodies. These data suggested that CD95 signal transduction was not affected by FAP-1 expression in A818-6 monolayer cells. In differentiated 3D hollow spheres, we found a polarisation-induced co-localisation of CD95 and FAP-1. A tight control of receptor surface representation and signalling induced apoptosis ensures controlled removal of individual cells instead of a "snowball effect" of apoptotic events. Copyright © 2011 International Society of Differentiation. Published by Elsevier B.V. All rights reserved.

Inner-Sphere Reorganization in Optical Electron Transfer.

DTIC Science & Technology

1984-03-01

systematic error on Et should not exceed *0.05 eV. Agreement between the & rG s and Et’s in Table I is as good as can be expected in view of the preceding...01.413183101 ~359/413-2 TECHNICAL REPORT DISTRIBUTION LIST, 359 Dr. David Aikens Dr. 0. H. Whitmore Chemistry Department Department of Materials

Providing Knowledge Recommendations: An Approach for Informal Electronic Mentoring

ERIC Educational Resources Information Center

Colomo-Palacios, Ricardo; Casado-Lumbreras, Cristina; Soto-Acosta, Pedro; Misra, Sanjay

2014-01-01

The use of Web 2.0 technologies for knowledge management is invading the corporate sphere. The Web 2.0 is the most adopted knowledge transfer tool within knowledge intensive firms and is starting to be used for mentoring. This paper presents IM-TAG, a Web 2.0 tool, based on semantic technologies, for informal mentoring. The tool offers…

On the Concentration Gradient across a Spherical Source Washed by Slow Flow

PubMed Central

Jaffe, Lionel

1965-01-01

A model has been numerically analyzed to help interpret the orienting effects of flow upon cells. The model is a sphere steadily and uniformly emitting a diffusible stuff into a medium otherwise free of it and moving past with Stokes flow. Its properties depend primarily upon the Peclet number, Pe, equal to a · v∞/D, i.e., the sphere's radius, a, times the free stream speed, v∞, over the stuff's diffusion constant, D. As Pe rises, and washing becomes more effective, the average surface concentration, C̄s a falls (Figs. 2 and 5) and the residual material becomes relatively concentrated on the sphere's lee pole (Figs. 2 and 4). Specifically, as Pe rises from 0.1 to 1, the relative concentration gradient, G, rises from 0.7 to 5.0 per cent and to the point where it is rising at about 8 per cent per decade; by Pe 1000, G = 22.1 per cent. From Pe 1 through 1000, G/(1 - C̄s a), or the gradient per concentration deficiency remains at about 26 per cent suggesting that G approaches a ceiling of about 26 per cent. Also from Pe 1 through 1000, the average mass transfer co-efficient nearly equals that previously calculated for spheres maintaining constant surface concentration instead of flux. The complete differential equation without approximations, the Gauss-Seidel method, and an approximation for the outer boundary condition were used. PMID:14268954

Solvothermal Synthesis of a Hollow Micro-Sphere LiFePO4/C Composite with a Porous Interior Structure as a Cathode Material for Lithium Ion Batteries

PubMed Central

Liu, Yang; Zhang, Jieyu; Li, Ying; Hu, Yemin; Li, Wenxian; Zhu, Mingyuan; Hu, Pengfei; Chou, Shulei; Wang, Guoxiu

2017-01-01

To overcome the low lithium ion diffusion and slow electron transfer, a hollow micro sphere LiFePO4/C cathode material with a porous interior structure was synthesized via a solvothermal method by using ethylene glycol (EG) as the solvent medium and cetyltrimethylammonium bromide (CTAB) as the surfactant. In this strategy, the EG solvent inhibits the growth of the crystals and the CTAB surfactant boots the self-assembly of the primary nanoparticles to form hollow spheres. The resultant carbon-coat LiFePO4/C hollow micro-spheres have a ~300 nm thick shell/wall consisting of aggregated nanoparticles and a porous interior. When used as materials for lithium-ion batteries, the hollow micro spherical LiFePO4/C composite exhibits superior discharge capacity (163 mAh g−1 at 0.1 C), good high-rate discharge capacity (118 mAh g−1 at 10 C), and fine cycling stability (99.2% after 200 cycles at 0.1 C). The good electrochemical performances are attributed to a high rate of ionic/electronic conduction and the high structural stability arising from the nanosized primary particles and the micro-sized hollow spherical structure. PMID:29099814

Spectroscopic and DFT Studies of Second Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Non-Local Electrostatic Contributions to Reduction Potentials

PubMed Central

Hadt, Ryan G.; Sun, Ning; Marshall, Nicholas M.; Hodgson, Keith O.; Hedman, Britt; Lu, Yi; Solomon, Edward I.

2012-01-01

The reduction potentials (E0) of type 1 (T1) or blue copper (BC) sites in proteins and enzymes with identical first coordination spheres around the redox active copper ion can vary by ~400 mV. Here, we use a combination of low temperature electronic absorption and magnetic circular dichroism, electron paramagnetic resonance, resonance Raman, and S K-edge X-ray absorption spectroscopies to investigate a series of second sphere variants—F114P, N47S, and F114N in Pseudomonas aeruginosa azurin (Az)—which modulate hydrogen bonding to and protein derived dipoles nearby the Cu-S(Cys) bond. Density functional theory (DFT) calculations correlated to the experimental data allow for the fractionation of the contributions to tuning E0 into covalent and non-local electrostatic components. These are found to be significant, comparable in magnitude, and additive for active H-bonds, while passive H-bonds are mostly non-local electrostatic in nature. For dipoles, these terms can be additive to or oppose one another. This study provides a methodology for uncoupling covalency from non-local electrostatics, which, when coupled to X-ray crystallographic data, distinguishes specific local interactions from more long range protein/active interactions, while affording further insight into the second sphere mechanisms available to the protein to tune the E0 of electron transfer sites in biology. PMID:22985400

Transferable ordered ni hollow sphere arrays induced by electrodeposition on colloidal monolayer.

PubMed

Duan, Guotao; Cai, Weiping; Li, Yue; Li, Zhigang; Cao, Bingqiang; Luo, Yuanyuan

2006-04-13

We report an electrochemical synthesis of two-dimensionally ordered porous Ni arrays based on polystyrene sphere (PS) colloidal monolayer. The morphology can be controlled from bowl-like to hollow sphere-like structure by changing deposition time under a constant current. Importantly, such ordered Ni arrays on a conducting substrate can be transferred integrally to any other desired substrates, especially onto an insulting substrate or curved surface. The magnetic measurements of the two-dimensional hollow sphere array show the coercivity values of 104 Oe for the applied field parallel to the film, and 87 Oe for the applied field perpendicular to the film, which is larger than those of bulk Ni and hollow Ni submicrometer-sized spheres. The formation of hollow sphere arrays is attributed to preferential nucleation on the interstitial sites between PS in the colloidal monolayer and substrate, and growth along PSs' surface. The transferability of the arrays originates from partial contact between the Ni hollow spheres and substrate. Such novel Ni ordered nanostructured arrays with transferability and high magnetic properties should be useful in applications such as data storage, catalysis, and magnetics.

Thermodynamic stability in elastic systems: Hard spheres embedded in a finite spherical elastic solid.

PubMed

Solano-Altamirano, J M; Goldman, Saul

2015-12-01

We determined the total system elastic Helmholtz free energy, under the constraints of constant temperature and volume, for systems comprised of one or more perfectly bonded hard spherical inclusions (i.e. "hard spheres") embedded in a finite spherical elastic solid. Dirichlet boundary conditions were applied both at the surface(s) of the hard spheres, and at the outer surface of the elastic solid. The boundary conditions at the surface of the spheres were used to describe the rigid displacements of the spheres, relative to their initial location(s) in the unstressed initial state. These displacements, together with the initial positions, provided the final shape of the strained elastic solid. The boundary conditions at the outer surface of the elastic medium were used to ensure constancy of the system volume. We determined the strain and stress tensors numerically, using a method that combines the Neuber-Papkovich spherical harmonic decomposition, the Schwartz alternating method, and Least-squares for determining the spherical harmonic expansion coefficients. The total system elastic Helmholtz free energy was determined by numerically integrating the elastic Helmholtz free energy density over the volume of the elastic solid, either by a quadrature, or a Monte Carlo method, or both. Depending on the initial position of the hard sphere(s) (or equivalently, the shape of the un-deformed stress-free elastic solid), and the displacements, either stationary or non-stationary Helmholtz free energy minima were found. The non-stationary minima, which involved the hard spheres nearly in contact with one another, corresponded to lower Helmholtz free energies, than did the stationary minima, for which the hard spheres were further away from one another.

Pseudo-bi-enzyme glucose sensor: ZnS hollow spheres and glucose oxidase concerted catalysis glucose.

PubMed

Shuai, Ying; Liu, Changhua; Wang, Jia; Cui, Xiaoyan; Nie, Ling

2013-06-07

This work creatively uses peroxidase-like ZnS hollow spheres (ZnS HSs) to cooperate with glucose oxidase (GOx) for glucose determinations. This approach is that the ZnS HSs electrocatalytically oxidate the enzymatically generated H2O2 to O2, and then the O2 circularly participates in the previous glucose oxidation by glucose oxidase. Au nanoparticles (AuNPs) and carbon nanotubes (CNTs) are used as electron transfer and enzyme immobilization matrices, respectively. The biosensor of glucose oxidase-carbon nanotubes-Au nanoparticles-ZnS hollow spheres-gold electrode (GOx-CNT-AuNPs-ZnS HSs-GE) exhibits a rapid response, a low detection limit (10 μM), a wide linear range (20 μM to 7 mM) as well as good anti-interference, long-term longevity and reproducibility.

A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C-C Multiple Bonds.

PubMed

Hossein Bagi, Amin; Khaledi, Yousef; Ghari, Hossein; Arndt, Sebastian; Hashmi, A Stephen K; Yates, Brian F; Ariafard, Alireza

2016-11-09

The gold-catalyzed direct functionalization of aromatic C-H bonds has attracted interest for constructing organic compounds which have application in pharmaceuticals, agrochemicals, and other important fields. In the literature, two major mechanisms have been proposed for these catalytic reactions: inner-sphere syn-addition and outer-sphere anti-addition (Friedel-Crafts-type mechanism). In this article, the AuCl 3 -catalyzed hydrofurylation of allenyl ketone, vinyl ketone, ketone, and alcohol substrates is investigated with the aid of density functional theory calculations, and it is found that the corresponding functionalizations are best rationalized in terms of a novel mechanism called "concerted electrophilic ipso-substitution" (CEIS) in which the gold(III)-furyl σ-bond produced by furan auration acts as a nucleophile and attacks the protonated substrate via an outer-sphere mechanism. This unprecedented mechanism needs to be considered as an alternative plausible pathway for gold(III)-catalyzed arene functionalization reactions in future studies.

Geochemical conditions and the occurrence of selected trace elements in groundwater basins used for public drinking-water supply, Desert and Basin and Range hydrogeologic provinces, 2006-11: California GAMA Priority Basin Project

USGS Publications Warehouse

Wright, Michael T.; Fram, Miranda S.; Belitz, Kenneth

2015-01-01

Concentrations of strontium, which exists primarily in a cationic form (Sr2+), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

NASA Astrophysics Data System (ADS)

Wang, Zheming; Shi, Zhi; Shi, Liang; White, Gaye F.; Richardson, David J.; Clarke, Thomas A.; Fredrickson, Jim K.; Zachara, John M.

2015-08-01

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin. However, the exact mechanism of flavin involvement is unclear; while some indicate that flavins mediate electron transfer (Marsili et al., 2008), others point to flavin serving as co-factors to outer membrane proteins (Okamoto et al., 2013). In this work, we used methyl viologen (MVrad +)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of microbially produced flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 μM) by MELs ([MVrad +] ∼ 40 μM and MtrABC ⩽ 1 nM) were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MVrad + and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where (i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and (ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 s. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (⩽1 μM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. For LEP, with the highest reduction potential among the three Fe(III)-oxides, its reduction by FMNH2 was completed in less than 10 min, suggesting that FMN was capable of mediating electron transfer to LEP. At higher FMN concentrations (>1 μM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction under these conditions. The implications of the observed kinetic behaviors to flavin-mediated Fe(III)-oxide reduction in natural environments are discussed.

An experimental study of laminar film condensation with Stefan number greater than unity

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

Mahajan, R.L.; Dickinson, D.A.; Chu, T.Y.

1990-01-01

Experimental laminar condensation heat transfer data is reported for fluids with Stefan number up to 3.5. The fluid is a member of a family of fluorinated fluids developed in the last decade which have been extensively used in the electronics industry for soldering, cooling, and testing applications. Experiments were performed by suddenly immersing cold copper spheres in the saturated vapor of this fluid, and heat transfer rates were calculated using the quasi-steady temperature response of the spheres. In these experiments, the difference between saturation and wall temperature varied from 0.5{degree}C to 190{degree}C. Over this range of temperature difference, the condensatemore » properties vary significantly. For example, viscosity of the condense varies by a factor of over 50. Corrections for the temperature dependent properties of the condensate therefore were incorporated in calculating the Nusselt number based on the average heat transfer coefficient. The results are discussed in light of past experimental data theory for Stefan number less than 1. To the knowledge of the authors, this is the first reported study of condensation heat transfer for Stefan number greater that unity. 24 refs., 7 figs., 2 tabs.« less

Triple differential cross section measurements for the outer valence molecular orbitals (1t2) of a methane molecule at 250 eV electron impact

NASA Astrophysics Data System (ADS)

Işık, N.; Doğan, M.; Bahçeli, S.

2016-03-01

In this study, detailed experimental research of triple differential cross section (TDCS) measurements is performed to investigate single ionization dynamics for the 1t2 orbital of methane molecule by 250 eV electron impact. In our experiments, the outgoing electrons are simultaneously measured in coincidence in a coplanar asymmetric geometry with the scattering angles of 10° and 20°. Therefore, TDCS measurements are performed for two different values of momentum transfer (K ≈ 0.9 au and 1.5 au). A detailed analysis of the dependence of the TDCS versus the momentum transfer is reported here.

F"orster-type mechanism of the redox-driven proton pump

NASA Astrophysics Data System (ADS)

Mourokh, Lev; Smirnov, Anatoly; Nori, Franco

2007-03-01

We propose a model to describe an electronically-driven proton pump in the cytochrome c oxidase (CcO). We examine the situation when the electron transport between the two sites embedded into the inner membrane of the mitochondrion occurs in parallel with the proton transfer from the protonable site that is close to the negative (inner) side of the membrane to the other protonable site located nearby the positive (outer) surface of the membrane. In addition to the conventional electron and proton tunnelings between the sites, the Coulomb interaction between electrons and protons localized on the corresponding sites leads to so-called F"orster transfer, i.e. to the process when the simultaneous electron and proton tunnelings are accompanied by the resonant energy transfer between the electrons and protons. Our calculations based on reasonable parameters have demonstrated that the F"orster process facilitates the proton pump at physiological temperatures. We have examined the effects of an electron voltage build-up, external temperature, and molecular electrostatics driving the electron and proton energies to the resonant conditions, and have shown that these parameters can control the proton pump operation.

Outer membrane cytochromes/flavin interactions in Shewanella spp.—A molecular perspective

DOE PAGES

Babanova, Sofia; Matanovic, Ivana; Cornejo, Jose; ...

2017-05-31

Extracellular electron transfer (EET) is intrinsically associated with the core phenomena of energy harvesting/energy conversion in natural ecosystems and biotechnology applications. But, the mechanisms associated with EET are complex and involve molecular interactions that take place at the “bionano interface” where biotic/abiotic interactions are usually explored. Our work provides molecular perspective on the electron transfer mechanism(s) employed by Shewanella oneidensis MR-1. Molecular docking simulations were used to explain the interfacial relationships between two outer-membrane cytochromes (OMC) OmcA and MtrC and riboflavin (RF) and flavin mononucleotide (FMN), respectively. OMC-flavin interactions were analyzed by studying the electrostatic potential, the hydrophilic/hydrophobic surface properties,more » and the van der Waals surface of the OMC proteins. As a result, it was proposed that the interactions between flavins and OMCs are based on geometrical recognition event. The possible docking positions of RF and FMN to OmcA and MtrC were also shown.« less

Plasma waves near the magnetopause

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

Anderson, R.R.; Haravey, C.C.; Hoppe, M.M.

1982-04-01

Plasma waves associated with the magnetopause, from the magnetosheath to the outer magnetosphere, are examined with an emphasis on high time resolution data and the comparison between measurements by using different antenna systems. An early ISEE crossing of the magnetopause region, including passage through two well-defined flux transfer events, the magentopause current layer, and boundary plasma, is studied in detail. The waves in these regions are compared and contrasted with the waves in the adjoining magnetosheath and outer magnetosphere. Four types of plamsa wave emissions are characteristic of the nominal magnetosheat: (1) a very low frequency continuum, (2) short wavelengthmore » spikes, (3) 'festoon-shaped' emissions below about 2 kHz, and (4) 'lion roars'. The latter two emissions are well correlated with ultra-low frequency magnetic field fluctuations. The dominant plasma wave features during flux transfer events are (1) an intense low-frequency continuum, which includes a substantial electromagnetic component, (2) a dramatic increase in the frequency of occurrence of the spikes, (3) quasi-periodic electron cyclotron harmonics correlated with approx.1-Hz magnetic field fluctuations, and (4) enhanced electron plasma oscillations. The plasma wave characteristics in the current layer and in the boundary layer are quite similar to the features in the flux transfer events. Upon entry into the outer magnetosphere, the plasma wave spectra are dominated by intense electromagnetic chorus bursts and electrosatic (n+1/2)f/sup -//sub g/ emissions. Wavelength determinations made by comparing the various antenna responses and polarization measurements for the different waves are also presented.« less

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

PubMed

Nie, Zhe; Finck, Nicolas; Heberling, Frank; Pruessmann, Tim; Liu, Chunli; Lützenkirchen, Johannes

2017-04-04

Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

Quantum State Transfer from a Single Photon to a Distant Quantum-Dot Electron Spin

NASA Astrophysics Data System (ADS)

He, Yu; He, Yu-Ming; Wei, Yu-Jia; Jiang, Xiao; Chen, Kai; Lu, Chao-Yang; Pan, Jian-Wei; Schneider, Christian; Kamp, Martin; Höfling, Sven

2017-08-01

Quantum state transfer from flying photons to stationary matter qubits is an important element in the realization of quantum networks. Self-assembled semiconductor quantum dots provide a promising solid-state platform hosting both single photon and spin, with an inherent light-matter interface. Here, we develop a method to coherently and actively control the single-photon frequency bins in superposition using electro-optic modulators, and measure the spin-photon entanglement with a fidelity of 0.796 ±0.020 . Further, by Greenberger-Horne-Zeilinger-type state projection on the frequency, path, and polarization degrees of freedom of a single photon, we demonstrate quantum state transfer from a single photon to a single electron spin confined in an InGaAs quantum dot, separated by 5 m. The quantum state mapping from the photon's polarization to the electron's spin is demonstrated along three different axes on the Bloch sphere, with an average fidelity of 78.5%.

Syntrophic anaerobic photosynthesis via direct interspecies electron transfer

DOE PAGES

Ha, Phuc T.; Lindemann, Stephen R.; Shi, Liang; ...

2017-01-09

Microbial phototrophs, key primary producers on Earth, use H 2O, H 2, H 2S and other reduced inorganic compounds as electron donors. Here we describe a form of metabolism linking anoxygenic photosynthesis to anaerobic respiration that we call ‘syntrophic anaerobic photosynthesis’. We show that photoautotrophy in the green sulfur bacterium Prosthecochloris aestaurii can be driven by either electrons from a solid electrode or acetate oxidation via direct interspecies electron transfer from a heterotrophic partner bacterium, Geobacter sulfurreducens. Photosynthetic growth of P. aestuarii using reductant provided by either an electrode or syntrophy is robust and light-dependent. In contrast, P. aestuarii doesmore » not grow in co-culture with a G. sulfurreducens mutant lacking a trans-outer membrane porin-cytochrome protein complex required for direct intercellular electron transfer. Syntrophic anaerobic photosynthesis is therefore a carbon cycling process that could take place in anoxic environments. Lastly, this process could be exploited for biotechnological applications, such as waste treatment and bioenergy production, using engineered phototrophic microbial communities.« less

Syntrophic anaerobic photosynthesis via direct interspecies electron transfer

PubMed Central

Ha, Phuc T.; Lindemann, Stephen R.; Shi, Liang; Dohnalkova, Alice C.; Fredrickson, James K.; Madigan, Michael T.; Beyenal, Haluk

2017-01-01

Microbial phototrophs, key primary producers on Earth, use H2O, H2, H2S and other reduced inorganic compounds as electron donors. Here we describe a form of metabolism linking anoxygenic photosynthesis to anaerobic respiration that we call ‘syntrophic anaerobic photosynthesis'. We show that photoautotrophy in the green sulfur bacterium Prosthecochloris aestaurii can be driven by either electrons from a solid electrode or acetate oxidation via direct interspecies electron transfer from a heterotrophic partner bacterium, Geobacter sulfurreducens. Photosynthetic growth of P. aestuarii using reductant provided by either an electrode or syntrophy is robust and light-dependent. In contrast, P. aestuarii does not grow in co-culture with a G. sulfurreducens mutant lacking a trans-outer membrane porin-cytochrome protein complex required for direct intercellular electron transfer. Syntrophic anaerobic photosynthesis is therefore a carbon cycling process that could take place in anoxic environments. This process could be exploited for biotechnological applications, such as waste treatment and bioenergy production, using engineered phototrophic microbial communities. PMID:28067226

Rotationally Vibrating Electric-Field Mill

NASA Technical Reports Server (NTRS)

Kirkham, Harold

2008-01-01

A proposed instrument for measuring a static electric field would be based partly on a conventional rotating-split-cylinder or rotating-split-sphere electric-field mill. However, the design of the proposed instrument would overcome the difficulty, encountered in conventional rotational field mills, of transferring measurement signals and power via either electrical or fiber-optic rotary couplings that must be aligned and installed in conjunction with rotary bearings. Instead of being made to rotate in one direction at a steady speed as in a conventional rotational field mill, a split-cylinder or split-sphere electrode assembly in the proposed instrument would be set into rotational vibration like that of a metronome. The rotational vibration, synchronized with appropriate rapid electronic switching of electrical connections between electric-current-measuring circuitry and the split-cylinder or split-sphere electrodes, would result in an electrical measurement effect equivalent to that of a conventional rotational field mill. A version of the proposed instrument is described.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate.

PubMed

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-02-04

In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. The results have shown that the reaction is first order with respect to both [IO4(-)] and the complex concentration, and the rate increases over the pH range 2.62 - 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 x 10(-3) s(-1)), is greater than the value of k1 (1.22 x 10(-3) s(-1)) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0 degrees C and I = 0.20 mol dm(-3). It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4(-) to chromium(III). The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between DeltaH* and DeltaS* values for these reactions.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate

PubMed Central

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-01-01

Background In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. Results The results have shown that the reaction is first order with respect to both [IO4-] and the complex concentration, and the rate increases over the pH range 2.62 – 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 × 10-3 s-1), is greater than the value of k1 (1.22 × 10-3 s-1) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0°C and I = 0.20 mol dm-3. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4- to chromium(III). Conclusion The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions. PMID:19193241

Advancing Fenton and photo-Fenton water treatment through the catalyst design.

PubMed

Vorontsov, Alexander V

2018-04-20

The review is devoted to modern Fenton, photo-Fenton, as well as Fenton-like and photo-Fenton-like reactions with participation of iron species in liquid phase and as heterogeneous catalysts. Mechanisms of these reactions were considered that include hydroxyl radical and oxoferryl species as the reactive intermediates. The barriers in the way of application of these reactions to wastewater treatment were discussed. The following fundamental problems need further research efforts: inclusion of more mechanism steps and quantum calculations of all rate constants lacking in the literature, checking the outer sphere electron transfer contribution, determination of the causes for the key changes in the homogeneous Fenton reaction mechanism with a change in the reagents concentration. The key advances for Fenton reactions implementation for the water treatment are related to tremendous hydrodynamical effects on the catalytic activity, design of ligands for high rate and completeness of mineralization in short time, and design of highly active heterogeneous catalysts. While both homogeneous and heterogeneous Fenton and photo-Fenton systems are open for further improvements, heterogeneous photo-Fenton systems are most promising for practical applications because of the inherent higher catalyst stability. Modern methods of quantum chemistry are expected to play a continuously increasing role in development of such catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

High photocatalytic activity of hierarchical SiO2@C-doped TiO2 hollow spheres in UV and visible light towards degradation of rhodamine B.

PubMed

Zhang, Ying; Chen, Juanrong; Hua, Li; Li, Songjun; Zhang, Xuanxuan; Sheng, Weichen; Cao, Shunsheng

2017-10-15

Ongoing research activities are targeted to explore high photocatalytic activity of TiO 2 -based photocatalysts for the degradation of environmental contaminants under UV and visible light irradiation. In this work, we devise a facile, cost-effective technique to in situ synthesize hierarchical SiO 2 @C-doped TiO 2 (SCT) hollow spheres for the first time. This strategy mainly contains the preparation of monodisperse cationic polystyrene spheres (CPS), sequential deposition of inner SiO 2 , the preparation of the sandwich-like CPS@SiO 2 @CPS particles, and formation of outer TiO 2 . After the one-step removal of CPS templates by calcination at 450°C, hierarchical SiO 2 @C-doped TiO 2 hollow spheres are in situ prepared. The morphology, hierarchical structure, and properties of SCT photocatalyst were characterized by TEM. SEM, STEM Mapping, BET, XRD, UV-vis spectroscopy, and XPS. Results strongly confirm the carbon doping in the outer TiO 2 lattice of SCT hollow spheres. When the as-synthesized SCT hollow spheres were employed as a photocatalyst for the degradation of Rhodamine B under visible-light and ultraviolet irradiation, the SCT photocatalyst exhibits a higher photocatalytic activity than commercial P25, effectively overcoming the limitations of poorer UV activity for many previous reported TiO 2 -based photocatalysts due to doping. Copyright © 2017 Elsevier B.V. All rights reserved.

Optimizing conditions for utilization of an H 2 oxidation catalyst with outer coordination sphere functionalities

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

Dutta, Arnab; Ginovska, Bojana; Raugei, Simone

2016-01-01

Hydrogenase enzymes use abundant metals such as nickel and iron to efficiently interconvert H2 and protons. In this work, we demonstrate that a Ni-based catalyst can exceed the rates of enzymes with only slightly higher overpotentials using [Ni(PCy2Narginine2)2]7, containing an amino acid-based outer coordination sphere. Under conditions of high pressure, elevated temperature, and aqueous acidic solutions, conditions similar to those found in fuel cells, this electrocatalyst exhibits the fastest H2 oxidation reported to date for any homogeneous catalyst (TOF 1.1×106 s-1) operating at a moderate overpotential (240 mV). Control experiments demonstrate that both the appended outer coordination sphere and watermore » are important to achieve this impressive catalytic performance. This work was funded by the Office of Science Early Career Research Program through the US Department of Energy, Office of Science, Office of Basic Energy Sciences (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (JASR) located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US Department of Energy.« less

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

PubMed

Cannon, Roderick D; Jayasooriya, Upali A; Tilford, Claire; Anson, Christopher E; Sowrey, Frank E; Rosseinsky, David R; Stride, John A; Tasset, Francis; Ressouche, Eric; White, Ross P; Ballou, Rafik

2004-11-01

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.

Monomer functionalized silica coated with Ag nanoparticles for enhanced SERS hotspots

NASA Astrophysics Data System (ADS)

Newmai, M. Boazbou; Verma, Manoj; Kumar, P. Senthil

2018-05-01

Mesoporous silica (SiO2) spheres are well-known for their excellent chromatographic properties such as the relatively high specific surface, large pore volume, uniform particle size, narrow pore size distribution with favorable pore connectivity; whereas the noble metal Ag nanoparticles have unique size/shape dependant surface plasmon resonance with wide ranging applications. Thus, the desire to synchronize both their properties for specific applications has naturally prompted research in the design and synthesis of core-shell type novel nanoAg@mesoSiO2 nanocomposites, which display potential utility in applications such as photothermal therapy, photocatalysis, molecular sensing, and photovoltaics. In the present work, SiO2 spheres were carefully functionalized with the monomer, N-vinyl pyrrolidone (NVP), which cohesively controls the uniform mass transfer of Ag+ metal ions, thereby enabling its sequential reduction to zerovalent Ag (in the presence of slightly excess NaOH) by electron transfer from nucleophilic attack of the NVP vinyl group by the water molecules even under ambient conditions. Complete metal nanoshell coverage of the silica surface was obtained after multiple Ag deposition cycles, as systematically confirmed from the BET, TEM, optical and FTIR characterization. Our present Ag-coated silica spheres were directly utilized as viable SERS substrates with high sensitivity in contrast with other long chain polymer/surfactant coated silica spheres, owing to the presence of significant number of nanogaps enhanced SERS 'hotspots', which were methodically analyzed utilizing two example analytes, such as crystal violet (CV) and calendula officinalis (CaF).

The effect of ultrasound irradiation on the convective heat transfer rate during immersion cooling of a stationary sphere.

PubMed

Kiani, Hossein; Sun, Da-Wen; Zhang, Zhihang

2012-11-01

It has been proven that ultrasound irradiation can enhance the rate of heat transfer processes. The objective of this work was to study the heat transfer phenomenon, mainly the heat exchange at the surface, as affected by ultrasound irradiation around a stationary copper sphere (k=386W m(-1)K(-1), C(p)=384J kg(-1)K(-1), ρ=8660kg m(-3)) during cooling. The sphere (0.01m in diameter) was immersed in an ethylene glycol-water mixture (-10°C) in an ultrasonic cooling system that included a refrigerated circulator, a flow meter, an ultrasound generator and an ultrasonic bath. The temperature of the sphere was recorded using a data logger equipped with a T-type thermocouple in the center of the sphere. The temperature of the cooling medium was also monitored by four thermocouples situated at different places in the bath. The sphere was located at different positions (0.02, 0.04 and 0.06m) above the transducer surface of the bath calculated considering the center of the sphere as the center of the reference system and was exposed to different intensities of ultrasound (0, 120, 190, 450, 890, 1800, 2800, 3400 and 4100W m(-2)) during cooling. The frequency of the ultrasound was 25kHz. It was demonstrated that ultrasound irradiation can increase the rate of heat transfer significantly, resulting in considerably shorter cooling times. Higher intensities caused higher cooling rates, and Nu values were increased from about 23-27 to 25-108 depending on the intensity of ultrasound and the position of the sphere. However, high intensities of ultrasound led to the generation of heat at the surface of the sphere, thus limiting the lowest final temperature achieved. An analytical solution was developed considering the heat generation and was fitted to the experimental data with R(2) values in the range of 0.910-0.998. Visual observations revealed that both cavitation and acoustic streaming were important for heat transfer phenomenon. Cavitation clouds at the surface of the sphere were the main cause of heating effect. The results showed that closer distances to the transducer surface showed higher cooling rates. On the other hand, despite having a bigger distance from the transducer, when the sphere was located close to the gas-liquid interface the enhancement factor of heat transfer was higher. Ultrasound irradiation showed promising effect for the enhancement of convective heat transfer rate during immersion cooling. More investigations are required to demonstrate the behavior of ultrasound assisted heat transfer and resolve the proper way of the application of ultrasound to assist the cooling and/or freezing processes. Copyright © 2012 Elsevier B.V. All rights reserved.

Effect of acoustic streaming on the mass transfer from a sublimating sphere

NASA Astrophysics Data System (ADS)

Kawahara, N.; Yarin, A. L.; Brenn, G.; Kastner, O.; Durst, F.

2000-04-01

The effect of the acoustic streaming on the mass transfer from the surface of a sphere positioned in an ultrasonic acoustic levitator is studied both experimentally and theoretically. Acoustic levitation using standing ultrasonic waves is an experimental tool for studying the heat and mass transfer from small solid or liquid samples, because it allows an almost steady positioning of a sample at a fixed location in space. However, the levitator introduces some difficulties. One of the main problems with acoustic levitation is that an acoustic streaming is induced near the sample surface, which affects the heat and mass transfer rates, as characterized by increased Nusselt and Sherwood numbers. The transfer rates are not uniform along the sample surface, and the aim of the present study is to quantify the spatial Sherwood number distribution over the surface of a sphere. The experiments are based on the measurement of the surface shape of a sphere layered with a solid substance as a function of time using a charge-coupled device (CCD) camera with backlighting. The sphere used in this research is a glass sphere layered with a volatile solid substance (naphthalene or camphor). The local mass transfer from the surface both with and without an ultrasonic acoustic field is investigated in order to evaluate the effect of the acoustic streaming. The experimental results are compared with predictions following from the theory outlined [A. L. Yarin, M. Pfaffenlehner, and C. Tropea, J. Fluid Mech. 356, 65 (1998); A. L. Yarin, G. Brenn, O. Kastner, D. Rensink, and C. Tropea, ibid. 399, 151 (1999)] which describes the acoustic field and the resulting acoustic streaming, and the mass transfer at the surface of particles and droplets located in an acoustic levitator. The results are also compared with the experimental data and with the theoretical predictions of Burdukov and Nakoryakov [J. Appl. Mech. Tech. Phys. 6, 51 (1965)], which are valid only in the case of spherical particles much smaller than the sound wavelength. Good agreement between experiment and the theory of Yarin et al. is demonstrated. The time-averaged heat and mass transfer rates over a sphere surface are greatest at the sphere's equator and least at its poles in the experiment as predicted by the theory (the ultrasonic standing wave spans the vertical axis passing through the poles). The measured distribution of the mass transfer rate over the sphere surface also agrees with the theoretical predictions, which shows that in strong acoustic fields sublimation (or evaporation) results from the acoustic streaming.

Active space debris charging for contactless electrostatic disposal maneuvers

NASA Astrophysics Data System (ADS)

Schaub, Hanspeter; Sternovsky, Zoltán

2014-01-01

The remote charging of a passive object using an electron beam enables touchless re-orbiting of large space debris from geosynchronous orbit (GEO) using electrostatic forces. The advantage of this method is that it can operate with a separation distance of multiple craft radii, thus reducing the risk of collision. The charging of the tug-debris system to high potentials is achieved by active charge transfer using a directed electron beam. Optimal potential distributions using isolated- and coupled-sphere models are discussed. A simple charging model takes into account the primary electron beam current, ultra-violet radiation induced photoelectron emission, collection of plasma particles, secondary electron emission and the recapture of emitted particles. The results show that through active charging in a GEO space environment high potentials can be both achieved and maintained with about a 75% transfer efficiency. Further, the maximum electrostatic tractor force is shown to be insensitive to beam current levels. This latter later result is important when considering debris with unknown properties.

Improved method for producing small hollow spheres

DOEpatents

Rosencwaig, A.; Koo, J.C.; Dressler, J.L.

An improved method and apparatus for producing small hollow spheres of glass having an outer diameter ranging from about 100..mu.. to about 500..mu.. with a substantially uniform wall thickness in the range of about 0.5 to 20..mu.. are described. The method involves introducing aqueous droplets of a glass-forming solution into a long vertical drop oven or furnace having varying temperature regions.

Exploring the molecular mechanisms of electron shuttling across the microbe/metal space

PubMed Central

Paquete, Catarina M.; Fonseca, Bruno M.; Cruz, Davide R.; Pereira, Tiago M.; Pacheco, Isabel; Soares, Cláudio M.; Louro, Ricardo O.

2014-01-01

Dissimilatory metal reducing organisms play key roles in the biogeochemical cycle of metals as well as in the durability of submerged and buried metallic structures. The molecular mechanisms that support electron transfer across the microbe-metal interface in these organisms remain poorly explored. It is known that outer membrane proteins, in particular multiheme cytochromes, are essential for this type of metabolism, being responsible for direct and indirect, via electron shuttles, interaction with the insoluble electron acceptors. Soluble electron shuttles such as flavins, phenazines, and humic acids are known to enhance extracellular electron transfer. In this work, this phenomenon was explored. All known outer membrane decaheme cytochromes from Shewanella oneidensis MR-1 with known metal terminal reductase activity and a undecaheme cytochrome from Shewanella sp. HRCR-6 were expressed and purified. Their interactions with soluble electron shuttles were studied using stopped-flow kinetics, NMR spectroscopy, and molecular simulations. The results show that despite the structural similarities, expected from the available structural data and sequence homology, the detailed characteristics of their interactions with soluble electron shuttles are different. MtrC and OmcA appear to interact with a variety of different electron shuttles in the close vicinity of some of their hemes, and with affinities that are biologically relevant for the concentrations typical found in the medium for this type of compounds. All data support a view of a distant interaction between the hemes of MtrF and the electron shuttles. For UndA a clear structural characterization was achieved for the interaction with AQDS a humic acid analog. These results provide guidance for future work of the manipulation of these proteins toward modulation of their role in metal attachment and reduction. PMID:25018753

Does Harcus-Hush theory really work The solvent dependence of intervalence charge-transfer energetics in (NH[sub 3])[sub 5]Ru[sup II]-4,4'-bipyridine-Ru[sup III](NH[sub 3] )[sub 5][sup 5+] in the limit of infinite dilution

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

Hupp, J.T.; Dong, Y.; Blackbourn, R.L.

1993-04-01

Because of concern about ion-pairing artifacts, the solvent dependence of the intervalence charge-transfer absorption energy for a prototypical mixed-valence system, (NH[sub 3])[sub 5]Ru[sup III]-4,4'-bipyridine-Ru[sup II](NH[sub 3])[sub 5][sup 5+], has been reexamined in the limit of infinite dilution. New data are reported for 14 solvents. While one of these (hexamethylphosphoramide) yields anomalous energetics, the absorption energies for the remaining 13 solvents agree qualitatively with the predictions of the Marcus-Hush theory (i.e., two-sphere dielectric continuum theory). On a quantitative basis, however, there is substantial disagreement with theory, at least when the charge-transfer distance is equated with the metal-to-metal separation distance (as conventionallymore » done). Replacement of this distance with a much shorter distance inferred from by electronic Stark-effect spectroscopy leads to a 3-fold decrease in the magnitude of calculated solvent reorganizational contributions to the overall intervalence energy (and therefore, very good agreement with experiment). Unfortunately, the use of such a short charge-transfer distance (d = 5.1 [+-] 0.7 A) also leads to a violation of one of the boundary conditions for use of the two-sphere model. Reformulation of the problem in terms of a generalized dipole-inversion, dielectric cavity problem, however, leads to nearly perfect agreement between theory and experiment. Additional analysis shows that experiment now also agrees reasonably well with theory regarding the magnitude of solvent-independent energy contributions. Finally, it is noted that downward revision in the estimated charge-transfer distance (from 11.3 to 5.1 A) leads to a substantial upward revision in the experimental (i.e., oscillator-strength based) estimate of the electronic coupling element, H[sub if], for intervalence transfer. 33 refs., 3 figs., 2 tabs.« less

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

PubMed

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

2018-01-16

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

Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

PubMed

Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin

2010-09-21

In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

Thermal Management of Vehicle Electronic Payloads Using Nanofluids and Thermoelectric Devices--Modeling and Analysis (PREPRINT)

DTIC Science & Technology

2011-03-01

Transfer Engineering, Vol. 30, No. 14, pp. 1136-1150. Chang, Y.W., Chang, C.C., Ke, M.T. and Chen, S.L. (2009) ’ Thermoelectric air-cooling module for...2005) ’An assessment of module cooling enhancement with thermoelectric coolers’, Journal of Heat Transfer-Transactions of the Asme, Vol. 127, No. 1, pp...nanoparticle out outer loop p nanoparticle TEC thermoelectric module w water UNCLASSIFIED UNCLASSIFIED Page 23 of 28 Tables Table 1

Heat-Transfer in Reflector-type Self-Ballasted Compact Fluorescent Lamps

NASA Astrophysics Data System (ADS)

Yasuda, Takeo; Toda, Masahiro; Matsumoto, Shinichiro; Takahara, Yuichiro

Self-ballasted compact fluorescent lamps (SBCFL) are widely used to replace incandescent lamps (IL) to save energy. We studied the heat-transfer phenomena of SBCFLs with outer envelopes by measuring the temperatures of the lamp parts, the power consumption, and the luminous output, and by calculating the energy balance. The methods applied were heat-transfer network analysis and computational fluid dynamics (CFD) using FLUENT® software. The heat loss increased in reflector-type SBCFLs as compared to SBCFLs with non-reflective outer envelopes, and was estimated at about 3 W when the total lamp power was 22 W. This results in a temperature rise of 20 K in the plastic holder, and a maximum rise of 10 K at the electronic components on the circuit board. Accordingly, we have developed a 12 W reflector-type SBCFL, which replaces a 60 W incandescent, not a 22 W SBCFL replacing a 100 W incandescent R-lamp, due to the importance of thermal reliability.

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

Promoting the Adsorption of Metal Ions on Kaolinite by Defect Sites: A Molecular Dynamics Study

PubMed Central

Li, Xiong; Li, Hang; Yang, Gang

2015-01-01

Defect sites exist abundantly in minerals and play a crucial role for a variety of important processes. Here molecular dynamics simulations are used to comprehensively investigate the adsorption behaviors, stabilities and mechanisms of metal ions on defective minerals, considering different ionic concentrations, defect sizes and contents. Outer-sphere adsorbed Pb2+ ions predominate for all models (regular and defective), while inner-sphere Na+ ions, which exist sporadically only at concentrated solutions for regular models, govern the adsorption for all defective models. Adsorption quantities and stabilities of metal ions on kaolinite are fundamentally promoted by defect sites, thus explaining the experimental observations. Defect sites improve the stabilities of both inner- and outer-sphere adsorption, and (quasi) inner-sphere Pb2+ ions emerge only at defect sites that reinforce the interactions. Adsorption configurations are greatly altered by defect sites but respond weakly by changing defect sizes or contents. Both adsorption quantities and stabilities are enhanced by increasing defect sizes or contents, while ionic concentrations mainly affect adsorption quantities. We also find that adsorption of metal ions and anions can be promoted by each other and proceeds in a collaborative mechanism. Results thus obtained are beneficial to comprehend related processes for all types of minerals. PMID:26403873

Flow and heat transfer in a curved channel

NASA Technical Reports Server (NTRS)

Brinich, P. F.; Graham, R. W.

1977-01-01

Flow and heat transfer in a curved channel of aspect ratio 6 and inner- to outer-wall radius ratio 0.96 were studied. Secondary currents and large longitudinal vortices were found. The heat-transfer rates of the outer and inner walls were independently controlled to maintain a constant wall temperature. Heating the inner wall increased the pressure drop along the channel length, whereas heating the outer wall had little effect. Outer-wall heat transfer was as much as 40 percent greater than the straight-channel correlation, and inner-wall heat transfer was 22 percent greater than the straight-channel correlation.

Investigation and application of multiple reactions between molybdoniobium heteropoly acid and di- or trimethylthionines

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

Mirzoyam, F.B.; Karapetyan, A.A.

1986-03-01

This paper presents the results of the study and use of reactions of molybdoniobic acid (MNA) with di- and trimethylthiones (DMT and TMT, respectively). It was found that light absorption of acetone solutions of the products of outer-sphere interaction between MNA and DMT or TMT enabled the determination of optimum acidity for MNA formation. Reaction between TMT and MNA gives two different compounds containing two and five associated dye cations, different in molar extinction coefficient and optimum reaction acidity (pH 0.05-0.25 and 0.35-0.90). Formation of the 6th and 8th molybdenum series with an identical composition of the outer sphere ismore » shown. A highly sensitive photometric method for determining niobium has been developed.« less

Kinetic and mechanism of the oxidation of chromium(III) complex with anthranil- N, N-diacetic acid by periodate ion in acidic aqueous solutions

NASA Astrophysics Data System (ADS)

Ali, Ismat H.

2015-06-01

The kinetics of oxidation of [CrIII(atda)(H2O)2] (atda = anthranil- N, N-diacetato) complex by IO{4/-} was studied spectrophotometrically in aqueous solutions with pH range 2.20-3.34, 0.30 M ionic strength and in 20.0-40.0°C temperature range. The rate law of the reaction exhibited saturation kinetics. Values of the rate constant for the electron transfer process, the equilibrium constant for dissociation of [CrIII (atda)(H2O)2] to [CrIII (atda) (H2O)OH]+ + H+ and the pre-equilibrium formation constant were calculated. The thermodynamic activation parameters are reported. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of the IVII to chromium(III).

Solvent extraction: the coordination chemistry behind extractive metallurgy.

PubMed

Wilson, A Matthew; Bailey, Phillip J; Tasker, Peter A; Turkington, Jennifer R; Grant, Richard A; Love, Jason B

2014-01-07

The modes of action of the commercial solvent extractants used in extractive hydrometallurgy are classified according to whether the recovery process involves the transport of metal cations, M(n+), metalate anions, MXx(n-), or metal salts, MXx into a water-immiscible solvent. Well-established principles of coordination chemistry provide an explanation for the remarkable strengths and selectivities shown by most of these extractants. Reagents which achieve high selectivity when transporting metal cations or metal salts into a water-immiscible solvent usually operate in the inner coordination sphere of the metal and provide donor atom types or dispositions which favour the formation of particularly stable neutral complexes that have high solubility in the hydrocarbons commonly used in recovery processes. In the extraction of metalates, the structures of the neutral assemblies formed in the water-immiscible phase are usually not well defined and the cationic reagents can be assumed to operate in the outer coordination spheres. The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bonding interactions are favoured by the low polarity of the water-immiscible solvents.

Tungsten species in natural ferromanganese oxides related to its different behavior from molybdenum in oxic ocean

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Takahashi, Yoshio; Marcus, Matthew A.; Uruga, Tomoya; Tanida, Hajime; Terada, Yasuko; Usui, Akira

2013-04-01

The tungsten (W) species in marine ferromanganese oxides were investigated by wavelength dispersive XAFS method. We found that the W species are in distorted Oh symmetry in natural ferromanganese oxides. The host phase of W is suggested to be Mn oxides by μ-XRF mapping. We also found that the W species forms inner-sphere complexes in hexavalent state and distorted Oh symmetry on synthetic ferrihydrite, goethite, hematite, and δ-MnO2. The molecular-scale information of W indicates that the negatively-charged WO42- ion mainly adsorbs on the negatively-charged Mn oxides phase in natural ferromanganese oxides due to the strong chemical interaction. In addition, preferential adsorption of lighter W isotopes is expected based on the molecular symmetry of the adsorbed species, implying the potential significance of the W isotope systems similar to Mo. Adsorption experiments of W on synthetic ferrihydrite and δ-MnO2 were also conducted. At higher equilibrium concentration, W exhibits behaviors similar to Mo on δ-MnO2 due to their formations of inner-sphere complexes. On the other hand, W shows a much larger adsorption on ferrihydrite than Mo. This is due to the formation of the inner- and outer-sphere complexes for W and Mo on ferrihydrite, respectively. Considering the lower equilibrium concentration such as in oxic seawater, however, the enrichment of W into natural ferromanganese oxides larger than Mo may be controlled by the different stabilities of their inner-sphere complexes on the Mn oxides. These two factors, (i) the stability of inner-sphere complexes on the Mn oxides and (ii) the mode of attachment on ferrihydrite (inner- or outer-sphere complex), are the causes of the different behaviors of W and Mo on the surface of the Fe/Mn (oxyhydr)oxides.

Ultraviolet photodetector using pn junction formed by transferrable hollow n-TiO2 nano-spheres monolayer.

PubMed

Yang, Taeyoung; Park, Seong-Jin; Kim, Taek Gon; Shin, Dong Su; Suh, Kyung-do; Park, Jinsub

2017-12-11

We report an ultraviolet (UV) photodetector with a universally transferable monolayer film with ordered hollow TiO 2 spheres on p-GaN. After forming a TiO 2 monolayer film by unidirectional rubbing of hollow TiO 2 spheres on a polydimethylsiloxane (PDMS) supporting plate, we used a 5% polyvinyl alcohol (PVA) aqueous solution to transfer the film onto the target substrate. The PVA/TiO 2 monolayer film was detached from the PDMS film and transferred to the p-GaN/Al 2 O 3 substrate. To investigate the effects of crystallized phases of the TiO 2 hollow spheres, anatase and rutile TiO 2 sphere monolayers prepared by combining template synthesis and thermal treatment. The responsiveness of the UV photodetectors using anatase and rutile hollow n-TiO 2 monolayer/p-GaN was 0.203 A/W at 312 nm and 0.093 A/W at 327 nm, respectively.

Heterogeneous Catalysis for Thermochemical Conversion Publications |

Science.gov Websites

pentagons is an upside-down Y shape and H2 +with a sideways Y shape with two lines at the base. A gold arrow a photo of woody biomass. In the center is a diamond shape composed of four outer triangle sections blue spheres. In the upper left is a large molecule shape made up of a hexagon of black spheres

Testing giant planet formation in the transitional disk of SAO 206462 using deep VLT/SPHERE imaging

NASA Astrophysics Data System (ADS)

Maire, A.-L.; Stolker, T.; Messina, S.; Müller, A.; Biller, B. A.; Currie, T.; Dominik, C.; Grady, C. A.; Boccaletti, A.; Bonnefoy, M.; Chauvin, G.; Galicher, R.; Millward, M.; Pohl, A.; Brandner, W.; Henning, T.; Lagrange, A.-M.; Langlois, M.; Meyer, M. R.; Quanz, S. P.; Vigan, A.; Zurlo, A.; van Boekel, R.; Buenzli, E.; Buey, T.; Desidera, S.; Feldt, M.; Fusco, T.; Ginski, C.; Giro, E.; Gratton, R.; Hubin, N.; Lannier, J.; Le Mignant, D.; Mesa, D.; Peretti, S.; Perrot, C.; Ramos, J. R.; Salter, G.; Samland, M.; Sissa, E.; Stadler, E.; Thalmann, C.; Udry, S.; Weber, L.

2017-05-01

Context. The SAO 206462 (HD 135344B) disk is one of the few known transitional disks showing asymmetric features in scattered light and thermal emission. Near-infrared scattered-light images revealed two bright outer spiral arms and an inner cavity depleted in dust. Giant protoplanets have been proposed to account for the disk morphology. Aims: We aim to search for giant planets responsible for the disk features and, in the case of non-detection, to constrain recent planet predictions using the data detection limits. Methods: We obtained new high-contrast and high-resolution total intensity images of the target spanning the Y to the K bands (0.95-2.3 μm) using the VLT/SPHERE near-infrared camera and integral field spectrometer. Results: The spiral arms and the outer cavity edge are revealed at high resolutions and sensitivities without the need for aggressive image post-processing techniques, which introduce photometric biases. We do not detect any close-in companions. For the derivation of the detection limits on putative giant planets embedded in the disk, we show that the knowledge of the disk aspect ratio and viscosity is critical for the estimation of the attenuation of a planet signal by the protoplanetary dust because of the gaps that these putative planets may open. Given assumptions on these parameters, the mass limits can vary from 2-5 to 4-7 Jupiter masses at separations beyond the disk spiral arms. The SPHERE detection limits are more stringent than those derived from archival NaCo/L' data and provide new constraints on a few recent predictions of massive planets (4-15 MJ) based on the spiral density wave theory. The SPHERE and ALMA data do not favor the hypotheses on massive giant planets in the outer disk (beyond 0.6''). There could still be low-mass planets in the outer disk and/or planets inside the cavity. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere under ESO programmes 095.C-0298 and 090.C-0443.

Chemoselective Hydrogenation of Aldehydes under Mild, Base-Free Conditions: Manganese Outperforms Rhenium

PubMed Central

2018-01-01

Several hydride Mn(I) and Re(I) PNP pincer complexes were applied as catalysts for the homogeneous chemoselective hydrogenation of aldehydes. Among these, [Mn(PNP-iPr)(CO)2(H)] was found to be one of the most efficient base metal catalysts for this process and represents a rare example which permits the selective hydrogenation of aldehydes in the presence of ketones and other reducible functionalities, such as C=C double bonds, esters, or nitriles. The reaction proceeds at room temperature under base-free conditions with catalyst loadings between 0.1 and 0.05 mol% and a hydrogen pressure of 50 bar (reaching TONs of up to 2000). A mechanism which involves an outer-sphere hydride transfer and reversible PNP ligand deprotonation/protonation is proposed. Analogous isoelectronic and isostructural Re(I) complexes were only poorly active. PMID:29755828

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

Hoffeditz, William L.; Katz, Michael J.; Deria, Pravas

Dye-sensitized solar cells (DSCs) are an established alternative photovoltaic technology that offers numerous potential advantages in solar energy applications. However, this technology has been limited by the availability of molecular redox couples that are both noncorrosive/nontoxic and do not diminish the performance of the device. In an effort to overcome these shortcomings, a copper-containing redox shuttle derived from 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (PDTO) ligand and the common DSC additive 4-tert-butylpyridine (TBP) was investigated. Electrochemical measurements, single-crystal X-ray diffraction, and absorption and electron paramagnetic resonance spectroscopies reveal that, upon removal of one metal-centered electron, PDTO-enshrouded copper ions completely shed the tetradentate PDTO ligand andmore » replace it with four or more TBP ligands. Thus, the Cu(I) and Cu(II) forms of the electron shuttle have completely different coordination spheres and are characterized by widely differing Cu(II/I) formal potentials and reactivities for forward versus reverse electron transfer. Notably, the coordination-sphere replacement process is fully reversed upon converting Cu(II) back to Cu(I). In cells featuring an adsorbed organic dye and a nano- and mesoparticulate, TiO2-based, photoelectrode, the dual species redox shuttle system engenders performance superior to that obtained with shuttles based on the (II/I) forms of either of the coordination complexes in isolation.« less

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

NASA Astrophysics Data System (ADS)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral-water interface.

A Comparison of Two Yeast MnSODs: Mitochondrial Saccharomyces cerevisiae versus Cytosolic Candida albicans

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

Sheng Y.; Cabelli D.; Stich, T.A.

Human MnSOD is significantly more product-inhibited than bacterial MnSODs at high concentrations of superoxide (O{sub 2}{sup -}). This behavior limits the amount of H{sub 2}O{sub 2} produced at high [O{sub 2}{sup -}]; its desirability can be explained by the multiple roles of H{sub 2}O{sub 2} in mammalian cells, particularly its role in signaling. To investigate the mechanism of product inhibition in MnSOD, two yeast MnSODs, one from Saccharomyces cerevisiae mitochondria (ScMnSOD) and the other from Candida albicans cytosol (CaMnSODc), were isolated and characterized. ScMnSOD and CaMnSODc are similar in catalytic kinetics, spectroscopy, and redox chemistry, and they both rest predominantlymore » in the reduced state (unlike most other MnSODs). At high [O{sub 2}{sup -}], the dismutation efficiencies of the yeast MnSODs surpass those of human and bacterial MnSODs, due to very low level of product inhibition. Optical and parallel-mode electron paramagnetic resonance (EPR) spectra suggest the presence of two Mn{sup 3+} species in yeast Mn{sup 3+}SODs, including the well-characterized 5-coordinate Mn{sup 3+} species and a 6-coordinate L-Mn{sup 3+} species with hydroxide as the putative sixth ligand (L). The first and second coordination spheres of ScMnSOD are more similar to bacterial than to human MnSOD. Gln154, an H-bond donor to the Mn-coordinated solvent molecule, is slightly further away from Mn in yeast MnSODs, which may result in their unusual resting state. Mechanistically, the high efficiency of yeast MnSODs could be ascribed to putative translocation of an outer-sphere solvent molecule, which could destabilize the inhibited complex and enhance proton transfer from protein to peroxide. Our studies on yeast MnSODs indicate the unique nature of human MnSOD in that it predominantly undergoes the inhibited pathway at high [O{sub 2}{sup -}].« less

A Comparison of Two Yeast MnSODs: Mitochondrial Saccharomyces cerevisiae versus Cytosolic Candida albicans

PubMed Central

Sheng, Yuewei; Stich, Troy A.; Barnese, Kevin; Gralla, Edith B.; Cascio, Duilio; Britt, R. David; Cabelli, Diane E.; Valentine, Joan Selverstone

2011-01-01

Human MnSOD is significantly more product-inhibited than bacterial MnSODs at high concentrations of superoxide (O2−). This behavior limits the amount of H2O2 produced at high [O2−]; its desirability can be explained by the multiple roles of H2O2 in mammalian cells, particularly its role in signaling. To investigate the mechanism of product inhibition in MnSOD, two yeast MnSODs, one from Saccharomyces cerevisiae mitochondria (ScMnSOD) and the other from Candida albicans cytosol (CaMnSODc), were isolated and characterized. ScMnSOD and CaMnSODc are similar in catalytic kinetics, spectroscopy and redox chemistry, and they both rest predominantly in the reduced state (unlike most other MnSODs). At high [O2−] the dismutation efficiencies of the yeast MnSODs surpass those of human and bacterial MnSODs, due to very low level of product inhibition. Optical and parallel-mode electron paramagnetic resonance (EPR) spectra suggest the presence of two Mn3+ species in yeast Mn3+SODs, including the well-characterized 5-coordinate Mn3+ species and a 6-coordinate L-Mn3+ species with hydroxide as the putative sixth ligand (L). The first and second coordination spheres of ScMnSOD are more similar to bacterial than to human MnSOD. Gln154, an H-bond donor to the Mn-coordinated solvent molecule, is slightly further away from Mn in yeast MnSODs, which may result in their unusual resting state. Mechanistically, the high efficiency of yeast MnSODs could be ascribed to putative translocation of an outer-sphere solvent molecule, which could destabilize the inhibited complex and enhance proton transfer from protein to peroxide. Our studies on yeast MnSODs indicate the unique nature of human MnSOD in that it predominantly undergoes the inhibited pathway at high [O2−]. PMID:22077216

"Outer-sphere to inner-sphere" redox cycling for ultrasensitive immunosensors.

PubMed

Akanda, Md Rajibul; Choe, Yu-Lim; Yang, Haesik

2012-01-17

This paper reports chemical-chemical (CC) and electrochemical-chemical-chemical (ECC) redox cycling, for use in ultrasensitive biosensor applications. A triple chemical amplification approach using an enzymatic reaction, CC redox cycling, and ECC redox cycling is applied toward electrochemical immunosensors of cardiac troponin I. An enzymatic reaction, in which alkaline phosphatase converts 4-aminophenyl phosphate to 4-aminophenol (AP), triggers CC redox cycling in the presence of an oxidant and a reductant, and electrochemical signals are measured with ECC redox cycling after an incubation period of time in an air-saturated solution. To obtain high, selective, and reproducible redox cycling without using redox enzymes, two redox reactions [the reaction between AP and the oxidant and the reaction between the oxidized form of AP (4-quinone imine, QI) and the reductant] should be fast, but an unwanted reaction between the oxidant and reductant should be very slow. Because species that undergo outer-sphere reactions (OSR-philic species) react slowly with species that undergo inner-sphere reactions (ISR-philic species), highly OSR-philic Ru(NH(3))(6)(3+) and highly ISR-philic tris(2-carboxyethyl)phosphine (TCEP) are chosen as the oxidant and reductant, respectively. The OSR- and ISR-philic QI/AP couple allows fast redox reactions with both the OSR-philic Ru(NH(3))(6)(3+) and the ISR-philic TCEP. Highly OSR-philic indium-tin oxide (ITO) electrodes minimize unwanted electrochemical reactions with highly ISR-philic species. Although the formal potential of the Ru(NH(3))(6)(3+)/Ru(NH(3))(6)(2+) couple is lower than that of the QI/AP couple, the endergonic reaction between Ru(NH(3))(6)(3+) and AP is driven by the highly exergonic reaction between TCEP and QI (via a coupled reaction mechanism). Overall, the "outer-sphere to inner-sphere" redox cycling in the order of highly OSR-philic ITO, highly OSR-philic Ru(NH(3))(6)(3+)/Ru(NH(3))(6)(2+) couple, OSR- and ISR-philic QI/AP couple, and highly ISR-philic TCEP allows high, selective, and reproducible signal amplification. The electrochemical data obtained by chronocoulometry permit a lower detection limits than those obtained by cyclic voltammetry. The detection limit of an immunosensor for troponin I in serum, calculated from the anodic charges in chronocoulometry, is ca. 10 fg/mL.

An inner warp in the DoAr 44 T Tauri transition disc

NASA Astrophysics Data System (ADS)

Casassus, Simon; Avenhaus, Henning; Pérez, Sebastián; Navarro, Víctor; Cárcamo, Miguel; Marino, Sebastián; Cieza, Lucas; Quanz, Sascha P.; Alarcón, Felipe; Zurlo, Alice; Osses, Axel; Rannou, Fernando R.; Román, Pablo E.; Barraza, Marcelo

2018-07-01

Optical/IR images of transition discs (TDs) have revealed deep intensity decrements in the rings of HAeBes HD 142527 and HD 100453 that can be interpreted as shadowing from sharply tilted inner discs, such that the outer discs are directly exposed to stellar light. Here we report similar dips in SPHERE+IRDIS differential polarized imaging (DPI) of T Tauri DoAr 44. With a fairly axially symmetric ring in the sub-mm radio continuum, DoAr 44 is likely also a warped system. We constrain the warp geometry by comparing radiative transfer predictions with the DPI data in H band (Qϕ(H)) and with a re-processing of archival 336 GHz ALMA observations. The observed DPI shadows have coincident radio counterparts, but the intensity drops are much deeper in Qϕ(H) (˜88 per cent), compared to the shallow drops at 336 GHz (˜24 per cent). Radiative transfer predictions with an inner disc tilt of ˜30 ± 5 deg approximately account for the observations. ALMA long-baseline observations should allow the observation of the warped gas kinematics inside the cavity of DoAr 44.

An inner warp in the DoAr 44 T Tauri transition disk

NASA Astrophysics Data System (ADS)

Casassus, Simon; Avenhaus, Henning; Pérez, Sebastián; Navarro, Víctor; Cárcamo, Miguel; Marino, Sebastián; Cieza, Lucas; Quanz, Sascha P.; Alarcón, Felipe; Zurlo, Alice; Osses, Axel; Rannou, Fernando R.; Román, Pablo E.; Barraza, Marcelo

2018-04-01

Optical/IR images of transition disks (TDs) have revealed deep intensity decrements in the rings of HAeBes HD 142527 and HD 100453, that can be interpreted as shadowing from sharply tilted inner disks, such that the outer disks are directly exposed to stellar light. Here we report similar dips in SPHERE+IRDIS differential polarized imaging (DPI) of TTauri DoAr 44. With a fairly axially symmetric ring in the sub mm radio continuum, DoAr 44 is likely also a warped system. We constrain the warp geometry by comparing radiative transfer predictions with the DPI data in H band (Qϕ(H)) and with a re-processing of archival 336 GHz ALMA observations. The observed DPI shadows have coincident radio counterparts, but the intensity drops are much deeper in Qϕ(H) (˜88%), compared to the shallow drops at 336 GHz (˜24%). Radiative transfer predictions with an inner disk tilt of ˜30 ± 5 deg approximately account for the observations. ALMA long-baseline observations should allow the observation of the warped gas kinematics inside the cavity of DoAr 44.

Flipping of the coordinated triazine moiety in Cu(I)-L2 and the small electronic factor, κel, for direct outer-sphere cross reactions: syntheses, crystal structures and redox behaviour of copper(II)/(I)-L2 complexes (L = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine).

PubMed

Yamada, Atsutoshi; Mabe, Takuya; Yamane, Ryohei; Noda, Kyoko; Wasada, Yuko; Inamo, Masahiko; Ishihara, Koji; Suzuki, Takayoshi; Takagi, Hideo D

2015-08-21

Six-coordinate [Cu(pdt)2(H2O)2](2+) and four-coordinate [Cu(pdt)2](+) complexes were synthesized and the cross redox reactions were studied in acetonitrile (pdt = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine). Single crystal analyses revealed that [Cu(pdt)2(H2O)2](BF4)2 was of pseudo-D2h symmetry with two axial water molecules and two symmetrically coordinated equatorial pdt ligands, while the coordination structure of [Cu(pdt)2]BF4 was a squashed tetrahedron (dihedral angle = 54.87°) with an asymmetric coordination by two pdt ligands: one pdt ligand was coordinated to Cu(i) through pyridine-N and triazine-N2 while another pdt ligand was coordinated through pyridine-N and triazine-N4, and a stacking interaction between the phenyl ring on one pdt ligand and the triazine ring on another pdt ligand caused the squashed structure and non-equivalent Cu-N bond lengths. The cyclic voltammograms for [Cu(pdt)2(H2O)2](2+) and [Cu(pdt)2](+) in acetonitrile were identical to each other and quasi-reversible. The reduction of [Cu(pdt)2(H2O)2](2+) by decamethylferrocene and the oxidation of [Cu(pdt)2](+) by [Co(2,2'-bipyridine)3](3+) in acetonitrile revealed that both cross reactions were sluggish through a gated process (the structural change took place prior to the electron transfer) accompanied by slow direct electron transfer processes. It was found that the triazine ring of the coordinated pdt ligand rotates around the C-C bond between the triazine and pyridine rings with the kinetic parameters k = 51 ± 5 s(-1) (297.8 K), ΔH(‡) = 6.2 ± 1.1 kJ mol(-1) and ΔS(‡) = -192 ± 4 J mol(-1) K(-1). The electron self-exchange process was directly measured using the line-broadening method: kex = (9.9 ± 0.5) × 10(4) kg mol(-1) s(-1) (297.8 K) with ΔH(‡) = 44 ± 7 kJ mol(-1) and ΔS(‡) = 0.2 ± 2.6 J mol(-1) K(-1). By comparing this rate constant with the self-exchange rate constants estimated from the cross reactions using the Marcus cross relation, the non-adiabaticity (electronic) factors, κel, for the direct electron transfer processes between [Cu(pdt)2](+/2+) and non-copper metal (Fe(2+) and Co(3+)) complexes were estimated as ca. 10(-7), indicating that the electronic coupling between the d orbitals of copper and of non-copper metals is very small.

Simulations of the kinematic dynamo onset of spherical Couette flows with smooth and rough boundaries.

PubMed

Finke, K; Tilgner, A

2012-07-01

We study numerically the dynamo transition of an incompressible electrically conducting fluid filling the gap between two concentric spheres. In a first series of simulations, the fluid is driven by the rotation of a smooth inner sphere through no-slip boundary conditions, whereas the outer sphere is stationary. In a second series a volume force intended to simulate a rough surface drives the fluid next to the inner sphere within a layer of thickness one-tenth of the gap width. We investigate the effect of the boundary layer thickness on the dynamo threshold in the turbulent regime. The simulations show that the boundary forcing simulating the rough surface lowers the necessary rotation rate, which may help to improve spherical dynamo experiments.

One-pot template-free synthesis of uniform-sized fullerene-like magnetite hollow spheres

NASA Astrophysics Data System (ADS)

Zhu, Qing; Zhang, Yue; Liu, Zheng; Zhou, Xinrui; Zhang, Xinmei; Zeng, Lintao

2015-11-01

Uniform-sized Fe3O4 hollow spheres with average diameter of 250 nm and shell thickness of ∼50 nm have been successfully synthesized through a simple hydrothermal route with the presence of di-n-propylamine (DPA) as a weak-base. The reaction time and DPA amount play important roles in the formation of the magnetite hollow spheres. The structures of the products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectra, scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The results show that the single-crystalline Fe3O4 hollow spheres are composed of well-aligned magnetite nanoparticles (NPs). The magnetic property investigation shows that these hollow spheres have a higher saturation magnetization (Ms) than the solid spheres. Furthermore, a possible mechanism for the formation of magnetite hollow spheres is proposed based on the experimental observations.

Two Isoforms of Geobacter sulfurreducens PilA Have Distinct Roles in Pilus Biogenesis, Cytochrome Localization, Extracellular Electron Transfer, and Biofilm Formation

PubMed Central

Richter, Lubna V.; Sandler, Steven J.

2012-01-01

Type IV pili of Geobacter sulfurreducens are composed of PilA monomers and are essential for long-range extracellular electron transfer to insoluble Fe(III) oxides and graphite anodes. A previous analysis of pilA expression indicated that transcription was initiated at two positions, with two predicted ribosome-binding sites and translation start codons, potentially producing two PilA preprotein isoforms. The present study supports the existence of two functional translation start codons for pilA and identifies two isoforms (short and long) of the PilA preprotein. The short PilA isoform is found predominantly in an intracellular fraction. It seems to stabilize the long isoform and to influence the secretion of several outer-surface c-type cytochromes. The long PilA isoform is required for secretion of PilA to the outer cell surface, a process that requires coexpression of pilA with nine downstream genes. The long isoform was determined to be essential for biofilm formation on certain surfaces, for optimum current production in microbial fuel cells, and for growth on insoluble Fe(III) oxides. PMID:22408162

In vitro and in vivo study of the application of volvox spheres to co-culture vehicles in liver tissue engineering.

PubMed

Chang, Siou Han; Huang, Han Hsiang; Kang, Pei Leun; Wu, Yu Chian; Chang, Ming-Huang; Kuo, Shyh Ming

2017-11-01

Volvox sphere is a biomimetic concept of a natural Volvox, wherein a large outer sphere contains smaller inner spheres, which can encapsulate cells and provide a double-layer three-dimensional environment for culturing cells. This study simultaneously encapsulated rat mesenchymal stem cells (MSCs) and AML12 hepatocytes in volvox spheres and extensively evaluated the effects of various culturing modes on cell functions and fates. The results showed that compared with a static flask culture, MSCs encapsulated in volvox spheres differentiated into hepatocyte-like cells with a 2-fold increase in albumin (ALB) expression and a 2.5-fold increase in cytokeratin 18 expression in a dynamic bioreactor. Moreover, the restorative effects of volvox spheres encapsulating cells on retrorsine-exposed CCl 4 -induced liver injuries in rats were evaluated. The data presented significant reductions in AST and ALT levels after the implantation of volvox spheres encapsulating both MSCs and AML12 hepatocytes in vivo. In contrast to the negative control group, histopathological analysis demonstrated liver repair and formation of the new liver tissue in groups implanted with volvox spheres containing cells. These results demonstrate that liver cells implanted with volvox spheres encapsulating both MSCs and AML12 hepatocytes promote liver repair and liver tissue regeneration in liver failure caused by necrotizing agents such as retrorsine and CCl 4 . Hence, volvox spheres encapsulating MSCs and liver cells can be a promising and clinically effective therapy for liver injury. In this study, we used a volvox sphere, which is a unique design that mimics the natural Volvox, that consists of a large outer sphere that contains smaller inner spheres, which provide a three-dimensional environment to culture cells. The purpose of this study is to co-culture mesenchymal stem cells (MSCs) and AML12 liver cells in volvox spheres and evaluate two different culture methods, dynamic bioreactor and static culture flask,on the cultured cells. In addition, we aimed to evaluate the restorative effects of volvox spheres encapsulating MSCs and/or AML12 liver cells on rats with retrorsine-exposed CCl 4 -induced liver injuries. The results showed that MSCs encapsulated in volvox spheres differentiated into hepatocyte-like cells with a 2-fold increase in albumin expression and a 2.5-fold increase in cytokeratin 18 expression ina dynamic bioreactor. Moreover, the data presented significant reductions in AST and ALT levels after the implantation of volvox spheres encapsulating both MSCs and AML12 hepatocytes in vivo. In contrast to the negative control group, histopathological analysis demonstrated liver repair and formation of new liver tissue in groups implanted with volvox spheres containing cells. These results demonstrate that liver cells implanted with volvox spheres encapsulating both MSCs and AML12 hepatocytes promote liver repair and liver tissue regeneration in liver failure caused by necrotizing agents such as retrorsine and CCl 4 . Hence, volvox spheres encapsulating MSCs and liver cells can be a promising and clinically effective therapy for liver injury. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Extracting electron transfer coupling elements from constrained density functional theory

NASA Astrophysics Data System (ADS)

Wu, Qin; Van Voorhis, Troy

2006-10-01

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculations on the Zn2+ and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives Hab≈17kcal /mol, which qualitatively disagrees with experimental results, the Hab calculated from constrained DFT is about 3kcal /mol and the generated ground state has a barrier height of 1.70kcal/mol, successfully predicting (Q-TTF-Q)- to be a class II mixed-valence compound.

Sphere based fluid systems

NASA Technical Reports Server (NTRS)

Elleman, Daniel D. (Inventor); Wang, Taylor G. (Inventor)

1989-01-01

Systems are described for using multiple closely-packed spheres. In one system for passing fluid, a multiplicity of spheres lie within a container, with all of the spheres having the same outside diameter and with the spheres being closely nested in one another to create multiple interstitial passages of a known size and configuration and smooth walls. The container has an inlet and outlet for passing fluid through the interstitial passages formed between the nested spheres. The small interstitial passages can be used to filter out material, especially biological material such as cells in a fluid, where the cells can be easily destroyed if passed across sharp edges. The outer surface of the spheres can contain a material that absorbs a constitutent in the flowing fluid, such as a particular contamination gas, or can contain a catalyst to chemically react the fluid passing therethrough, the use of multiple small spheres assuring a large area of contact of these surfaces of the spheres with the fluid. In a system for storing and releasing a fluid such as hydrogen as a fuel, the spheres can include a hollow shell containing the fluid to be stored, and located within a compressable container that can be compressed to break the shells and release the stored fluid.

Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

PubMed Central

White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice C.; Marshall, Matthew J.; Fredrickson, James K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

2013-01-01

The mineral-respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes, MtrC and MtrA, brought together inside a transmembrane porin, MtrB, to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system containing a pool of internalized electron carriers was used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, the established in vivo orientation, electron transfer from the interior electron carrier pool through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The rates were 103 times higher than those reported for reduction of goethite, hematite, and lepidocrocite by S. oneidensis, and the order of the reaction rates was consistent with those observed in S. oneidensis cultures. In contrast, established rates for single turnover reactions between purified MtrC and Fe(III) oxides were 103 times lower. By providing a continuous flow of electrons, the proteoliposome experiments demonstrate that conduction through MtrCAB directly to Fe(III) oxides is sufficient to support in vivo, anaerobic, solid-phase iron respiration. PMID:23538304

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

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

Wang, Zheming; Shi, Zhi; Shi, Liang

2015-08-25

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, some evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin that are proposed to mediate electron transfer (Marsili et al., 2008). In this work, we used methyl viologen (MV•+)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of secreted flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 µM) by MELs ([MV•+] ~ 42 µM and MtrABC ≤ 1 nM)more » were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MV•+ and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 seconds. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (≤ 1 µM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. However, at higher FMN concentrations (> 1 µM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction. The implications of the observed kinetic behaviors to flavin-mediated Fe(III) oxide reduction in natural environments are discussed.« less

Rapid Dye Regeneration Mechanism of Dye-Sensitized Solar Cells.

PubMed

Jeon, Jiwon; Park, Young Choon; Han, Sang Soo; Goddard, William A; Lee, Yoon Sup; Kim, Hyungjun

2014-12-18

During the light-harvesting process of dye-sensitized solar cells (DSSCs), the hole localized on the dye after the charge separation yields an oxidized dye, D(+). The fast regeneration of D(+) using the redox pair (typically the I(-)/I3(-) couple) is critical for the efficient DSSCs. However, the kinetic processes of dye regeneration remain uncertain, still promoting vigorous debates. Here, we use molecular dynamics simulations to determine that the inner-sphere electron-transfer pathway provides a rapid dye regeneration route of ∼4 ps, where penetration of I(-) next to D(+) enables an immediate electron transfer, forming a kinetic barrier. This explains the recently reported ultrafast dye regeneration rate of a few picoseconds determined experimentally. We expect that our MD based comprehensive understanding of the dye regeneration mechanism will provide a helpful guideline in designing TiO2-dye-electrolyte interfacial systems for better performing DSSCs.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

The mitochondrial outer membrane protein mitoNEET is a redox enzyme catalyzing electron transfer from FMNH2 to oxygen or ubiquinone.

PubMed

Wang, Yiming; Landry, Aaron P; Ding, Huangen

2017-06-16

Increasing evidence suggests that mitoNEET, a target of the type II diabetes drug pioglitazone, is a key regulator of energy metabolism in mitochondria. MitoNEET is anchored to the mitochondrial outer membrane via its N-terminal α helix domain and hosts a redox-active [2Fe-2S] cluster in its C-terminal cytosolic region. The mechanism by which mitoNEET regulates energy metabolism in mitochondria, however, is not fully understood. Previous studies have shown that mitoNEET specifically interacts with the reduced flavin mononucleotide (FMNH 2 ) and that FMNH 2 can quickly reduce the mitoNEET [2Fe-2S] clusters. Here we report that the reduced mitoNEET [2Fe-2S] clusters can be readily oxidized by oxygen. In the presence of FMN, NADH, and flavin reductase, which reduces FMN to FMNH 2 using NADH as the electron donor, mitoNEET mediates oxidation of NADH with a concomitant reduction of oxygen. Ubiquinone-2, an analog of ubiquinone-10, can also oxidize the reduced mitoNEET [2Fe-2S] clusters under anaerobic or aerobic conditions. Compared with oxygen, ubiquinone-2 is more efficient in oxidizing the mitoNEET [2Fe-2S] clusters, suggesting that ubiquinone could be an intrinsic electron acceptor of the reduced mitoNEET [2Fe-2S] clusters in mitochondria. Pioglitazone or its analog NL-1 appears to inhibit the electron transfer activity of mitoNEET by forming a unique complex with mitoNEET and FMNH 2 The results suggest that mitoNEET is a redox enzyme that may promote oxidation of NADH to facilitate enhanced glycolysis in the cytosol and that pioglitazone may regulate energy metabolism in mitochondria by inhibiting the electron transfer activity of mitoNEET. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

The Heat and Mass Transfer Processes at the Cooling of Strong Heated Sphere in a Cold Liquid

NASA Astrophysics Data System (ADS)

Puzina, Yu Yu

2017-10-01

Some new experimental results of continuum mechanics problems in two-phase systems are described. The processes of heat and mass transfer during cooling of strong heated sphere in the subcooled liquid are studied. Due to high level of heater temperature the stable vapor film is formed on the sphere surface. Calculation of steady-state transport processes at vapor - water interface is carried out using methods of molecular-kinetic theory. Heat transfer in vapor by thermal conductivity and natural convection in liquid are considered. Pressure balance is provided by hydrostatic pressure and non-equilibrium boundary condition. The results of the calculations are analyzed by comparison with previous data and experimental results.

Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry.

PubMed

Le Pleux, Loïc; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Harriman, Anthony

2011-05-26

A series of multiporphyrin clusters has been synthesized and characterized in which there exists a logical gradient for either energy or electron transfer between the porphyrins. A central free-base porphyrin (FbP), for example, is equipped with peripheral zinc(II) porphyrins (ZnP) which act as ancillary light harvesters and transfer excitation energy to the FbP under visible light illumination. Additional energy-transfer steps occur at the triplet level, and the series is expanded by including magnesium(II) porphyrins and/or tin(IV) porphyrins as chromophores. Light-induced electron transfer is made possible by incorporating a gold(III) porphyrin (AuP(+)) into the array. Although interesting by themselves, these clusters serve as control compounds by which to understand the photophysical processes occurring within a three-stage dendrimer comprising an AuP(+) core, a second layer formed from four FbP units, and an outer layer containing 12 ZnP residues. Here, illumination into a peripheral ZnP leads to highly efficient electronic energy transfer to FbP, followed by charge transfer to the central AuP(+). Charge recombination within the resultant charge-shift state is intercepted by secondary hole transfer to the ZnP, which occurs with a quantum yield of around 20%. The final charge-shift state survives for some microseconds in fluid solution at room temperature.

Curious case of gravitational lensing by binary black holes: A tale of two photon spheres, new relativistic images, and caustics

NASA Astrophysics Data System (ADS)

Patil, Mandar; Mishra, Priti; Narasimha, D.

2017-01-01

Binary black holes have been in the limelight of late due to the detection of gravitational waves from coalescing compact binaries in the events GW150914 and GW151226. In this paper we study gravitational lensing by the binary black holes modeled as an equal mass Majumdar-Papapetrou dihole metric and show that this system displays features that are quite unprecedented and absent in any other lensing configuration investigated so far in the literature. We restrict our attention to the light rays which move on the plane midway between the two identical black holes, which allows us to employ various techniques developed for the equatorial lensing in the spherically symmetric spacetimes. If distance between the two black holes is below a certain threshold value, then the system admits two photon spheres. As in the case of a single black hole, infinitely many relativistic images are formed due to the light rays which turn back from the region outside the outer (unstable) photon sphere, all of which lie beyond a critical angular radius with respect to the lens. However, in the presence of the inner (stable) photon sphere, the effective potential after admitting minimum turns upwards and blows up for the smaller values of radii and the light rays that enter the outer photon sphere can turn back, leading to the formation of a new set of infinitely many relativistic images, all of which lie below the critical radius from the lens mentioned above. As the distance between the two black holes is increased, two photon spheres approach one another, merge and eventually disappear. In the absence of the photon sphere, apart from the formation of a finite number of discrete relativistic images, the system remarkably admits a radial caustic, which has never been observed in the context of relativistic lensing before. Thus the system of the binary black hole admits novel features both in the presence and absence of photon spheres. We discuss possible observational signatures and implications of the binary black hole lensing.

Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibria for self-exchange of anionic (dinitrobenzenide) donors.

PubMed

Rosokha, Sergiy V; Lü, Jian-Ming; Newton, Marshall D; Kochi, Jay K

2005-05-25

Definitive X-ray structures of "separated" versus "contact" ion pairs, together with their spectral (UV-NIR, ESR) characterizations, provide the quantitative basis for evaluating the complex equilibria and intrinsic (self-exchange) electron-transfer rates for the potassium salts of p-dinitrobenzene radical anion (DNB(-)). Three principal types of ion pairs, K(L)(+)DNB(-), are designated as Classes S, M, and C via the specific ligation of K(+) with different macrocyclic polyether ligands (L). For Class S, the self-exchange rate constant for the separated ion pair (SIP) is essentially the same as that of the "free" anion, and we conclude that dinitrobenzenide reactivity is unaffected when the interionic distance in the separated ion pair is r(SIP) > or =6 Angstroms. For Class M, the dynamic equilibrium between the contact ion pair (with r(CIP) = 2.7 Angstroms) and its separated ion pair is quantitatively evaluated, and the rather minor fraction of SIP is nonetheless the principal contributor to the overall electron-transfer kinetics. For Class C, the SIP rate is limited by the slow rate of CIP right arrow over left arrow SIP interconversion, and the self-exchange proceeds via the contact ion pair by default. Theoretically, the electron-transfer rate constant for the separated ion pair is well-accommodated by the Marcus/Sutin two-state formulation when the precursor in Scheme 2 is identified as the "separated" inner-sphere complex (IS(SIP)) of cofacial DNB(-)/DNB dyads. By contrast, the significantly slower rate of self-exchange via the contact ion pair requires an associative mechanism (Scheme 3) in which the electron-transfer rate is strongly governed by cationic mobility of K(L)(+) within the "contact" precursor complex (IS(CIP)) according to the kinetics in Scheme 4.

RadBall Technology Testing and MCNP Modeling of the Tungsten Collimator.

PubMed

Farfán, Eduardo B; Foley, Trevor Q; Coleman, J Rusty; Jannik, G Timothy; Holmes, Christopher J; Oldham, Mark; Adamovics, John; Stanley, Steven J

2010-01-01

The United Kingdom's National Nuclear Laboratory (NNL) has developed a remote, non-electrical, radiation-mapping device known as RadBall(™), which can locate and quantify radioactive hazards within contaminated areas of the nuclear industry. RadBall(™) consists of a colander-like outer shell that houses a radiation-sensitive polymer sphere. The outer shell works to collimate radiation sources and those areas of the polymer sphere that are exposed react, becoming increasingly more opaque, in proportion to the absorbed dose. The polymer sphere is imaged in an optical-CT scanner, which produces a high resolution 3D map of optical attenuation coefficients. Subsequent analysis of the optical attenuation matrix provides information on the spatial distribution of sources in a given area forming a 3D characterization of the area of interest. RadBall(™) has no power requirements and can be positioned in tight or hard-to reach locations. The RadBall(™) technology has been deployed in a number of technology trials in nuclear waste reprocessing plants at Sellafield in the United Kingdom and facilities of the Savannah River National Laboratory (SRNL). This study focuses on the RadBall(™) testing and modeling accomplished at SRNL.

RadBall™ Technology Testing and MCNP Modeling of the Tungsten Collimator

PubMed Central

Farfán, Eduardo B.; Foley, Trevor Q.; Coleman, J. Rusty; Jannik, G. Timothy; Holmes, Christopher J.; Oldham, Mark; Adamovics, John; Stanley, Steven J.

2010-01-01

The United Kingdom’s National Nuclear Laboratory (NNL) has developed a remote, non-electrical, radiation-mapping device known as RadBall™, which can locate and quantify radioactive hazards within contaminated areas of the nuclear industry. RadBall™ consists of a colander-like outer shell that houses a radiation-sensitive polymer sphere. The outer shell works to collimate radiation sources and those areas of the polymer sphere that are exposed react, becoming increasingly more opaque, in proportion to the absorbed dose. The polymer sphere is imaged in an optical-CT scanner, which produces a high resolution 3D map of optical attenuation coefficients. Subsequent analysis of the optical attenuation matrix provides information on the spatial distribution of sources in a given area forming a 3D characterization of the area of interest. RadBall™ has no power requirements and can be positioned in tight or hard-to reach locations. The RadBall™ technology has been deployed in a number of technology trials in nuclear waste reprocessing plants at Sellafield in the United Kingdom and facilities of the Savannah River National Laboratory (SRNL). This study focuses on the RadBall™ testing and modeling accomplished at SRNL. PMID:21617740

Reservoir computer predictions for the Three Meter magnetic field time evolution

NASA Astrophysics Data System (ADS)

Perevalov, A.; Rojas, R.; Lathrop, D. P.; Shani, I.; Hunt, B. R.

2017-12-01

The source of the Earth's magnetic field is the turbulent flow of liquid metal in the outer core. Our experiment's goal is to create Earth-like dynamo, to explore the mechanisms and to understand the dynamics of the magnetic and velocity fields. Since it is a complicated system, predictions of the magnetic field is a challenging problem. We present results of mimicking the three Meter experiment by a reservoir computer deep learning algorithm. The experiment is a three-meter diameter outer sphere and a one-meter diameter inner sphere with the gap filled with liquid sodium. The spheres can rotate up to 4 and 14 Hz respectively, giving a Reynolds number near to 108. Two external electromagnets apply magnetic fields, while an array of 31 external and 2 internal Hall sensors measure the resulting induced fields. We use this magnetic probe data to train a reservoir computer to predict the 3M time evolution and mimic waves in the experiment. Surprisingly accurate predictions can be made for several magnetic dipole time scales. This shows that such a complicated MHD system's behavior can be predicted. We gratefully acknowledge support from NSF EAR-1417148.

Sphere Drag and Heat Transfer

NASA Astrophysics Data System (ADS)

Duan, Zhipeng; He, Boshu; Duan, Yuanyuan

2015-07-01

Modelling fluid flows past a body is a general problem in science and engineering. Historical sphere drag and heat transfer data are critically examined. The appropriate drag coefficient is proposed to replace the inertia type definition proposed by Newton. It is found that the appropriate drag coefficient is a desirable dimensionless parameter to describe fluid flow physical behavior so that fluid flow problems can be solved in the simple and intuitive manner. The appropriate drag coefficient is presented graphically, and appears more general and reasonable to reflect the fluid flow physical behavior than the traditional century old drag coefficient diagram. Here we present drag and heat transfer experimental results which indicate that there exists a relationship in nature between the sphere drag and heat transfer. The role played by the heat flux has similar nature as the drag. The appropriate drag coefficient can be related to the Nusselt number. This finding opens new possibilities in predicting heat transfer characteristics by drag data. As heat transfer for flow over a body is inherently complex, the proposed simple means may provide an insight into the mechanism of heat transfer for flow past a body.

Sphere Drag and Heat Transfer.

PubMed

Duan, Zhipeng; He, Boshu; Duan, Yuanyuan

2015-07-20

Modelling fluid flows past a body is a general problem in science and engineering. Historical sphere drag and heat transfer data are critically examined. The appropriate drag coefficient is proposed to replace the inertia type definition proposed by Newton. It is found that the appropriate drag coefficient is a desirable dimensionless parameter to describe fluid flow physical behavior so that fluid flow problems can be solved in the simple and intuitive manner. The appropriate drag coefficient is presented graphically, and appears more general and reasonable to reflect the fluid flow physical behavior than the traditional century old drag coefficient diagram. Here we present drag and heat transfer experimental results which indicate that there exists a relationship in nature between the sphere drag and heat transfer. The role played by the heat flux has similar nature as the drag. The appropriate drag coefficient can be related to the Nusselt number. This finding opens new possibilities in predicting heat transfer characteristics by drag data. As heat transfer for flow over a body is inherently complex, the proposed simple means may provide an insight into the mechanism of heat transfer for flow past a body.

Effect of packing material on methane activation in a dielectric barrier discharge reactor

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

Jo, Sungkwon; Hoon Lee, Dae; Seok Kang, Woo

2013-12-15

The conversion of methane is measured in a planar-type dielectric barrier discharge reactor using γ-Al{sub 2}O{sub 3} (sphere), α-Al{sub 2}O{sub 3} (sphere), and γ-Al{sub 2}O{sub 3} (16–20 mesh). Investigations on the surface properties and shape of the three packing materials clearly indicate that methane activation is considerably affected by the material used. Capacitances inside the discharge gap are estimated from charge–voltage plots, and a comparison of the generated and transferred charges for different packing conditions show that the difference in surface properties between γ- and α-phase Al{sub 2}O{sub 3} affects the discharge characteristics. Moreover, all packing conditions show different chargemore » characteristics that are related to the electron density. Finally, the packing material's shape affects the local electron temperature, which is strongly related to methane conversion. The combined results indicate that both microscale and macroscale variations in a packing material affect the discharge characteristics, and a packing material should be considered carefully for effective methane activation.« less

Highly efficient decomposition of organic dye by aqueous-solid phase transfer and in situ photocatalysis using hierarchical copper phthalocyanine hollow spheres.

PubMed

Zhang, Mingyi; Shao, Changlu; Guo, Zengcai; Zhang, Zhenyi; Mu, Jingbo; Zhang, Peng; Cao, Tieping; Liu, Yichun

2011-07-01

The hierarchical tetranitro copper phthalocyanine (TNCuPc) hollow spheres were fabricated by a simple solvothermal method. The formation mechanism was proposed based on the evolution of morphology as a function of solvothermal time, which involved the initial formation of nanoparticles followed by their self-aggregation to microspheres and transformation into hierarchical hollow spheres by Ostwald ripening. Furthermore, the hierarchical TNCuPc hollow spheres exhibited high adsorption capacity and excellent simultaneously visible-light-driven photocatalytic performance for Rhodamine B (RB) under visible light. A possible mechanism for the "aqueous-solid phase transfer and in situ photocatalysis" was suggested. Repetitive tests showed that the hierarchical TNCuPc hollow spheres maintained high catalytic activity over several cycles, and it had a better regeneration capability under mild conditions.

Bacterial social networks: structure and composition of Myxococcus xanthus outer membrane vesicle chains.

PubMed

Remis, Jonathan P; Wei, Dongguang; Gorur, Amita; Zemla, Marcin; Haraga, Jessica; Allen, Simon; Witkowska, H Ewa; Costerton, J William; Berleman, James E; Auer, Manfred

2014-02-01

The social soil bacterium, Myxococcus xanthus, displays a variety of complex and highly coordinated behaviours, including social motility, predatory rippling and fruiting body formation. Here we show that M. xanthus cells produce a network of outer membrane extensions in the form of outer membrane vesicle chains and membrane tubes that interconnect cells. We observed peritrichous display of vesicles and vesicle chains, and increased abundance in biofilms compared with planktonic cultures. By applying a range of imaging techniques, including three-dimensional (3D) focused ion beam scanning electron microscopy, we determined these structures to range between 30 and 60 nm in width and up to 5 μm in length. Purified vesicle chains consist of typical M. xanthus lipids, fucose, mannose, N-acetylglucosamine and N-acetylgalactoseamine carbohydrates and a small set of cargo protein. The protein content includes CglB and Tgl outer membrane proteins known to be transferable between cells in a contact-dependent manner. Most significantly, the 3D organization of cells within biofilms indicates that cells are connected via an extensive network of membrane extensions that may connect cells at the level of the periplasmic space. Such a network would allow the transfer of membrane proteins and other molecules between cells, and therefore could provide a mechanism for the coordination of social activities. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

Synthesis of hollow silica spheres with hierarchical shell structure by the dual action of liquid indium microbeads in vapor-liquid-solid growth.

PubMed

Wang, Jian-Tao; Wang, Hui; Ou, Xue-Mei; Lee, Chun-Sing; Zhang, Xiao-Hong

2011-07-05

Geometry-based adhesion arising from hierarchical surface structure enables microspheres to adhere to cells strongly, which is essential for inorganic microcapsules that function as drug delivery or diagnostic imaging agents. However, constructing a hierarchical structure on the outer shell of the products via the current microcapsule synthesis method is difficult. This work presents a novel approach to fabricating hollow microspheres with a hierarchical shell structure through the vapor-liquid-solid (VLS) process in which liquid indium droplets act as both templates for the formation of silica capsules and catalysts for the growth of hierarchical shell structure. This hierarchical shell structure offers the hollow microsphere an enhanced geometry-based adhesion. The results provide a facile method for fabricating hollow spheres and enriching their function through tailoring the geometry of their outer shells. © 2011 American Chemical Society

Monostatic lidar/radar invisibility using coated spheres.

PubMed

Zhai, Peng-Wang; You, Yu; Kattawar, George W; Yang, Ping

2008-02-04

The Lorenz-Mie theory is revisited to explicitly include materials whose permeability is different from unity. The expansion coefficients of the scattered field are given for light scattering by both homogeneous and coated spheres. It is shown that the backscatter is exactly zero if the impedance of the spherical particles is equal to the intrinsic impedance of the surrounding medium. If spherical particles are sufficiently large, the zero backscatter can be explained as impedance matching using the asymptotic expression for the radar backscattering cross section. In the case of a coated sphere, the shell can be regarded as a cloak if the product of the thickness and the imaginary part of the refractive index of the outer shell is large.

Optical trapping forces of a focused azimuthally polarized Bessel-Gaussian beam on a double-layered sphere

NASA Astrophysics Data System (ADS)

Wu, F. P.; Zhang, B.; Liu, Z. L.; Tang, Y.; Zhang, N.

2017-12-01

We calculate the trapping forces exerted by a highly focused Bessel-Gaussian beam on a double-layered sphere by means of vector diffraction integral, T-matrix method and Maxwell stress tensor integral. The Bessel-Gaussian beam is azimuthally polarized. Numerical results predicate that the double-layered sphere with air core can be stably trapped in three-dimensions. The trapping forces and efficiencies are dependent on the refraction index and size of the inner core. The trapping efficiency can be optimized by choosing the refraction indices of the inner core and outer layer. Our computational method can be easily modified for other laser beams and particles with arbitrary geometries and multilayers.

Targeted Protein Degradation of Outer Membrane Decaheme Cytochrome MtrC Metal Reductase in Shewanella oneidensis MR-1 Measured Using Biarsenical Probe CrAsH-EDT2

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

Xiong, Yijia; Chen, Baowei; Shi, Liang

2011-10-14

Development of efficient microbial biofuel cells requires an ability to exploit interfacial electron transfer reactions to external electron acceptors, such as metal oxides; such reactions occur in the facultative anaerobic gram-negative bacterium Shewanella oneidensis MR-1 through the catalytic activity of the outer membrane decaheme c-type cytochrome MtrC. Central to the utility of this pathway to synthetic biology is an understanding of cellular mechanisms that maintain optimal MtrC function, cellular localization, and renewal by degradation and resynthesis. In order to monitor trafficking to the outer membrane, and the environmental sensitivity of MtrC, we have engineered a tetracysteine tag (i.e., CCPGCC) atmore » its C-terminus that permits labeling by the cell impermeable biarsenical fluorophore, carboxy-FlAsH (CrAsH) of MtrC at the surface of living Shewanella oneidensis MR-1 cells. In comparison, the cell permeable reagent FlAsH permits labeling of the entire population of MtrC, including proteolytic fragments resulting from incorrect maturation. We demonstrate specific labeling by CrAsH of engineered MtrC which is dependent on the presence of a functional type-2 secretion system (T2S), as evidenced by T2S system gspD or gspG deletion mutants which are incapable of CrAsH labeling. Under these latter conditions, MtrC undergoes proteolytic degradation to form a large 35-38 kDa fragment; this degradation product is also resolved during normal turnover of the CrAsH-labeled MtrC protein. No MtrC protein is released into the medium during turnover, suggesting the presence of cellular turnover systems involving MtrC reuptake and degradation. The mature MtrC localized on the outer membrane is a long-lived protein, with a turnover rate of 0.043 hr-1 that is insensitive to O2 concentration. Maturation of MtrC is relatively inefficient, with substantial rates of turnover of the immature protein prior to export to the outer membrane (i.e., 0.028 hr-1) that are consistent with the inherent complexity associated with correct heme insertion and acylation of MtrC that occurs in the periplasm prior to its targeting to the outer membrane. These latter results suggest that MtrC protein trafficking to the outer membrane and its subsequent degradation are tightly regulated, which is consistent with cellular processing pathways that target MtrC to extracellular structures and their possible role in promoting electron transfer from Shewanella to extracellular acceptors.« less

Electric field-assisted formation of organically modified hydroxyapatite (ormoHAP) spheres in carboxymethylated gelatin gels.

PubMed

Heinemann, C; Heinemann, S; Kruppke, B; Worch, H; Thomas, J; Wiesmann, H P; Hanke, T

2016-10-15

A biomimetic strategy was developed in order to prepare organically modified hydroxyapatite (ormoHAP) with spherical shape. The technical approach is based on electric field-assisted migration of calcium ions and phosphate ions into a hydrogel composed of carboxymethylated gelatin. The electric field as well as the carboxymethylation using glucuronic acid (GlcA) significantly accelerates the mineralization process, which makes the process feasible for lab scale production of ormoHAP spheres and probably beyond. A further process was developed for gentle separation of the ormoHAP spheres from the gelatin gel without compromising the morphology of the mineral. The term ormoHAP was chosen since morphological analyses using electron microscopy (SEM, TEM) and element analysis (EDX, FT-IR, XRD) confirmed that carboxymethylated gelatin molecules use to act as organic templates for the formation of nanocrystalline HAP. The hydroxyapatite (HAP) crystals self-organize to form hollow spheres with diameters ranging from 100 to 500nm. The combination of the biocompatible chemical composition and the unique structure of the nanocomposites is considered to be a useful basis for future applications in functionalized degradable biomaterials. A novel bioinspired mineralization process was developed based on electric field-assisted migration of calcium and phosphate ions into biochemically carboxymethylated gelatin acting as organic template. Advantages over conventional hydroxyapatite include particle size distribution and homogeneity as well as achievable mechanical properties of relevant composites. Moreover, specifically developed calcium ion or phosphate ion release during degradation can be useful to adjust the fate of bone cells in order to manipulate remodeling processes. The hollow structure of the spheres can be useful for embedding drugs in the core, encapsulated by the highly mineralized outer shell. In this way, controlled drug release could be achieved, which enables advanced strategies for threating bone-related diseases, e.g. osteoporosis and multiple myeloma. Copyright © 2016. Published by Elsevier Ltd.

PLEs in Higher Education: Exploring the Transference of Web 2.0 Social Affordances

ERIC Educational Resources Information Center

Casquero, Oskar; Portillo, Javier; Ovelar, Ramón; Romo, Jesús; Benito, Manuel

2013-01-01

Knowing whether Personal Learning Environments (PLEs) could transfer Web 2.0 affordances, which have been focused on the non-educational or recreational sphere, to the institutional sphere is important to move the research agenda beyond "cool uses" and to understand how the learning process is affected when students use this new type of…

Magnetic field transfer device and method

DOEpatents

Wipf, S.L.

1990-02-13

A magnetic field transfer device includes a pair of oppositely wound inner coils which each include at least one winding around an inner coil axis, and an outer coil which includes at least one winding around an outer coil axis. The windings may be formed of superconductors. The axes of the two inner coils are parallel and laterally spaced from each other so that the inner coils are positioned in side-by-side relation. The outer coil is outwardly positioned from the inner coils and rotatable relative to the inner coils about a rotational axis substantially perpendicular to the inner coil axes to generate a hypothetical surface which substantially encloses the inner coils. The outer coil rotates relative to the inner coils between a first position in which the outer coil axis is substantially parallel to the inner coil axes and the outer coil augments the magnetic field formed in one of the inner coils, and a second position 180[degree] from the first position, in which the augmented magnetic field is transferred into the other inner coil and reoriented 180[degree] from the original magnetic field. The magnetic field transfer device allows a magnetic field to be transferred between volumes with negligible work being required to rotate the outer coil with respect to the inner coils. 16 figs.

Magnetic field transfer device and method

DOEpatents

Wipf, Stefan L.

1990-01-01

A magnetic field transfer device includes a pair of oppositely wound inner coils which each include at least one winding around an inner coil axis, and an outer coil which includes at least one winding around an outer coil axis. The windings may be formed of superconductors. The axes of the two inner coils are parallel and laterally spaced from each other so that the inner coils are positioned in side-by-side relation. The outer coil is outwardly positioned from the inner coils and rotatable relative to the inner coils about a rotational axis substantially perpendicular to the inner coil axes to generate a hypothetical surface which substantially encloses the inner coils. The outer coil rotates relative to the inner coils between a first position in which the outer coil axis is substantially parallel to the inner coil axes and the outer coil augments the magnetic field formed in one of the inner coils, and a second position 180.degree. from the first position, in which the augmented magnetic field is transferred into the other inner coil and reoriented 180.degree. from the original magnetic field. The magnetic field transfer device allows a magnetic field to be transferred between volumes with negligible work being required to rotate the outer coil with respect to the inner coils.

Tuning the pure monoclinic phase of WO3 and WO3-Ag nanostructures for non-enzymatic glucose sensing application with theoretical insight from electronic structure simulations

NASA Astrophysics Data System (ADS)

Ponnusamy, Rajeswari; Gangan, Abhijeet; Chakraborty, Brahmananda; Sekhar Rout, Chandra

2018-01-01

Here, we report the controlled hydrothermal synthesis and tuning of the pure monoclinic phase of WO3 and WO3-Ag nanostructures. Comparative electrochemical nonenzymatic glucose sensing properties of WO3 and WO3-Ag were investigated by cyclic voltammetry and chronoamperometric tests. We observed enhanced glucose sensing performance of WO3-Ag porous spheres as compared to bare WO3 nanoslabs. The sensitivity of the pure WO3 nanoslabs is 11.1 μA μM-1 cm-2 whereas WO3-Ag porous spheres exhibit sensitivity of 23.3 μA μM-1 cm-2. The WO3-Ag porous spheres exhibited a good linear range (5-375 μM) with excellent anti-interference property. Our experimental observations are qualitatively supported by density functional theory simulations through investigation of bonding and charge transfer mechanism of glucose on WO3 and Ag doped WO3. As the binding energy of glucose is more on the Ag doped WO3 (100) surface compared to the bare WO3 (100) surface and the Ag doped WO3 (100) surface becomes more conducting due to enhancement of density of states near the Fermi level, we can infer that Ag doped WO3 exhibits a better charge transfer media compared to bare WO3 resulting in enhanced glucose sensitivity in consistency with our experimental data.

Nanoscale Hollow Spheres: Microemulsion-Based Synthesis, Structural Characterization and Container-Type Functionality

PubMed Central

Gröger, Henriette; Kind, Christian; Leidinger, Peter; Roming, Marcus; Feldmann, Claus

2010-01-01

A wide variety of nanoscale hollow spheres can be obtained via a microemulsion approach. This includes oxides (e.g., ZnO, TiO2, SnO2, AlO(OH), La(OH)3), sulfides (e.g., Cu2S, CuS) as well as elemental metals (e.g., Ag, Au). All hollow spheres are realized with outer diameters of 10−60 nm, an inner cavity size of 2−30 nm and a wall thickness of 2−15 nm. The microemulsion approach allows modification of the composition of the hollow spheres, fine-tuning their diameter and encapsulation of various ingredients inside the resulting “nanocontainers”. This review summarizes the experimental conditions of synthesis and compares them to other methods of preparing hollow spheres. Moreover, the structural characterization and selected properties of the as-prepared hollow spheres are discussed. The latter is especially focused on container-functionalities with the encapsulation of inorganic salts (e.g., KSCN, K2S2O8, KF), biomolecules/bioactive molecules (e.g., phenylalanine, quercetin, nicotinic acid) and fluorescent dyes (e.g., rhodamine, riboflavin) as representative examples. PMID:28883333

Coordinate measuring machine test standard apparatus and method

DOEpatents

Bieg, L.F.

1994-08-30

A coordinate measuring machine test standard apparatus and method are disclosed which includes a rotary spindle having an upper phase plate and an axis of rotation, a kinematic ball mount attached to the phase plate concentric with the axis of rotation of the phase plate, a groove mounted at the circumference of the phase plate, and an arm assembly which rests in the groove. The arm assembly has a small sphere at one end and a large sphere at the other end. The small sphere may be a coordinate measuring machine probe tip and may have variable diameters. The large sphere is secured in the kinematic ball mount and the arm is held in the groove. The kinematic ball mount includes at least three mounting spheres and the groove is an angular locating groove including at least two locking spheres. The arm may have a hollow inner core and an outer layer. The rotary spindle may be a ratio reducer. The device is used to evaluate the measuring performance of a coordinate measuring machine for periodic recertification, including 2 and 3 dimensional accuracy, squareness, straightness, and angular accuracy. 5 figs.

Coordinate measuring machine test standard apparatus and method

DOEpatents

Bieg, Lothar F.

1994-08-30

A coordinate measuring machine test standard apparatus and method which iudes a rotary spindle having an upper phase plate and an axis of rotation, a kinematic ball mount attached to the phase plate concentric with the axis of rotation of the phase plate, a groove mounted at the circumference of the phase plate, and an arm assembly which rests in the groove. The arm assembly has a small sphere at one end and a large sphere at the other end. The small sphere may be a coordinate measuring machine probe tip and may have variable diameters. The large sphere is secured in the kinematic ball mount and the arm is held in the groove. The kinematic ball mount includes at least three mounting spheres and the groove is an angular locating groove including at least two locking spheres. The arm may have a hollow inner core and an outer layer. The rotary spindle may be a ratio reducer. The device is used to evaluate the measuring performance of a coordinate measuring machine for periodic recertification, including 2 and 3 dimensional accuracy, squareness, straightness, and angular accuracy.

Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

PubMed

Adamovich, Igor V; Li, Ting; Lempert, Walter R

2015-08-13

This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate 'conventional' chemistry mechanism. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Large-scale synthesis of monodisperse magnesium ferrite via an environmentally friendly molten salt route.

PubMed

Lou, Zhengsong; He, Minglong; Wang, Ruikun; Qin, Weiwei; Zhao, Dejian; Chen, Changle

2014-02-17

Sub-micrometer-sized magnesium ferrite spheres consisting of uniform small particles have been prepared using a facile, large-scale solid-state reaction employing a molten salt technique. Extensive structural characterization of the as-prepared samples has been performed using scanning electron microscope, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, and X-ray diffraction. The yield of the magnesium ferrite sub-micrometer spheres is up to 90%, and these sub-micrometer spheres are made up of square and rectangular nanosheets. The magnetic properties of magnesium ferrite sub-micrometer spheres are investigated, and the magnetization saturation value is about 24.96 emu/g. Moreover, the possible growth mechanism is proposed based on the experimental results.

Direct Numerical Simulation of Fluid Flow and Mass Transfer in Particle Clusters

PubMed Central

2018-01-01

In this paper, an efficient ghost-cell based immersed boundary method is applied to perform direct numerical simulation (DNS) of mass transfer problems in particle clusters. To be specific, a nine-sphere cuboid cluster and a random-generated spherical cluster consisting of 100 spheres are studied. In both cases, the cluster is composed of active catalysts and inert particles, and the mutual influence of particles on their mass transfer performance is studied. To simulate active catalysts the Dirichlet boundary condition is imposed at the external surface of spheres, while the zero-flux Neumann boundary condition is applied for inert particles. Through our studies, clustering is found to have negative influence on the mass transfer performance, which can be then improved by dilution with inert particles and higher Reynolds numbers. The distribution of active/inert particles may lead to large variations of the cluster mass transfer performance, and individual particle deep inside the cluster may possess a high Sherwood number. PMID:29657359

Hypervelocity Heat-Transfer Measurements in an Expansion Tube

NASA Technical Reports Server (NTRS)

Hollis, Brian R.; Perkins, John N.

1996-01-01

A series of experiments has been conducted in the NASA HYPULSE Expansion Tube, in both CO2 and air test gases, in order to obtain data for comparison with computational results and to assess the capability for performing hypervelocity heat-transfer studies in this facility. Heat-transfer measurements were made in both test gases on 70 deg sphere-cone models and on hemisphere models of various radii. HYPULSE freestream flow conditions in these test gases were found to be repeatable to within 3-10%, and aerothermodynamic test times of 150 microsec in CO2 and 125 microsec in air were identified. Heat-transfer measurement uncertainty was estimated to be 10-15%. Comparisons were made with computational results from the non-equilibrium Navier-Stokes solver NEQ2D. Measured and computed heat-transfer rates agreed to within 10% on the hemispheres and on the sphere-cone forebodies, and to within 10% in CO2 and 25% in air on the afterbodies and stings of the sphere-cone models.

Shape-controlled synthesis and properties of dandelion-like manganese sulfide hollow spheres

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

Ma, Wei; State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083; Chen, Gen

2012-09-15

Graphical abstract: Dandelion-like MnS hollow spheres assembled with nanorods could be successfully synthesized in large quantities through a simple and convenient hydrothermal synthetic method under mild conditions using soluble hydrated manganese chloride as Mn source, L-cysteine as both a precipitator and complexing reagent. The dandelion-like MnS hollow spheres might have potential applications in microdevices and magnetic cells. Highlights: ► MnS hollow spheres assembled with nanorods could be synthesized. ► The morphologies and sizes of final products could be controlled. ► Possible formation mechanism of MnS hollow spheres is proposed. -- Abstract: Dandelion-like gamma-manganese (II) sulfide (MnS) hollow spheres assembled withmore » nanorods have been prepared via a hydrothermal process in the presence of L-cysteine and polyvinylpyrrolidone (PVP). L-cysteine was employed as not only sulfur source, but also coordinating reagent for the synthesis of dandelion-like MnS hollow spheres. The morphology, structure and properties of as-prepared products have been investigated in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM) and photoluminescence spectra (PL). The probable formation mechanism of as-prepared MnS hollow spheres was discussed on the basis of the experimental results. This strategy may provide an effective method for the fabrication of other metal sulfides hollow spheres.« less

Near-field radiative heat transfer in scanning thermal microscopy computed with the boundary element method

NASA Astrophysics Data System (ADS)

Nguyen, K. L.; Merchiers, O.; Chapuis, P.-O.

2017-11-01

We compute the near-field radiative heat transfer between a hot AFM tip and a cold substrate. This contribution to the tip-sample heat transfer in Scanning Thermal Microscopy is often overlooked, despite its leading role when the tip is out of contact. For dielectrics, we provide power levels exchanged as a function of the tip-sample distance in vacuum and spatial maps of the heat flux deposited into the sample which indicate the near-contact spatial resolution. The results are compared to analytical expressions of the Proximity Flux Approximation. The numerical results are obtained by means of the Boundary Element Method (BEM) implemented in the SCUFF-EM software, and require first a thorough convergence analysis of the progressive implementation of this method to the thermal emission by a sphere, the radiative transfer between two spheres, and the radiative exchange between a sphere and a finite substrate.

Method for producing small hollow spheres

DOEpatents

Rosencwaig, Allen; Koo, Jackson C.; Dressler, John L.

1981-01-01

A method for producing small hollow spheres of glass having an outer diameter ranging from about 100.mu. to about 500.mu. with a substantially uniform wall thickness in the range of about 0.5-20.mu.. The method involves introducing aqueous droplets of a glass-forming solution into a long vertical drop oven or furnace having varying temperature regions. In one embodiment, one of the temperature regions is lower than both the preceeding region and the subsequent region. One region utilizes a temperature of at least 200.degree. C. higher than the melting point of the glass-forming material in the solution and, for example, may be at least 3 times higher than the temperature of the preceeding region. In addition, there is a sharp temperature gradient between these regions. As each droplet of solution passes through a first region it forms into a gel membrane having a spherical shape and encapsulates the rest of the drop retained in the elastic outer surface and the water entrapped within diffuses rapidly through the thin gel membrane which causes more of the glass-forming material to go out of solution and is incorporated into the gel membrane causing it to grow in size and become hollow. thus produced hollow glass sphere has a sphericity, concentricity, and wall uniformity of better than 5%. The sphere is capable of retaining material of up to at least 100 atmospheres therein over long periods of time. In one embodiment.

Speciation of aqueous Ni(II)-carboxylate and Ni(II)-fulvic acid solutions: Combined ATR-FTIR and XAFS analysis

NASA Astrophysics Data System (ADS)

Strathmann, Timothy J.; Myneni, Satish C. B.

2004-09-01

Aqueous solutions containing Ni(II) and a series of structurally related carboxylic acids were analyzed using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Ni K-edge X-ray absorption fine structure spectroscopy (XAFS). XAFS spectra were also collected for solutions containing Ni 2+ and chelating ligands (ethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA)) as well as soil fulvic acid. Limited spectral changes are observed for aqueous Ni(II) complexes with monocarboxylates (formate, acetate) and long-chain polycarboxylates (succinate, tricarballylate), where individual donor groups are separated by multiple bridging methylene groups. These spectral changes indicate weak interactions between Ni(II) and carboxylates, and the trends are similar to some earlier reports for crystalline Ni(II)-acetate solids, for which X-ray crystallography studies have indicated monodentate Ni(II)-carboxylate coordination. Nonetheless, electrostatic or outer-sphere coordination cannot be ruled out for these complexes. However, spectral changes observed for short-chain dicarboxylates (oxalate, malonate) and carboxylates that contain an alcohol donor group adjacent to one of the carboxylate groups (lactate, malate, citrate) demonstrate inner-sphere metal coordination by multiple donor groups. XAFS spectral fits of Ni(II) solutions containing soil fulvic acid are consistent with inner-sphere Ni(II) coordination by one or more carboxylate groups, but spectra are noisy and outer-sphere modes of coordination cannot be ruled out. These molecular studies refine our understanding of the interactions between carboxylates and weakly complexing divalent transition metals, such as Ni(II).

Competition Between Co(NH3)63+ and Inner Sphere Mg2+ Ions in the HDV Ribozyme

PubMed Central

Gong, Bo; Chen, Jui-Hui; Bevilacqua, Philip C.; Golden, Barbara L.; Carey, Paul R.

2009-01-01

Divalent cations play critical structural and functional roles in many RNAs. While the hepatitis delta virus (HDV) ribozyme can undergo self-cleavage in the presence of molar concentrations of monovalent cations, divalent cations such as Mg2+ are required for efficient catalysis under physiological conditions. Moreover, the cleavage reaction can be inhibited with Co(NH3)63+, an analog of Mg(H2O)62+. Here, the binding of Mg2+ and Co(NH3)63+ to the HDV ribozyme are studied by Raman microscopic analysis of crystals. Raman difference spectra acquired at different metal ion conditions reveal changes in the ribozyme. When Mg2+ alone is introduced to the ribozyme, inner sphere coordination of Mg(H2O)x2+ (x≤5) to non-bridging PO2− oxygen, and changes in base stretches and phosphodiester group conformation are observed. In addition, binding of Mg2+ induces deprotonation of a cytosine assigned to the general acid C75, consistent with solution studies. When Co(NH3)63+ alone is introduced, deprotonation of C75 is again observed, as are distinctive changes in base vibrational ring modes and phosphodiester backbone conformation. In contrast to Mg2+ binding, Co(NH3)63+ binding does not perturb PO2− group vibrations, consistent with its ability to make only outer sphere contacts. Surprisingly, competitive binding studies reveal that Co(NH3)63+ ions displace some inner sphere-coordinated magnesium species, including ions coordinated to PO2− groups or the N7 of a guanine, likely G1 at the active site. These observations contrast with the tenet that Co(NH3)63+ ions displace only outer sphere magnesium ions. Overall, our data support two classes of inner sphere Mg2+-PO2− binding sites: sites that Co(NH3)63+ can displace, and others it cannot. PMID:19888753

Comparative Dosimetric Estimates of a 25 keV Electron Micro-beam with three Monte Carlo Codes

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

Mainardi, Enrico; Donahue, Richard J.; Blakely, Eleanor A.

2002-09-11

The calculations presented compare the different performances of the three Monte Carlo codes PENELOPE-1999, MCNP-4C and PITS, for the evaluation of Dose profiles from a 25 keV electron micro-beam traversing individual cells. The overall model of a cell is a water cylinder equivalent for the three codes but with a different internal scoring geometry: hollow cylinders for PENELOPE and MCNP, whereas spheres are used for the PITS code. A cylindrical cell geometry with scoring volumes with the shape of hollow cylinders was initially selected for PENELOPE and MCNP because of its superior simulation of the actual shape and dimensions ofmore » a cell and for its improved computer-time efficiency if compared to spherical internal volumes. Some of the transfer points and energy transfer that constitute a radiation track may actually fall in the space between spheres, that would be outside the spherical scoring volume. This internal geometry, along with the PENELOPE algorithm, drastically reduced the computer time when using this code if comparing with event-by-event Monte Carlo codes like PITS. This preliminary work has been important to address dosimetric estimates at low electron energies. It demonstrates that codes like PENELOPE can be used for Dose evaluation, even with such small geometries and energies involved, which are far below the normal use for which the code was created. Further work (initiated in Summer 2002) is still needed however, to create a user-code for PENELOPE that allows uniform comparison of exact cell geometries, integral volumes and also microdosimetric scoring quantities, a field where track-structure codes like PITS, written for this purpose, are believed to be superior.« less

Update on Science Results from CubeSat: Colorado Student Space Weather Experiment (CSSWE)

NASA Astrophysics Data System (ADS)

Li, X.; Schiller, Q.; Blum, L. W.; Califf, S.; Zhao, H.; Jaynes, A. N.; Tu, W.; Turner, D. L.; Gerhardt, D.; Palo, S. E.; Selesnick, R.; Kanekal, S. G.; Baker, D. N.; Fennell, J. F.; Blake, J. B.; Looper, M. D.; Reeves, G. D.; Spence, H.

2013-12-01

Measurements from the Relativistic Electron and Proton Telescope integrated little experiment (REPTile) onboard CSSWE, which was launched into a highly inclined (65 deg) low Earth orbit on 13 September 2012, are analyzed along with measurements from the Relativistic Electron and Proton Telescope (REPT) and the Magnetic Electron Ion Spectrometer (MagEIS) instruments aboard the Van Allen Probes, which are in a low inclination (10 deg) geo-transfer-like orbit. Both REPT and MagEIS measure the full distribution of energetic electrons as they traverse the heart of the outer radiation belt. However, due to the small equatorial loss cone (only a few deg), it is difficult for REPT and MagEIS to directly determine which electrons will precipitate into the atmosphere, a major loss process. REPTile, a miniaturized version of REPT, measures the fraction of the total electron population that has small enough equatorial pitch angles to reach the altitude, 480km x 780 km, of CSSWE, thus measuring the precipitating population as well as the trapped and quasi-trapped populations. These newly available measurements provide an unprecedented opportunity to investigate the source, loss, and energization processes that are responsible for the dynamic behavior of outer radiation belt electrons. The focus of presentation will be on the characteristics of relativistic electrons measured by REPTile during the October 2012 storms, and results during other events will also be summarized.

Diagnosis of a Poorly Performing Liquid Hydrogen Bulk Storage Sphere

NASA Technical Reports Server (NTRS)

Krenn, Angela G.

2011-01-01

There are two 850,000 gallon Liquid Hydrogen (LH2) storage spheres used to support the Space Shuttle Program; one residing at Launch Pad A and the other at Launch Pad B. The LH2 Sphere at Pad B has had a high boiloff rate since being brought into service in the 1960's. The daily commodity loss was estimated to be approximately double that of the Pad A sphere, and well above the minimum required by the sphere's specification. Additionally, after being re-painted in the late 1990's a "cold spot" appeared on the outer sphere which resulted in a poor paint bond, and mold formation. Thermography was used to characterize the area, and the boiloff rate was continually evaluated. All evidence suggested that the high boiloff rate was caused by an excessive heat leak into the inner sphere due to an insulation void in the annulus. Pad B was recently taken out of Space Shuttle program service which provided a unique opportunity to diagnose the sphere's poor performance. The sphere was drained and inerted, and then opened from the annular relief device on the top where a series of boroscoping operations were accomplished. Boroscoping revealed a large Perlite insulation void in the region of the sphere where the cold spot was apparent. Perlite was then trucked in and off-loaded into the annular void region until the annulus was full. The sphere has not yet been brought back into service.

Extracting electron transfer coupling elements from constrained density functional theory

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

Wu Qin; Van Voorhis, Troy

2006-10-28

Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (H{sub ab}) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculationsmore » on the Zn{sub 2}{sup +} and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the unconstrained DFT curve has no reaction barrier and gives H{sub ab}{approx_equal}17 kcal/mol, which qualitatively disagrees with experimental results, the H{sub ab} calculated from constrained DFT is about 3 kcal/mol and the generated ground state has a barrier height of 1.70 kcal/mol, successfully predicting (Q-TTF-Q){sup -} to be a class II mixed-valence compound.« less

A framework for stochastic simulations and visualization of biological electron-transfer dynamics

NASA Astrophysics Data System (ADS)

Nakano, C. Masato; Byun, Hye Suk; Ma, Heng; Wei, Tao; El-Naggar, Mohamed Y.

2015-08-01

Electron transfer (ET) dictates a wide variety of energy-conversion processes in biological systems. Visualizing ET dynamics could provide key insight into understanding and possibly controlling these processes. We present a computational framework named VizBET to visualize biological ET dynamics, using an outer-membrane Mtr-Omc cytochrome complex in Shewanella oneidensis MR-1 as an example. Starting from X-ray crystal structures of the constituent cytochromes, molecular dynamics simulations are combined with homology modeling, protein docking, and binding free energy computations to sample the configuration of the complex as well as the change of the free energy associated with ET. This information, along with quantum-mechanical calculations of the electronic coupling, provides inputs to kinetic Monte Carlo (KMC) simulations of ET dynamics in a network of heme groups within the complex. Visualization of the KMC simulation results has been implemented as a plugin to the Visual Molecular Dynamics (VMD) software. VizBET has been used to reveal the nature of ET dynamics associated with novel nonequilibrium phase transitions in a candidate configuration of the Mtr-Omc complex due to electron-electron interactions.

A combined electrochemical and optical trapping platform for measuring single cell respiration rates at electrode interfaces.

PubMed

Gross, Benjamin J; El-Naggar, Mohamed Y

2015-06-01

Metal-reducing bacteria gain energy by extracellular electron transfer to external solids, such as naturally abundant minerals, which substitute for oxygen or the other common soluble electron acceptors of respiration. This process is one of the earliest forms of respiration on earth and has significant environmental and technological implications. By performing electron transfer to electrodes instead of minerals, these microbes can be used as biocatalysts for conversion of diverse chemical fuels to electricity. Understanding such a complex biotic-abiotic interaction necessitates the development of tools capable of probing extracellular electron transfer down to the level of single cells. Here, we describe an experimental platform for single cell respiration measurements. The design integrates an infrared optical trap, perfusion chamber, and lithographically fabricated electrochemical chips containing potentiostatically controlled transparent indium tin oxide microelectrodes. Individual bacteria are manipulated using the optical trap and placed on the microelectrodes, which are biased at a suitable oxidizing potential in the absence of any chemical electron acceptor. The potentiostat is used to detect the respiration current correlated with cell-electrode contact. We demonstrate the system with single cell measurements of the dissimilatory-metal reducing bacterium Shewanella oneidensis MR-1, which resulted in respiration currents ranging from 15 fA to 100 fA per cell under our measurement conditions. Mutants lacking the outer-membrane cytochromes necessary for extracellular respiration did not result in any measurable current output upon contact. In addition to the application for extracellular electron transfer studies, the ability to electronically measure cell-specific respiration rates may provide answers for a variety of fundamental microbial physiology questions.

A combined electrochemical and optical trapping platform for measuring single cell respiration rates at electrode interfaces

NASA Astrophysics Data System (ADS)

Gross, Benjamin J.; El-Naggar, Mohamed Y.

2015-06-01

Metal-reducing bacteria gain energy by extracellular electron transfer to external solids, such as naturally abundant minerals, which substitute for oxygen or the other common soluble electron acceptors of respiration. This process is one of the earliest forms of respiration on earth and has significant environmental and technological implications. By performing electron transfer to electrodes instead of minerals, these microbes can be used as biocatalysts for conversion of diverse chemical fuels to electricity. Understanding such a complex biotic-abiotic interaction necessitates the development of tools capable of probing extracellular electron transfer down to the level of single cells. Here, we describe an experimental platform for single cell respiration measurements. The design integrates an infrared optical trap, perfusion chamber, and lithographically fabricated electrochemical chips containing potentiostatically controlled transparent indium tin oxide microelectrodes. Individual bacteria are manipulated using the optical trap and placed on the microelectrodes, which are biased at a suitable oxidizing potential in the absence of any chemical electron acceptor. The potentiostat is used to detect the respiration current correlated with cell-electrode contact. We demonstrate the system with single cell measurements of the dissimilatory-metal reducing bacterium Shewanella oneidensis MR-1, which resulted in respiration currents ranging from 15 fA to 100 fA per cell under our measurement conditions. Mutants lacking the outer-membrane cytochromes necessary for extracellular respiration did not result in any measurable current output upon contact. In addition to the application for extracellular electron transfer studies, the ability to electronically measure cell-specific respiration rates may provide answers for a variety of fundamental microbial physiology questions.

A detailed study of intermolecular interactions, electronic and vibrational properties of the metal complex bis(uracilato)diammine copper(ii) dihydrate

NASA Astrophysics Data System (ADS)

Gramajo Feijoo, M.; Fernández-Liencres, M. P.; Gil, D. M.; Gómez, M. I.; Ben Altabef, A.; Navarro, A.; Tuttolomondo, M. E.

2018-03-01

Density Functional Theory (DFT) calculations were performed with the aim of investigating the vibrational, electronic and structural properties of [Cu(uracilato-N1)2 (NH3)2]ṡ2H2O complex. The IR and Raman spectra were recorded leading to a complete analysis of the normal modes of vibration of the metal complex. A careful study of the intermolecular interactions observed in solid state was performed by using the Hirshfeld surface analysis and their associated 2D fingerprint plots. The results indicated that the crystal packing is stabilized by Nsbnd H⋯O hydrogen bonds and π-stacking interactions. In addition, Csbnd H···π interactions were also observed. Time-dependent density functional theory (TD-DFT) calculations revealed that all the low-lying electronic states correspond to a mixture of intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions. Finally, Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analysis were performed to shed light on the intermolecular interactions in the coordination sphere.

Propagation of a shock wave in a radiating spherically symmetric distribution of matter

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

Herrera, L.; Nunez, L.

1987-08-01

A method used to study the evolution of radiating spheres reported by Herrera et al. (1980) is extended to the case in which the sphere is divided in two regions by a shock wave front. The equations of state at both sides of the shock are different, and the solutions are matched on it via the Rankine-Hugoniot conditions. The outer-region metric is matched with a Vaidya solution on the boundary surface of the sphere. As an example of the procedure, two known solutions for radiating systems are considered. The matter distribution is free of singularities everywhere within the sphere andmore » a Gaussian-like pulse is assumed to carry out a fraction of the total mass. Exploding models are then obtained. Finally, the results are discussed in the light of recent work on gravitational collapse and supernovae. 29 references.« less

Acoustic radiation force on a heated sphere including effects of heat transfer and acoustic streaming

NASA Technical Reports Server (NTRS)

Lee, Chun P.; Wang, Taylor G.

1988-01-01

A previous theoretical result on the subject of the acoustic radiation force on a heated sphere (Lee and Wang, 1984) is reexamined. For a more complete understanding, effects of heat transfer and acoustic streaming are taken into consideration. Essentially, it was found that, at high sound-pressure levels in a steady situation, the force is not affected significantly by the temperature profile, consistent with the result of an experimental work (Leung and Wang, 1985). This resolves the earlier apparent contradiction between the theory and the experiment. If excessive hot air is accumulated around the sphere, which can happen in transient situations, the force can be weakened or reversed in sign. A heat transfer model due to acoustic streaming was also found.

Electron transfer at the cell-uranium interface in Geobacter spp.

PubMed

Reguera, Gemma

2012-12-01

The in situ stimulation of Fe(III) oxide reduction in the subsurface stimulates the growth of Geobacter spp. and the precipitation of U(VI) from groundwater. As with Fe(III) oxide reduction, the reduction of uranium by Geobacter spp. requires the expression of their conductive pili. The pili bind the soluble uranium and catalyse its extracellular reductive precipitation along the pili filaments as a mononuclear U(IV) complexed by carbon-containing ligands. Although most of the uranium is immobilized by the pili, some uranium deposits are also observed in discreet regions of the outer membrane, consistent with the participation of redox-active foci, presumably c-type cytochromes, in the extracellular reduction of uranium. It is unlikely that cytochromes released from the outer membrane could associate with the pili and contribute to the catalysis, because scanning tunnelling microscopy spectroscopy did not reveal any haem-specific electronic features in the pili, but, rather, showed topographic and electronic features intrinsic to the pilus shaft. Pili not only enhance the rate and extent of uranium reduction per cell, but also prevent the uranium from traversing the outer membrane and mineralizing the cell envelope. As a result, pili expression preserves the essential respiratory activities of the cell envelope and the cell's viability. Hence the results support a model in which the conductive pili function as the primary mechanism for the reduction of uranium and cellular protection in Geobacter spp.

Prompt enhancement of the Earth's outer radiation belt due to substorm electron injections

DOE PAGES

Tang, C. L.; Zhang, J. -C.; Reeves, G. D.; ...

2016-12-17

Here, we present multipoint simultaneous observations of the near-Earth magnetotail and outer radiation belt during the substorm electron injection event on 16 August 2013. Time History of Events and Macroscale Interactions during Substorms A in the near-Earth magnetotail observed flux-enhanced electrons of 300 keV during the magnetic field dipolarization. Geosynchronous orbit satellites also observed the intensive electron injections. Located in the outer radiation belt, RBSP-A observed enhancements of MeV electrons accompanied by substorm dipolarization. The phase space density (PSD) of MeV electrons at L* ~5.4 increased by 1 order of magnitude in 1 h, resulting in a local PSD peakmore » of MeV electrons, which was caused by the direct effect of substorm injections. We also detected an enhanced MeV electrons in the heart of the outer radiation belt within 2 h, which may be associated with intensive substorm electron injections and subsequent local acceleration by chorus waves. Multipoint observations have shown that substorm electron injections not only can be the external source of MeV electrons at the outer edge of the outer radiation belt (L* ~5.4) but also can provide the intensive seed populations in the outer radiation belt. These initial higher-energy electrons from injection can reach relativistic energy much faster. Furthermore, these observations also provide evidence that enhanced substorm electron injections can explain rapid enhancements of MeV electrons in the outer radiation belt.« less

Prompt enhancement of the Earth's outer radiation belt due to substorm electron injections

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

Tang, C. L.; Zhang, J. -C.; Reeves, G. D.

Here, we present multipoint simultaneous observations of the near-Earth magnetotail and outer radiation belt during the substorm electron injection event on 16 August 2013. Time History of Events and Macroscale Interactions during Substorms A in the near-Earth magnetotail observed flux-enhanced electrons of 300 keV during the magnetic field dipolarization. Geosynchronous orbit satellites also observed the intensive electron injections. Located in the outer radiation belt, RBSP-A observed enhancements of MeV electrons accompanied by substorm dipolarization. The phase space density (PSD) of MeV electrons at L* ~5.4 increased by 1 order of magnitude in 1 h, resulting in a local PSD peakmore » of MeV electrons, which was caused by the direct effect of substorm injections. We also detected an enhanced MeV electrons in the heart of the outer radiation belt within 2 h, which may be associated with intensive substorm electron injections and subsequent local acceleration by chorus waves. Multipoint observations have shown that substorm electron injections not only can be the external source of MeV electrons at the outer edge of the outer radiation belt (L* ~5.4) but also can provide the intensive seed populations in the outer radiation belt. These initial higher-energy electrons from injection can reach relativistic energy much faster. Furthermore, these observations also provide evidence that enhanced substorm electron injections can explain rapid enhancements of MeV electrons in the outer radiation belt.« less

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

USGS Publications Warehouse

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (???5-9), even at the partial pressure of carbon dioxide of ambient air (pCO2 = 10-3.45 atm). ?? 2006 Elsevier Inc. All rights reserved.

Magnesium-binding architectures in RNA crystal structures: validation, binding preferences, classification and motif detection

PubMed Central

Zheng, Heping; Shabalin, Ivan G.; Handing, Katarzyna B.; Bujnicki, Janusz M.; Minor, Wladek

2015-01-01

The ubiquitous presence of magnesium ions in RNA has long been recognized as a key factor governing RNA folding, and is crucial for many diverse functions of RNA molecules. In this work, Mg2+-binding architectures in RNA were systematically studied using a database of RNA crystal structures from the Protein Data Bank (PDB). Due to the abundance of poorly modeled or incorrectly identified Mg2+ ions, the set of all sites was comprehensively validated and filtered to identify a benchmark dataset of 15 334 ‘reliable’ RNA-bound Mg2+ sites. The normalized frequencies by which specific RNA atoms coordinate Mg2+ were derived for both the inner and outer coordination spheres. A hierarchical classification system of Mg2+ sites in RNA structures was designed and applied to the benchmark dataset, yielding a set of 41 types of inner-sphere and 95 types of outer-sphere coordinating patterns. This classification system has also been applied to describe six previously reported Mg2+-binding motifs and detect them in new RNA structures. Investigation of the most populous site types resulted in the identification of seven novel Mg2+-binding motifs, and all RNA structures in the PDB were screened for the presence of these motifs. PMID:25800744

Modelling mass diffusion for a multi-layer sphere immersed in a semi-infinite medium: application to drug delivery.

PubMed

Carr, Elliot J; Pontrelli, Giuseppe

2018-04-12

We present a general mechanistic model of mass diffusion for a composite sphere placed in a large ambient medium. The multi-layer problem is described by a system of diffusion equations coupled via interlayer boundary conditions such as those imposing a finite mass resistance at the external surface of the sphere. While the work is applicable to the generic problem of heat or mass transfer in a multi-layer sphere, the analysis and results are presented in the context of drug kinetics for desorbing and absorbing spherical microcapsules. We derive an analytical solution for the concentration in the sphere and in the surrounding medium that avoids any artificial truncation at a finite distance. The closed-form solution in each concentric layer is expressed in terms of a suitably-defined inverse Laplace transform that can be evaluated numerically. Concentration profiles and drug mass curves in the spherical layers and in the external environment are presented and the dependency of the solution on the mass transfer coefficient at the surface of the sphere analyzed. Copyright © 2018 Elsevier Inc. All rights reserved.

Impairment of extramitochondrial oxidative phosphorylation in mouse rod outer segments by blue light irradiation.

PubMed

Calzia, Daniela; Panfoli, Isabella; Heinig, Nora; Schumann, Ulrike; Ader, Marius; Traverso, Carlo Enrico; Funk, Richard H W; Roehlecke, Cora

2016-06-01

Exposure to short wavelength light causes increased reactive oxygen intermediates production in the outer retina, particularly in the rod Outer Segments (OS). Consistently, the OS were shown to conduct aerobic ATP production through the ectopic expression of the electron transfer chain complexes I-IV and F1Fo-ATP synthase. These facts prompted us to verify if the oxidative phosphorylation in the OS is implied in the oxidative damage of the blue-light (BL) treated OS, in an organotypic model of mouse retina. Whole mouse eyeball cultures were treated with short wavelength BL (peak at 405 nm, output power 1 mW/cm(2)) for 6 h. Immunogold transmission electron microscopy confirmed the expression of Complex I and F1Fo-ATP synthase in the OS. In situ histochemical assays on unfixed sections showed impairment of respiratory Complexes I and II after BL exposure, both in the OS and IS, utilized as a control. Basal O2 consumption and ATP synthesis were impaired in the OS purified from blue-light irradiated eyeball cultures. Electron transfer capacity between Complex I and II as well as activity of Complexes I and II was decreased in blue-light irradiated purified OS. The severe malfunctioning of the OS aerobic respiratory capacity after 6 h BL treatment may be the consequence of a self-induced damage. BL exposure would cause an initial over-functioning of both the phototransduction and respiratory chain, with reactive oxygen species production. In a self-renewal vicious cycle, membrane and protein oxidative damage, proton leakage and uncoupling, would impair redox chains, perpetuating the damage and causing hypo-metabolism with eventual apoptosis of the rod. Data may shed new light on the rod-driven retinopathies such as Age Related Macular Degeneration, of which blue-light irradiated retina represents a model. Copyright © 2016 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

Particle size effect and the mechanism of hematite reduction by the outer membrane cytochrome OmcA of Shewanella oneidensis MR-1

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

Liu, Juan; Pearce, Carolyn I.; Shi, Liang

The cycling of iron at the Earth’s near surface is profoundly influenced by dissimilatory metal reducing microorganisms, and many studies have focused on unraveling electron transfer mechanisms between these bacteria and Fe(III)-(oxyhydr)oxides. However, these efforts have been complicated by the fact that these minerals often occur in the micro- to nanosize regime, and in relevant natural environments as well as in the laboratory are subject to aggregation. The nature of the physical interface between the cellular envelope, the outer-membrane cytochromes responsible for facilitating the interfacial electron transfer step, and these complex mineral particulates is thus difficult to probe. Previous studiesmore » using whole cells have reported reduction rates that do not correlate with particle size. In the present study we isolate the interaction between the decaheme outer-membrane cytochrome OmcA of Shewanella oneidensis and nanoparticulate hematite, examining the reduction rate as a function of particle size and reaction products through detailed characterization of the electron balance and the structure and valence of iron at particle surfaces. By comparison with abiotic reduction via the smaller molecule ascorbic acid, we show that the reduction rate is systematically controlled by the sterically accessible interfacial contact area between OmcA and hematite in particle aggregates; rates increase once pore throat sizes in aggregates become as large as OmcA. Simultaneous measure of OmcA oxidation against Fe(II) release shows a ratio of 1:10, consistent with a cascade OmcA oxidation mechanism heme by heme. X-ray absorption spectroscopies reveal incipient magnetite on the reacted surfaces of the hematite nanoparticles after reaction. The collective findings establish the importance of accessibility of physical contact between the terminal reductases and iron oxide surfaces, and through apparent consistency of observations help reconcile behavior reported at the larger more complex scale of whole cell studies.« less

Particle size effect and the mechanism of hematite reduction by the outer membrane cytochrome OmcA of Shewanella oneidensis MR-1

NASA Astrophysics Data System (ADS)

Liu, Juan; Pearce, Carolyn I.; Shi, Liang; Wang, Zheming; Shi, Zhi; Arenholz, Elke; Rosso, Kevin M.

2016-11-01

The cycling of iron at the Earth's near surface is profoundly influenced by dissimilatory metal reducing microorganisms, and many studies have focused on unraveling electron transfer mechanisms between these bacteria and Fe(III)-(oxyhydr)oxides. However, these efforts have been complicated by the fact that these minerals often occur in the micro- to nanosize regime, and in relevant natural environments as well as in the laboratory are subject to aggregation. The nature of the physical interface between the cellular envelope, the outer-membrane cytochromes responsible for facilitating the interfacial electron transfer step, and these complex mineral particulates is thus difficult to probe. Previous studies using whole cells have reported reduction rates that do not correlate with particle size. In the present study we isolate the interaction between the decaheme outer-membrane cytochrome OmcA of Shewanella oneidensis and nanoparticulate hematite, examining the reduction rate as a function of particle size and reaction products through detailed characterization of the electron balance and the structure and valence of iron at particle surfaces. By comparison with abiotic reduction via the smaller molecule ascorbic acid, we show that the reduction rate is systematically controlled by the sterically accessible interfacial contact area between OmcA and hematite in particle aggregates; rates increase once pore throat sizes in aggregates become as large as OmcA. Simultaneous measure of OmcA oxidation against Fe(II) release shows a ratio of 1:10, consistent with a cascade OmcA oxidation mechanism heme by heme. X-ray absorption spectroscopies reveal incipient magnetite on the reacted surfaces of the hematite nanoparticles after reaction. The collective findings establish the importance of accessibility of physical contact between the terminal reductases and iron oxide surfaces, and through apparent consistency of observations help reconcile behavior reported at the larger more complex scale of whole cell studies.

Interesting electron storage phenomenon in the spherical Ag/TiO{sub 2} nanocomposites and its application for the decomposition of acetaldehyde in the dark

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

Wang, Xinyan; State Key Laboratory of Electroanalytical Chemistry, c/o Engineering Laboratory for Modern Analytical Techniques, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022; Wu, Tongshun

2016-01-15

Highlights: • The Ag/TiO{sub 2} composites have been prepared by a facile solvothermal method. • The photogenerated charges transfer behaviors between the Ag and TiO{sub 2}. • The Ag/TiO{sub 2} composites can store photogenerated electrons for a relative long time. • The Ag/TiO{sub 2} composite could be further used to decompose acetaldehyde in the dark. - Abstract: Ag/TiO{sub 2} nanocomposite has been prepared by a facile one-step low-temperature solvothermal method. The powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements have been used to characterize the detailed structure of the as-synthesized nanocomposite and the results indicate that the nanocompoistemore » is with the spherical structure and Ag and TiO{sub 2} nanoparticles are homogeneously dispersed in the sphere. Surface photovoltage (SPV) and transient photovoltage (TPV) techniques were used to further investigate the charge transfer behavior between the TiO{sub 2} and Ag in this composite material, and the results reveal that the nanocomposites could store the electrons for a relative long time even under air. Furthermore, these stored electrons in the nanocomposites have been successfully applied to decompose the acetaldehyde in the dark.« less

Radiometric Measurement Comparisons Using Transfer Radiometers in Support of the Calibration of NASA's Earth Observing System (EOS) Sensors

NASA Technical Reports Server (NTRS)

Butler, James J.; Johnson, B. Carol; Brown, Steven W.; Yoon, Howard W.; Barnes, Robert A.; Markham, Brian L.; Biggar, Stuart F.; Zalewski, Edward F.; Spyak, Paul R.; Cooper, John W.;

Mass transfer from a sphere in an oscillating flow with zero mean velocity

NASA Technical Reports Server (NTRS)

Drummond, Colin K.; Lyman, Frederic A.

1990-01-01

A pseudospectral numerical method is used for the solution of the Navier-Stokes and mass transport equations for a sphere in a sinusoidally oscillating flow with zero mean velocity. The flow is assumed laminar and axisymmetric about the sphere's polar axis. Oscillating flow results were obtained for Reynolds numbers (based on the free-stream oscillatory flow amplitude) between 1 and 150, and Strouhal numbers between 1 and 1000. Sherwood numbers were computed and their dependency on the flow frequency and amplitude discussed. An assessment of the validity of the quasi-steady assumption for mass transfer is based on these results.

Mass and heat transfer in crushed oil shale

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

Carley, J.F.; Ott, L.L.; Swecker, J.L.

1995-03-01

Studies of heat and mass transfer in packed beds, which disagree substantially in their findings, have nearly all been done with beds of regular particles of uniform size, whereas oil-shale retorting involves particles of diverse irregular shapes and sizes. The authors, in 349 runs, measured mass-transfer rates front naphthalene particles buried in packed beds by passing through air at room temperature. An exact catalog between convection of heat and mass makes it possible to infer heat-transfer coefficients from measured mass-transfer coefficients and fluid properties. Some beds consisted of spheres, naphthalene and inert, of the same, contrasting or distributed sizes. Inmore » some runs, naphthalene spheres were buried in beds of crushed shale, some in narrow screen ranges and others with a wide size range. In others, naphthalene lozenges of different shapes were buried in beds of crushed shale in various bed axis orientations. This technique permits calculation of the mass-transfer coefficient for each active particle in the bed rather than, as in most past studies, for the bed as a whole. The data are analyzed by the traditional correlation of Colburn j{sub D} vs. Reynolds number and by multiple regression of the mass-transfer coefficient on air rate, sizes of active and inert particles, void fraction, and temperature. Principal findings are: local Reynolds number should be based on the active-particle size, not the average for the whole bed; differences between shallow and deep beds are not appreciable; mass transfer is 26% faster for spheres and lozenges buried in shale than in all-sphere beds; orientation of lozenges in shale beds has little or no effect on mass-transfer rate; and for mass or heat transfer in shale beds, log(j{center_dot}{epsilon}) = {minus}0.0747 - 0.6344 log N{sub Re} + 0. 0592 log {sup 2} N{sub Re}.« less

Feasibility study of low angle planetary entry. [probe design for Jovian entry

NASA Technical Reports Server (NTRS)

Defrees, R. E.

1975-01-01

The feasibility of a Jovian entry by a probe originally designed for Saturn and Uranus entries is examined. An entry probe is described which is capable of release near an outer planet's sphere of influence and descent to a predetermined target entry point in the planet's atmosphere. The probe is designed so as to survive the trapped particle radiation belts and an entry heating pulse. Data is gathered and relayed to an overflying spacecraft bus during descent. Probe variations for two similar missions are described. In the first flyby of Jupiter by a Pioneer spacecraft launched during the 1979 opportunity is examined parametrically. In the second mission an orbiter based on Pioneer and launched in 1980 is defined in specific terms. The differences rest in the science payloads and directly affected wiring and electronics packages.

The Thermal Evaluation of Air-Cooled Electronic Equipment

DTIC Science & Technology

1952-09-01

of Unit with Case-Envelope Heat Exchanger 233 VII-7 Storking Plot for Evaluation of Case Heat Transfer of Unit with Integrated or Separate... wing . 1. Case Cooled by Free Convection and Radiation Equipment of this type which depends on the natural heat dissipative capacity of the outer...described application, a tightly-fitting spring- clip is placed around the component, such as a tube, with the two thermocouple lead wires spot-welded

Oil exudation and histological structures of duck egg yolks during brining.

PubMed

Lai, K M; Chung, W H; Jao, C L; Hsu, K C

2010-04-01

Changes in oil exudation and histological structures of salted duck egg yolks during brining up to 5 wk were investigated. During brining, the salt contents of albumen, exterior yolk (hardened portion), and interior yolk (soft or liquid portion) gradually increased accompanied by slight decreases in moisture content. The hardening ratio of salted egg yolks increased rapidly to about 60% during the first week of brining and then reached 100% at the end of brining. After brining, part of the lipids in salted egg yolk became free due to the structural changes of low-density lipoprotein induced by dehydration and increase of salt content, and more free lipids in salted egg yolk were released after the cooking process. With the brining time increased up to 5 wk, the outer region of the cooked salted yolk gradually changed into dark brown, brown, orange, and then dark brown, whereas the center region changed into light yellow, yellow, dark yellow, and then yellow again. The microstructures of cooked salted egg yolks showed that the yolk spheres in the outer and middle regions retained their original shape, with some shrinking and being packed more loosely when brining time increased, and the exuded oil filled the space between the spheres. Furthermore, the yolk spheres in the center region transformed to a round shape but still showed granulation after 4 wk of brining, whereas they were mostly disrupted after 2 to 5 wk of brining. One of the most important characteristics of cooked salted egg yolks, gritty texture, contributed to oil exudation and granulated yolk spheres were observed at the brining time of 4 wk.

New constraints on the disk characteristics and companion candidates around T Chamaeleontis with VLT/SPHERE

NASA Astrophysics Data System (ADS)

Pohl, A.; Sissa, E.; Langlois, M.; Müller, A.; Ginski, C.; van Holstein, R. G.; Vigan, A.; Mesa, D.; Maire, A.-L.; Henning, Th.; Gratton, R.; Olofsson, J.; van Boekel, R.; Benisty, M.; Biller, B.; Boccaletti, A.; Chauvin, G.; Daemgen, S.; de Boer, J.; Desidera, S.; Dominik, C.; Garufi, A.; Janson, M.; Kral, Q.; Ménard, F.; Pinte, C.; Stolker, T.; Szulágyi, J.; Zurlo, A.; Bonnefoy, M.; Cheetham, A.; Cudel, M.; Feldt, M.; Kasper, M.; Lagrange, A.-M.; Perrot, C.; Wildi, F.

2017-09-01

Context. The transition disk around the T Tauri star T Cha possesses a large gap, making it a prime target for high-resolution imaging in the context of planet formation. Aims: We aim to find signs of disk evolutionary processes by studying the disk geometry and the dust grain properties at its surface, and to search for companion candidates. Methods: We analyze a set of VLT/SPHERE data at near-infrared and optical wavelengths. We performed polarimetric imaging of T Cha with IRDIS (1.6 μm) and ZIMPOL (0.5-0.9 μm), and obtained intensity images from IRDIS dual-band imaging with simultaneous spectro-imaging with IFS (0.9-1.3 μm). Results: The disk around T Cha is detected in all observing modes and its outer disk is resolved in scattered light with unprecedented angular resolution and signal-to-noise. The images reveal a highly inclined disk with a noticeable east-west brightness asymmetry. The significant amount of non-azimuthal polarization signal in the Uφ images, with a Uφ/Qφ peak-to-peak value of 14%, is in accordance with theoretical studies on multiple scattering in an inclined disk. Our optimal axisymmetric radiative transfer model considers two coplanar inner and outer disks, separated by a gap of 0.̋28 ( 30 au) in size, which is larger than previously thought. We derive a disk inclination of 69 deg and PA of 114 deg. In order to self-consistently reproduce the intensity and polarimetric images, the dust grains, responsible for the scattered light, need to be dominated by sizes of around ten microns. A point source is detected at an angular distance of 3.5'' from the central star. It is, however, found not to be co-moving. Conclusions: We confirm that the dominant source of emission is forward scattered light from the near edge of the outer disk. Our point source analysis rules out the presence of a companion with mass larger than 8.5 Mjup between 0.̋1 and 0.̋3. The detection limit decreases to 2 Mjup for 0.̋3 to 4.0''. Based on observations made with European Southern Observatory (ESO) telescopes at the Paranal Observatory in Chile, under program IDs 095.C-0298(B), 096.C-0248(B) and 096.C-0248(C).

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

NASA Astrophysics Data System (ADS)

Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

2003-04-01

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

Four second-sphere residues of Thermus thermophilus SG0.5JP17-16 laccase tune the catalysis by hydrogen-bonding networks.

PubMed

Liu, Huiping; Zhu, Yanyun; Yang, Xiaorong; Lin, Ying

2018-05-01

The multicopper oxidases catalyze 1-electron oxidation of four substrate molecules and concomitantly 4-electron reduction of dioxygen to water. The substrate loses the electrons at the type 1 copper (T1 Cu) site of the enzyme, while the dioxygen is reduced to water at the trinuclear copper center. A highly conserved Glu residue, which is at the dioxygen-entering channel, shuttles the proton to break the O-O bond of dioxygen. At the water-leaving channel, an Asp residue was found to be important in the protonation mechanism. In this study, laccase from Thermus thermophilus SG0.5JP17-16 (lacTT) was investigated to address how four second-sphere residues E356, E456, D106, and D423 affect the activity of the enzyme. Kinetic data indicate that catalytic activities of the enzyme are altered by site-directed mutagenesis on four second-sphere residues. The structural model of lacTT was generated by homology modeling. Structural and spectral data indicate that the E356 residue is situated at the substrate-binding site, responsible for the binding of the substrate and the geometry of the T1 Cu site by hydrogen-bonding networks; the E456 residue, located at the dioxygen-entering channel, plays a critical role in stabilizing the structure of all active copper centers and shuttling the proton to the trinuclear copper cluster (TNC) for the reductive reaction of dioxygen; the D106 and D423 residues are at the water-leaving channel, and they are important for the essential geometry of the TNC and the release of the water molecules. Altogether, this study contributes to the further understanding of the basic mechanism involving the oxidation of the substrate, electron transfer, and the reduction of dioxygen in lacTT.

Röntgen spheres around active stars

NASA Astrophysics Data System (ADS)

Locci, Daniele; Cecchi-Pestellini, Cesare; Micela, Giuseppina; Ciaravella, Angela; Aresu, Giambattista

2018-01-01

X-rays are an important ingredient of the radiation environment of a variety of stars of different spectral types and age. We have modelled the X-ray transfer and energy deposition into a gas with solar composition, through an accurate description of the electron cascade following the history of the primary photoelectron energy deposition. We test and validate this description studying the possible formation of regions in which X-rays are the major ionization channel. Such regions, called Röntgen spheres may have considerable importance in the chemical and physical evolution of the gas embedding the emitting star. Around massive stars the concept of Röntgen sphere appears to be of limited use, as the formation of extended volumes with relevant levels of ionization is efficient just in a narrow range of gas volume densities. In clouds embedding low-mass pre-main-sequence stars significant volumes of gas are affected by ionization levels exceeding largely the cosmic-ray background ionization. In clusters arising in regions of vigorous star formation X-rays create an ionization network pervading densely the interstellar medium, and providing a natural feedback mechanism, which may affect planet and star formation processes.

NiCo2O4 surface coating Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as cathode material for high-performance lithium ion battery

NASA Astrophysics Data System (ADS)

Ye, Pan; Dong, Hui; Xu, Yunlong; Zhao, Chongjun; Liu, Dong

2018-01-01

Here we report a novel transitional metal oxide (NiCo2O4) coated Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as high-performance Li-ion battery cathode material. A thin layer of ∼10 nm NiCo2O4 was formed by simple wet-chemistry approach adjacent to the surface of Li[Ni0.03Mn1.97]O4 micro-/nano- spheres, leading to significantly enhanced battery electrochemical performance. The optimized sample(1 wt%) not only delivers excellent discharge capacity and cycling stability improvement at both room temperature and elevated temperatures, but also effectively prevents Mn dissolution while retaining its coating structure intact according to XRF and TEM results. The CV and EIS break-down analysis indicated a much faster electrochemical reaction kinetics, more reversible electrode process and greatly reduced charge transfer and Warburg resistance, clearly illustrating the dual role of NiCo2O4 coating to boost electron transport and Li+ diffusion, and alleviation of manganese dissolving. This approach may render as an efficient technique to realize high-performance lithium ion battery cathode material.

Carbonaceous spheres—an unusual template for solid metal oxide mesoscale spheres: Application to ZnO spheres

NASA Astrophysics Data System (ADS)

Patrinoiu, Greta; Calderón-Moreno, Jose Maria; Culita, Daniela C.; Birjega, Ruxandra; Ene, Ramona; Carp, Oana

2013-06-01

A green template route for the synthesis of mesoscale solid ZnO spheres was ascertained. The protocol involves a double coating of the carbonaceous spheres with successive layers of zinc-containing species by alternating a non-ultrasound and ultrasound-assisted deposition, followed by calcination treatments. The composites were characterized by FTIR spectroscopy, thermal analysis, scanning electron microscopy while the obtained ZnO spheres by X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, N2 adsorption-desorption isotherms and photoluminescence investigations. A growth mechanism of the solid spheres is advanced based on these results. While the spheres' diameters and the mean size values of ZnO are independent on deposition order, the surface area and the external porosity are fairly dependent. The photoluminescence measurements showed interesting emission features, with emission bands in the violet to orange region. The spheres present high photocatalytical activity towards the degradation of phenol under UV irradiation, the main reaction being its mineralization.

Consolidation of metallic hollow spheres by electric sintering

NASA Astrophysics Data System (ADS)

Mironov, V.; Tatarinov, A.; Lapkovsky, V.

2017-07-01

This paper considers peculiarities of the technology of production of structures from metallic hollow spheres (MHS) using magnetic fields and electric sintering. In these studies, the raw material was MHS obtained by burning of polystyrene balls coated by carbon steel. MHS had an outer diameter of 3-5 mm and a steel wall thickness of 70-120 microns. Pulsed current generators were used for electric sintering of MHS to obtain different spatial structures. Since MHS have small strength, the compressive pressure during sintering should be minimal. To improve the adhesion strength and reduce the required energy for sintering, hollow spheres were coated with copper by ion-plasma sputtering in vacuum. The coating thickness was 10-15 microns. The ferromagnetic properties of MHS allowed using of magnet fields for orientation of the spheres in the structures, as well as using of perforated tapes acting as orienting magnetic cores. Ultrasonic testing of MHS structures has been tried using through propagation of ultrasound in low kilohertz frequency range. Sensitivity of the propagation parameters to water filling of inter-spheres space and sintering temperature was demonstrated.

Cell-secreted flavins bound to membrane cytochromes dictate electron transfer reactions to surfaces with diverse charge and pH.

PubMed

Okamoto, Akihiro; Kalathil, Shafeer; Deng, Xiao; Hashimoto, Kazuhito; Nakamura, Ryuhei; Nealson, Kenneth H

2014-07-11

The variety of solid surfaces to and from which microbes can deliver electrons by extracellular electron transport (EET) processes via outer-membrane c-type cytochromes (OM c-Cyts) expands the importance of microbial respiration in natural environments and industrial applications. Here, we demonstrate that the bifurcated EET pathway of OM c-Cyts sustains the diversity of the EET surface in Shewanella oneidensis MR-1 via specific binding with cell-secreted flavin mononucleotide (FMN) and riboflavin (RF). Microbial current production and whole-cell differential pulse voltammetry revealed that RF and FMN enhance EET as bound cofactors in a similar manner. Conversely, FMN and RF were clearly differentiated in the EET enhancement by gene-deletion of OM c-Cyts and the dependency of the electrode potential and pH. These results indicate that RF and FMN have specific binding sites in OM c-Cyts and highlight the potential roles of these flavin-cytochrome complexes in controlling the rate of electron transfer to surfaces with diverse potential and pH.

A combined electrochemical and optical trapping platform for measuring single cell respiration rates at electrode interfaces

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

Gross, Benjamin J.; El-Naggar, Mohamed Y., E-mail: mnaggar@usc.edu; Molecular and Computational Biology Section, Department of Biological Sciences, University of Southern California, Los Angeles, California 90089-0484

2015-06-15

Metal-reducing bacteria gain energy by extracellular electron transfer to external solids, such as naturally abundant minerals, which substitute for oxygen or the other common soluble electron acceptors of respiration. This process is one of the earliest forms of respiration on earth and has significant environmental and technological implications. By performing electron transfer to electrodes instead of minerals, these microbes can be used as biocatalysts for conversion of diverse chemical fuels to electricity. Understanding such a complex biotic-abiotic interaction necessitates the development of tools capable of probing extracellular electron transfer down to the level of single cells. Here, we describe anmore » experimental platform for single cell respiration measurements. The design integrates an infrared optical trap, perfusion chamber, and lithographically fabricated electrochemical chips containing potentiostatically controlled transparent indium tin oxide microelectrodes. Individual bacteria are manipulated using the optical trap and placed on the microelectrodes, which are biased at a suitable oxidizing potential in the absence of any chemical electron acceptor. The potentiostat is used to detect the respiration current correlated with cell-electrode contact. We demonstrate the system with single cell measurements of the dissimilatory-metal reducing bacterium Shewanella oneidensis MR-1, which resulted in respiration currents ranging from 15 fA to 100 fA per cell under our measurement conditions. Mutants lacking the outer-membrane cytochromes necessary for extracellular respiration did not result in any measurable current output upon contact. In addition to the application for extracellular electron transfer studies, the ability to electronically measure cell-specific respiration rates may provide answers for a variety of fundamental microbial physiology questions.« less

Effective on-site Coulomb interaction and electron configurations in transition-metal complexes from constraint density functional theory

NASA Astrophysics Data System (ADS)

Nawa, Kenji; Nakamura, Kohji; Akiyama, Toru; Ito, Tomonori; Weinert, Michael

Effective on-site Coulomb interactions (Ueff) and electron configurations in the localized d and f orbitals of metal complexes in transition-metal oxides and organometallic molecules, play a key role in the first-principles search for the true ground-state. However, wide ranges of values in the Ueff parameter of a material, even in the same ionic state, are often reported. Here, we revisit this issue from constraint density functional theory (DFT) by using the full-potential linearized augmented plane wave method. The Ueff parameters for prototypical transition-metal oxides, TMO (TM =Mn, Fe, Co, Ni), were calculated by the second derivative of the total energy functional with respect to the d occupation numbers inside the muffin-tin (MT) spheres as a function of the sphere radius. We find that the calculated Ueff values depend significantly on the MT radius, with a variation of more than 3 eV when the MT radius changes from 2.0 to 2.7 a.u., but importantly an identical valence band structure can be produced in all the cases, with an approximate scaling of Ueff. This indicates that a simple transferability of the Ueff value among different calculation methods is not allowed. We further extend the constraint DFT to treat various electron configurations of the localized d-orbitals in organometallic molecules, TMCp2 (TM =Cr, Mn, Fe, Co, Ni), and find that the calculated Ueff values can reproduce the experimentally determined ground-state electron configurations.

Characterization of the periplasmic redox network that sustains the versatile anaerobic metabolism of Shewanella oneidensis MR-1

PubMed Central

Alves, Mónica N.; Neto, Sónia E.; Alves, Alexandra S.; Fonseca, Bruno M.; Carrêlo, Afonso; Pacheco, Isabel; Paquete, Catarina M.; Soares, Cláudio M.; Louro, Ricardo O.

2015-01-01

The versatile anaerobic metabolism of the Gram-negative bacterium Shewanella oneidensis MR-1 (SOMR-1) relies on a multitude of redox proteins found in its periplasm. Most are multiheme cytochromes that carry electrons to terminal reductases of insoluble electron acceptors located at the cell surface, or bona fide terminal reductases of soluble electron acceptors. In this study, the interaction network of several multiheme cytochromes was explored by a combination of NMR spectroscopy, activity assays followed by UV-visible spectroscopy and comparison of surface electrostatic potentials. From these data the small tetraheme cytochrome (STC) emerges as the main periplasmic redox shuttle in SOMR-1. It accepts electrons from CymA and distributes them to a number of terminal oxidoreductases involved in the respiration of various compounds. STC is also involved in the electron transfer pathway to reduce nitrite by interaction with the octaheme tetrathionate reductase (OTR), but not with cytochrome c nitrite reductase (ccNiR). In the main pathway leading the metal respiration STC pairs with flavocytochrome c (FccA), the other major periplasmic cytochrome, which provides redundancy in this important pathway. The data reveals that the two proteins compete for the binding site at the surface of MtrA, the decaheme cytochrome inserted on the periplasmic side of the MtrCAB–OmcA outer-membrane complex. However, this is not observed for the MtrA homologues. Indeed, neither STC nor FccA interact with MtrD, the best replacement for MtrA, and only STC is able to interact with the decaheme cytochrome DmsE of the outer-membrane complex DmsEFABGH. Overall, these results shown that STC plays a central role in the anaerobic respiratory metabolism of SOMR-1. Nonetheless, the trans-periplasmic electron transfer chain is functionally resilient as a consequence of redundancies that arise from the presence of alternative pathways that bypass/compete with STC. PMID:26175726

Hydration entropy change from the hard sphere model.

PubMed

Graziano, Giuseppe; Lee, Byungkook

2002-12-10

The gas to liquid transfer entropy change for a pure non-polar liquid can be calculated quite accurately using a hard sphere model that obeys the Carnahan-Starling equation of state. The same procedure fails to produce a reasonable value for hydrogen bonding liquids such as water, methanol and ethanol. However, the size of the molecules increases when the hydrogen bonds are turned off to produce the hard sphere system and the volume packing density rises. We show here that the hard sphere system that has this increased packing density reproduces the experimental transfer entropy values rather well. The gas to water transfer entropy values for small non-polar hydrocarbons is also not reproduced by a hard sphere model, whether one uses the normal (2.8 A diameter) or the increased (3.2 A) size for water. At least part of the reason that the hard sphere model with 2.8 A size water produces too small entropy change is that the size of water is too small for a system without hydrogen bonds. The reason that the 3.2 A model also produces too small entropy values is that this is an overly crowded system and that the free volume introduced in the system by the addition of a solute molecule produces too much of a relief to this crowding. A hard sphere model, in which the free volume increase is limited by requiring that the average surface-to-surface distance between the solute and water molecules is the same as that between the increased-size water molecules, does approximately reproduce the experimental hydration entropy values. Copyright 2002 Elsevier Science B.V.

Structural and magnetic properties of multi-core nanoparticles analysed using a generalised numerical inversion method

PubMed Central

Bender, P.; Bogart, L. K.; Posth, O.; Szczerba, W.; Rogers, S. E.; Castro, A.; Nilsson, L.; Zeng, L. J.; Sugunan, A.; Sommertune, J.; Fornara, A.; González-Alonso, D.; Barquín, L. Fernández; Johansson, C.

2017-01-01

The structural and magnetic properties of magnetic multi-core particles were determined by numerical inversion of small angle scattering and isothermal magnetisation data. The investigated particles consist of iron oxide nanoparticle cores (9 nm) embedded in poly(styrene) spheres (160 nm). A thorough physical characterisation of the particles included transmission electron microscopy, X-ray diffraction and asymmetrical flow field-flow fractionation. Their structure was ultimately disclosed by an indirect Fourier transform of static light scattering, small angle X-ray scattering and small angle neutron scattering data of the colloidal dispersion. The extracted pair distance distribution functions clearly indicated that the cores were mostly accumulated in the outer surface layers of the poly(styrene) spheres. To investigate the magnetic properties, the isothermal magnetisation curves of the multi-core particles (immobilised and dispersed in water) were analysed. The study stands out by applying the same numerical approach to extract the apparent moment distributions of the particles as for the indirect Fourier transform. It could be shown that the main peak of the apparent moment distributions correlated to the expected intrinsic moment distribution of the cores. Additional peaks were observed which signaled deviations of the isothermal magnetisation behavior from the non-interacting case, indicating weak dipolar interactions. PMID:28397851

Tunneling explains efficient electron transport via protein junctions.

PubMed

Fereiro, Jerry A; Yu, Xi; Pecht, Israel; Sheves, Mordechai; Cuevas, Juan Carlos; Cahen, David

2018-05-15

Metalloproteins, proteins containing a transition metal ion cofactor, are electron transfer agents that perform key functions in cells. Inspired by this fact, electron transport across these proteins has been widely studied in solid-state settings, triggering the interest in examining potential use of proteins as building blocks in bioelectronic devices. Here, we report results of low-temperature (10 K) electron transport measurements via monolayer junctions based on the blue copper protein azurin (Az), which strongly suggest quantum tunneling of electrons as the dominant charge transport mechanism. Specifically, we show that, weakening the protein-electrode coupling by introducing a spacer, one can switch the electron transport from off-resonant to resonant tunneling. This is a consequence of reducing the electrode's perturbation of the Cu(II)-localized electronic state, a pattern that has not been observed before in protein-based junctions. Moreover, we identify vibronic features of the Cu(II) coordination sphere in transport characteristics that show directly the active role of the metal ion in resonance tunneling. Our results illustrate how quantum mechanical effects may dominate electron transport via protein-based junctions.

Bromine-doped DWNTs: A Molecular Faraday Cage

NASA Astrophysics Data System (ADS)

Chen, Gugang; Margine, Roxana; Gupta, Rajeev; Crespi, Vincent; Eklund, Peter; Sumanasekera, Gamini; Bandow, Shunji; Iijima, S.

2003-03-01

Raman scattering is used to probe the charge transfer distribution in Bromine-doped double-walled carbon nanotubes (DWNT). Using 1064 nm and 514.5 nm laser excitation we are able to study the charge-transfer sensitive phonons in the inner ( (5,5)) and outer ( (10,10)) tubes of the double-walled pair. The experimental results are compared to our tight binding band structure calculations that include a self-consistent electrostatic term sensitive to the average net charge density on each tube. Upon doping, the nanotube tangential and radial Raman bands from the outer (primary) tubes were observed to shift dramatically to higher frequencies, consistent with a C-C bond contraction driven by the acceptor-doping. The peak intensities of these bands significantly decreased with increasing doping exposure, and they eventually vanished, consistent with a deep depression in the Fermi energy that extinguishes the resonant Raman effect. Interestingly, at the same time, we observed little or no change for the tangential and radial Raman features identified with the inner (secondary) tubes during the bromine doping. Our electronic structure calculations show that the charge distribution between the outer and inner tubes depends on doping level and also, to some extent, on specific tube chirality combinations. In general, in agreement with experiment, the calculations find a very small net charge on the inner tube, consistent with a "Molecular Faraday Effect", e.g., a DWNT of (10, 10)/ (5, 5) configuration that exhibits 0.5 holes/Å total charge transfer, has only 0.04 holes/Å on the inner (secondary) tube.

Comparison of Experimental and Computational Aerothermodynamics of a 70-deg Sphere-Cone

NASA Technical Reports Server (NTRS)

Hollis, Brian R.; Perkins, John N.

1996-01-01

Numerical solutions for hypersonic flows of carbon-dioxide and air around a 70-deg sphere-cone have been computed using an axisymmetric non-equilibrium Navier-Stokes solver. Freestream flow conditions for these computations were equivalent to those obtained in an experimental blunt-body heat-transfer study conducted in a high-enthalpy, hypervelocity expansion tube. Comparisons have been made between the computed and measured surface heat-transfer rates on the forebody and afterbody of the sphere-cone and on the sting which supported the test model. Computed forebody heating rates were within the estimated experimental uncertainties of 10% on the forebody and 15% in the wake except for within the recirculating flow region of the wake.

Maxwell's second- and third-order equations of transfer for non-Maxwellian gases

NASA Technical Reports Server (NTRS)

Baganoff, D.

1992-01-01

Condensed algebraic forms for Maxwell's second- and third-order equations of transfer are developed for the case of molecules described by either elastic hard spheres, inverse-power potentials, or by Bird's variable hard-sphere model. These hardly reduced, yet exact, equations provide a new point of origin, when using the moment method, in seeking approximate solutions in the kinetic theory of gases for molecular models that are physically more realistic than that provided by the Maxwell model. An important by-product of the analysis when using these second- and third-order relations is that a clear mathematical connection develops between Bird's variable hard-sphere model and that for the inverse-power potential.

Hopkins with SPHERES RINGS

NASA Image and Video Library

2013-11-04

ISS037-E-025870 (4 Nov. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Michael Hopkins, Expedition 37 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

Hopkins with SPHERES RINGS

NASA Image and Video Library

2013-11-04

ISS037-E-025868 (4 Nov. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Michael Hopkins, Expedition 37 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

DOD SPHERES-RINGS Test Session

NASA Image and Video Library

2013-11-04

ISS037-E-025915 (4 Nov. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Michael Hopkins, Expedition 37 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

Hopkins with SPHERES RINGS

NASA Image and Video Library

2013-11-04

ISS037-E-025866 (4 Nov. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Michael Hopkins, Expedition 37 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

Hopkins with SPHERES RINGS

NASA Image and Video Library

2013-11-04

ISS037-E-025872 (4 Nov. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Michael Hopkins, Expedition 37 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

Hopkins with SPHERES RINGS

NASA Image and Video Library

2013-11-04

ISS037-E-025879 (4 Nov. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Michael Hopkins, Expedition 37 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

Molecular Simulation of Cesium Adsorption at the Basal Surface of Phyllosilicate Minerals

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

Kerisit, Sebastien N.; Okumura, Masahiko; Rosso, Kevin M.

2016-08-16

A better understanding of the thermodynamics of radioactive cesium uptake at the surfaces of phyllosilicate minerals is needed to understand mechanisms of its selective adsorption and help guide the development of practical and inexpensive decontamination techniques. In this work, molecular dynamics simulations were carried out to determine the thermodynamics of adsorption of Cs + at the basal surface of six 2:1 phyllosilicate minerals, namely pyrophyllite, illite, muscovite, phlogopite, celadonite, and margarite. These minerals were selected to isolate the effects of the magnitude of the permanent layer charge (≤ 2), its location (tetrahedral versus octahedral sheet), and the structure of themore » octahedral sheet (dioctahedral versus trioctahedral). Good agreement was obtained with experiment in terms of the hydration free energy of Cs + and the structure and thermodynamics of Cs + adsorption at the muscovite basal surface, for which published data were available for comparison. With the exception of pyrophyllite, which did not exhibit an inner-sphere free energy minimum, all phyllosilicate minerals showed similar behavior with respect to Cs + adsorption; notably, Cs + adsorption was predominantly inner-sphere whereas outer-sphere adsorption was very weak with the simulations predicting the formation of an extended outer-sphere complex. For a given location of the layer charge, the free energy of adsorption as an inner-sphere complex was found to vary linearly with the magnitude of the layer charge. For a given location and magnitude of the layer charge, adsorption at phlogopite (trioctahedral sheet structure) was much less favorable than at muscovite (dioctahedral sheet structure) due to the electrostatic repulsion between the adsorbed Cs + and the hydrogen atom of the hydroxyl group directly below the six-membered siloxane ring cavity. For a given magnitude of the layer charge and structure of the octahedral sheet, adsorption at celadonite (layer charge located in the octahedral sheet) was favored over muscovite (layer charge located in the tetrahedral sheet) due to the increased distance with surface potassium ions.« less

Theoretical Elastic Stress Distributions Arising from Discontinuities and Edge Loads in Several Shell-Type Structures

NASA Technical Reports Server (NTRS)

Johns, Robert H.; Orange, Thomas W.

1961-01-01

The deformation and complete stress distribution are determined for each of the following edge loaded thin shells of revolution: (1) a right circular cylinder, (2) a frustum of a right circular cone, and (3) a portion of a sphere. The locations of the maximum circumferential and meridional stresses on both the inner and outer surfaces are also found. The basic equations for the above were selected from the published literature on the subject and expanded to produce to resultant-stress equations in closed from where practicable to do so. Equations are also developed for the discontinuity shear force and bending moment at each of the following junction: (1) axial change of thickness in a circular cylinder, (2) axial change of thickness in a cone, (3) change of thickness in a portion of a sphere, (4) a cylinder and a cone, (5) a cylinder and a portion of a sphere(6) a cylinder and a flat head, and (7) a cone and a portion of a sphere.

Laboratory Experiments to Study Spherical, Iron Oxide Concretion Growth Without Solid Nuclei: Implications for Understanding Meridiani "Blueberries"

NASA Astrophysics Data System (ADS)

Ormö, J.; Souza-Egipsy, V.; Chan, M. A.; Park, A. J.; Stich, M.; Komatsu, G.

2006-03-01

Spherical hematite concretions can form without a nucleus. Self-organized zones of super-saturated solution cause spherical precipitates of amorphous iron-hydroxide. Diffusion of Fe ions towards the outer perimeter of the amorphous sphere forms a rind, which then grows inwards.

Dynamic domains of the Derviche Tourneur sodium experiment: Simulations of a spherical magnetized Couette flow

NASA Astrophysics Data System (ADS)

Kaplan, E. J.; Nataf, H.-C.; Schaeffer, N.

2018-03-01

The Derviche Tourneur sodium experiment, a spherical Couette magnetohydrodynamics experiment with liquid sodium as the medium and a dipole magnetic field imposed from the inner sphere, recently underwent upgrades to its diagnostics to better characterize the flow and induced magnetic fields with global rotation. In tandem with the upgrades, a set of direct numerical simulations were run to give a more complete view of the fluid and magnetic dynamics at various rotation rates of the inner and outer spheres. These simulations reveal several dynamic regimes, determined by the Rossby number. At positive differential rotation there is a regime of quasigeostrophic flow, with low levels of fluctuations near the outer sphere. Negative differential rotation shows a regime of what appear to be saturated hydrodynamic instabilities at low negative differential rotation, followed by a regime where filamentary structures develop at low latitudes and persist over five to ten differential rotation periods as they drift poleward. We emphasize that all these coherent structures emerge from turbulent flows. At least some of them seem to be related to linear instabilities of the mean flow. The simulated flows can produce the same measurements as those that the physical experiment can take, with signatures akin to those found in the experiment. This paper discusses the relation between the internal velocity structures of the flow and their magnetic signatures at the surface.

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

DOE PAGES

Ellis, Ross J.; Bera, Mrinal K.; Reinhart, Benjamin; ...

2016-11-07

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, thismore » presents a new route for controlling anion transfer in electrochemically-driven separation applications.« less

Extra-mitochondrial aerobic metabolism in retinal rod outer segments: new perspectives in retinopathies.

PubMed

Panfoli, I; Calzia, D; Ravera, S; Morelli, A M; Traverso, C E

2012-04-01

Vertebrate retinal rods are photoreceptors for dim-light vision. They display extreme sensitivity to light thanks to a specialized subcellular organelle, the rod outer segment. This is filled with a stack of membranous disks, expressing the proteins involved in visual transduction, a very energy demanding process. Our previous proteomic and biochemical studies have shed new light on the chemical energy processes that supply ATP to the outer segment, suggesting the presence of an extra-mitochondrial aerobic metabolism in rod outer segment, devoid of mitochondria, which would account for a quantitatively adequate ATP supply for phototransduction. Here the functional presence of an oxidative phosphorylation in the rod outer limb is examined for its relationship to many physiological and pathological data on the rod outer segment. We hypothesize that the rod outer limb is at risk of oxidative stress, in any case of impairment in the respiratory chain functioning, or of blood supply. In fact, the electron transfer chain is a major source of reactive O(2) species, known to produce severe alteration to the membrane lipids, especially those of the outer segment that are rich in polyunsaturated fatty acids. We propose that the disk membrane may become the target of reactive oxygen species that may be released by the electron transport chain under pathologic conditions. For example, during aging reactive oxygen species production increases, while cellular antioxidant capacity decreases. Also the apoptosis of the rod observed after exposure to bright or continuous illumination can be explained considering that an overfunctioning of phototransduction may damage the disk membrane to a point at which cytochrome c escapes from the intradiskal space, where it is presently supposed to be, activating a putative caspase 9 and the apoptosome. A pathogenic mechanism for many inherited and acquired retinal degenerations, representing a major problem in clinical ophthalmology, is proposed: a number of rod pathologies would be promoted by impairment of energy supply and/or oxidative stress in the rod outer segment. In conclusion we suppose that the damaging role of oxygen, be it hypoxia or hyperoxia invoked in most of the blinding diseases, acquired and even hereditary is to be seeked for inside the photoreceptor outer segment that would conceal a potential for cell death that is still to be recognized. Copyright © 2012 Elsevier Ltd. All rights reserved.

Theoretical and experimental studies on silica-coated carbon spheres composites

NASA Astrophysics Data System (ADS)

Guo, Xingmei; Liu, Haixing; Shen, Yinghua; Niu, Mei; Yang, Yongzhen; Liu, Xuguang

2013-10-01

In order to prepare carbon-based photonic crystals, first of all, theoretical modeling calculation was used to predict the bandgap characteristics of silica-coated carbon spheres. Then, silica-coated carbon spheres composites were synthesized using tetraethyl orthosilicate as precursor of silica by a sol-gel method combined with Stöber method. Effect of reaction conditions on surface coating of carbon spheres with silica, including the pH, the amount of precursor and reaction time, was emphasized. The morphology and structure of the composites and the effect coating of carbon spheres with silica were characterized by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Fourier-transform infrared spectrometry. The coating ratio of silica was investigated by thermogravimetry. The results show that pH value played an important role in coating reaction, the dosage of the precursor and reaction time had significant effect on coating layer thickness, that is, coating ratio. Carbon spheres coated with silica had good dispersibility and dispersion stability in water and ethanol, which is preconditions of reactivity of carbon spheres in liquid phase and lays the basis for the application of carbon spheres.

orbis (sphaera), circulus, via, iter, orbita -- on the terminological identification of the essential paradigm change in astronomy by Johannes Kepler. (German Title: orbis (sphaera), circulus, via, iter, orbita} -- zur terminologischen Kennzeichnung des wesentlichsten Paradigmawechsels in der Astronomie durch Johannes Kepler)

NASA Astrophysics Data System (ADS)

Krafft, Fritz

2011-08-01

The use of modern terminology hinders to understand historical astronomical texts and often misleads the reader. Therefore, this study tries to reconstruct the ideas of the way the planets seem to move against the sphere of fixed stars in a non-teleological manner, that means in the original view and with original terms. The study proceeds historically and explains: (1) Aristotle's system of homocentric spheres being hollow spheres of ether turning equally round the earth in the centre of the world, a number of which makes the apparatus of the movement of a planet which produces its apparently unequal motion. (2) Ptolemy's reductionistic system of geometric circles (eccentric deferents, epicycles etc.), which are indeed great circles on non-concentric hollow spheres, whereupon they turn around equally. The space which they take up in all is surrounded by an inner and an outer concentric spherical surface and makes the sphere of the planet. (3) John's of Sacrobosco transferring of the geometric astronomy to the Latin of Middle Ages and the commentators' precision of the Greek-Latin terms. (4) The tradition of the "Theorica planetarum" which makes this geometry physics by allotting every partial moving to a partial material hollow sphere (with spherical surfaces of different centricity) or full sphere of an epicycle (orbes particulares or partialis), a number of which makes the entire sphere of each planet (orbis totalis or totus). - Copernicus also stood within this tradition, except that his entire spheres differ from the earlier ones in size or thickness (because he eliminated the partly very big synodic epicycles and allocated their effect as a mere parallactic one to the yearly moving of the earth) and in the great intervening spaces between each other (a result of measuring the true distances of the planets on the basis of these parallactic effects). (5) Tycho Brahe's refutation of the unchangingness and unpermeableness and therefore solidity of all etherial spheres, what had been the fundamental condition for creating the indirect ways of the planets in all astronomical systems with partial or entire spheres engaging one another. It was particularly Kepler who recognizes that as a result celestial physics requires a complete change. (6) Kepler's replacement of celestial physics. He did not think any more that the apparent (unequal) way of a planet indirectly results from the combination of several equal movements of etherial partial and entire spheres. His planets move their true and real way caused directly by the joint effect of two corporal forces moving the planets both around the sun and to and from it, which latter makes the planet's speed indeed naturally unequal. For this "real way" he coins in late 1604 the specific term "orbita" (the modern "orbit", the German "Bahn". This term then little by little replaced the former non-specific, general description of the apparent or real way (as "via, iter, ambitus, circulus, circuitus" etc.), and Kepler used it increasingly from its introduction (initially frequently joined to a describing definition of this "way") up to the exclusive use in the fifth book of the "Epitome", after this "orbita" had changed its shape from a perfect eccentric circle to an oval and finally an elliptic form. This way Kepler marks the paradigm change of astronomy caused by himself also terminologically.

First results from CSSWE CubeSat: Characteristics of relativistic electrons in the near-Earth environment during the October 2012 magnetic storms

NASA Astrophysics Data System (ADS)

Li, X.; Schiller, Q.; Blum, L.; Califf, S.; Zhao, H.; Tu, W.; Turner, D. L.; Gerhardt, D.; Palo, S.; Kanekal, S.; Baker, D. N.; Fennell, J.; Blake, J. B.; Looper, M.; Reeves, G. D.; Spence, H.

2013-10-01

from the Relativistic Electron and Proton Telescope integrated little experiment (REPTile) on board the Colorado Student Space Weather Experiment (CSSWE) CubeSat mission, which was launched into a highly inclined (65°) low Earth orbit, are analyzed along with measurements from the Relativistic Electron and Proton Telescope (REPT) and the Magnetic Electron Ion Spectrometer (MagEIS) instruments aboard the Van Allen Probes, which are in a low inclination (10°) geo-transfer-like orbit. Both REPT and MagEIS measure the full distribution of energetic electrons as they traverse the heart of the outer radiation belt. However, due to the small equatorial loss cone (only a few degrees), it is difficult for REPT and MagEIS to directly determine which electrons will precipitate into the atmosphere, a major radiation belt loss process. REPTile, a miniaturized version of REPT, measures the fraction of the total electron population that has small enough equatorial pitch angles to reach the altitude of CSSWE, 480 km × 780 km, thus measuring the precipitating population as well as the trapped and quasi-trapped populations. These newly available measurements provide an unprecedented opportunity to investigate the source, loss, and energization processes that are responsible for the dynamic behavior of outer radiation belt electrons. The focus of this paper will be on the characteristics of relativistic electrons measured by REPTile during the October 2012 storms; also included are long-term measurements from the Solar Anomalous and Magnetospheric Particle Explorer to put this study into context.

Spectroscopic and structural study of novel interaction product of pyrrolidine-2-thione with molecular iodine. Presumable mechanisms of oxidation

NASA Astrophysics Data System (ADS)

Chernov'yants, Margarita S.; Burykin, Igor V.; Starikova, Zoya A.; Tereznikov, Alexander Yu.; Kolesnikova, Tatiana S.

2013-09-01

Synthesis, spectroscopic and structural characterization of novel interaction product of pyrrolidine-2-thione with molecular iodine is reported. The ability of pyrrolidine-2-thione to form the outer-sphere charge-transfer complex C4H7NS·I2 with iodine molecule in dilute chloroform solution has been studied by UV/vis spectroscopy. Oxidative desulfurization promotes ring fusion of two pyrrolidine-2-thione molecules. The product of iodine induced oxidative desulfurization has been studied by X-ray diffraction method. The crystal structure of the reaction product is formed by 5-(2-thioxopyrrolidine-1-yl)-3,4-dihydro-2H-pyrrolium (C8H13N2S+) cations and pentaiodide anions I5-, which are linked by the intermolecular I⋯Hsbnd C and I⋯C close contacts. The angular pentaiodide anions can be considered as structures formed by coordination of two iodine molecules to the iodide ion (type 1) or by the coordination of iodine molecule to the triiodide ion (type 2).

Electron dynamics in high energy density plasma bunch generation driven by intense picosecond laser pulse

NASA Astrophysics Data System (ADS)

Li, M.; Yuan, T.; Xu, Y. X.; Luo, S. N.

2018-05-01

When an intense picosecond laser pulse is loaded upon a dense plasma, a high energy density plasma bunch, including electron bunch and ion bunch, can be generated in the target. We simulate this process through one-dimensional particle-in-cell simulation and find that the electron bunch generation is mainly due to a local high energy density electron sphere originated in the plasma skin layer. Once generated the sphere rapidly expands to compress the surrounding electrons and induce high density electron layer, coupled with that, hot electrons are efficiently triggered in the local sphere and traveling in the whole target. Under the compressions of light pressure, forward-running and backward-running hot electrons, a high energy density electron bunch generates. The bunch energy density is as high as TJ/m3 order of magnitude in our conditions, which is significant in laser driven dynamic high pressure generation and may find applications in high energy density physics.

Chemical projectile-target interaction and liquid immiscibility in impact glass from the Wabar craters, Saudi Arabia

NASA Astrophysics Data System (ADS)

Hamann, Christopher; Hecht, Lutz; Ebert, Matthias; Wirth, Richard

2013-11-01

Impact glasses are usually strongly affected by secondary alteration and chemical weathering. Thus, in order to understand relevant formation processes, detailed petrographic studies on unweathered impact glasses are necessary as preserved heterogeneities in quenched impact glasses may serve as a tool to better understand their genesis. Here, we report on petrography and microchemistry of impact glasses from the Wabar impact craters (Saudi Arabia) that, with an age of ∼300 years, are among the youngest terrestrial impact craters. The fact that parts of the IIIAB iron meteorite have survived impact and subsequent weathering is granting Wabar a special role among the presently 184 confirmed terrestrial impact structures. Electron microprobe analysis (EMPA) and transmission electron microscopy (TEM) obtained on the black impact melt/glass variety at Wabar suggest that meteoritic Fe was selectively mixed with high-silica target melt at high temperatures due to selective oxidation, resulting in high Fe/Ni ratios for the black melt (37 on average, individual values range from 13 to 449) and low Fe/Ni ratios for projectile droplets ("FeNi spheres" with a Fe/Ni ratio of 3 on average; Fe/Ni ratio for the meteorite is ∼12). The black melt shows emulsion textures that are the result of silicate liquid immiscibility. Liquid-liquid phase-separation resulted in the formation of a poorly polymerized, ultrabasic melt (Lfe) rich in divalent cations like Fe2+, Ca2+, or Mg2+, that is dispersed in a highly polymerized, high-silica melt (Lsi) matrix. The typical Wabar black melt emulsion displays a spheres-in-a-matrix texture of ∼10-20% Lfe homogeneously dispersed in the form of two sets of spheres and droplets (10-30 nm and 0.1-0.4 μm in diameter) in ∼80-90% Lsi matrix, plus occasionally disseminated FeNi spheres. Around large (>10 μm) FeNi spheres, however, the typical emulsion texture changes to ∼21% Lsi dispersed in ∼79% Lfe. This change of texture is interpreted as evidence for the transfer of meteoritic Fe from the meteoritic FeNi spheres into the target melt due to selective oxidation of Fe over Ni and Co. Variations in the bulk composition of Wabar black melt largely depend on the volume ratios between immiscible ultrabasic Lfe, felsic Lsi, and remains of meteoritic FeNi spheres. Based on natural occurrences of phase-separated glasses (this work and literature) and quenching experiments (literature), there is growing evidence that liquid immiscibility is a major process in the formation of glassy impactites.

From Rising Bubble to RNA/DNA and Bacteria

NASA Astrophysics Data System (ADS)

Marks, Roman; Cieszyńska, Agata; Wereszka, Marzena; Borkowski, Wojciech

2017-04-01

In this study we have focused on the movement of rising bubbles in a salty water body. Experiments reviled that free buoyancy movement of bubbles forces displacement of ions, located on the outer side of the bubble wall curvatures. During the short moment of bubble passage, all ions in the vicinity of rising bubble, are separated into anions that are gathered on the bubble upper half sphere and cations that slip along the bottom concave half-sphere of a bubble and develop a sub-bubble vortex. The principle of ions separation bases on the differences in displacement resistance. In this way, relatively heavier and larger, thus more resistant to displacement anions are gathered on the rising bubble upper half sphere, while smaller and lighter cations are assembled on the bottom half sphere and within the sub-bubble vortex. The acceleration of motion generates antiparallel rotary of bi-ionic domains, what implies that anions rotate in clockwise (CW) and cationic in counter-clockwise (CCW) direction. Then, both rotational systems may undergo splicing and extreme condensing by bi-pirouette narrowing of rotary. It is suggested that such double helix motion of bi-ionic domains creates RNA/DNA molecules. Finally, when the bubble reaches the water surface it burst and the preprocessed RNA/DNA matter is ejected into the droplets. Since that stage, droplet is suspended in positively charged troposphere, thus the cationic domain is located in the droplet center, whilst negative ions are attracted to configure the outer areola. According to above, the present study implies that the rising bubbles in salty waters may incept synergistic processing of matter resulting in its rotational/spherical organization that led to assembly of RNA/DNA molecules and bacteria cells.

Structural and spectroscopic characterizations on the charge-transfer interactions of the second generation poly(propylene amine) dendrimers with iodine and picric acid acceptors

NASA Astrophysics Data System (ADS)

El-Sayed, Mohamed Y.; Refat, Moamen S.

2015-02-01

Herein, this study was focused to get a knowledge about the intermolecular charge transfer complexes between the second generation of poly(propylene amine) dendrimer (PPD2) with picric acid (PA) and iodine (I2) as π and σ-acceptors. The charge-transfer interaction of the PPD2 electron donor and the PA acceptor has been studied in CHCl3. The resulted data refereed to the formation of the new CT-complex with the general formula [(PPD2)(PA)4]. The 1:4 stoichiometry of the reaction was discussed upon the on elemental analysis and photometric titration. On the other hand, the 1:3½ iodine-PPD2 heptaiodide (I7-) charge-transfer complex has been studied spectrophotometrically in chloroform at room temperature with general formula [(PPD2)]+I7-. The electronic absorption bands of 2I2·I3- (I7-) are observed at 358 and 294 nm. Raman laser spectrum of the brown solid heptaiodide complex has two clearly vibration bands at 155 and 110 cm-1 due to symmetric stretching νs(Isbnd I) outer and inner bonds, respectively. The 1H NMR spectra and differential scanning calorimetry (DSC) data of PPD2 charge-transfer complexes were discussed.

Use of high temperature insulation for ceramic matrix composites in gas turbines

DOEpatents

Morrison, Jay Alan; Merrill, Gary Brian; Ludeman, Evan McNeil; Lane, Jay Edgar

2001-01-01

A ceramic composition for insulating components, made of ceramic matrix composites, of gas turbines is provided. The composition comprises a plurality of hollow oxide-based spheres of various dimensions, a phosphate binder, and at least one oxide filler powder, whereby the phosphate binder partially fills gaps between the spheres and the filler powders. The spheres are situated in the phosphate binder and the filler powders such that each sphere is in contact with at least one other sphere and the arrangement of spheres is such that the composition is dimensionally stable and chemically stable at a temperature of approximately 1600.degree. C. A stationary vane of a gas turbine comprising the composition of the present invention bonded to the outer surface of the vane is provided. A combustor comprising the composition bonded to the inner surface of the combustor is provided. A transition duct comprising the insulating coating bonded to the inner surface of the transition is provided. Because of abradable properties of the composition, a gas turbine blade tip seal comprising the composition also is provided. The composition is bonded to the inside surface of a shroud so that a blade tip carves grooves in the composition so as to create a customized seal for the turbine blade tip.

Electron beam selectively seals porous metal filters

NASA Technical Reports Server (NTRS)

Snyder, J. A.; Tulisiak, G.

1968-01-01

Electron beam welding selectively seals the outer surfaces of porous metal filters and impedances used in fluid flow systems. The outer surface can be sealed by melting a thin outer layer of the porous material with an electron beam so that the melted material fills all surface pores.

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

Darmon, Jonathan M.; Kumar, Neeraj; Hulley, Elliott B.

Oxidation of hydrogen (H₂) to protons and electrons for energy production in fuel cells is catalyzed by platinum, but its low abundance and high cost present drawbacks to widespread adoption. Precisely controlled proton delivery and removal is critical in hydrogenase enzymes in nature that catalyze H₂ oxidation using earth-abundant metals (iron and nickel). Here we report a synthetic iron complex, (Cp C5F4N)Fe(P EtN (CH2)3NMe2PEt)(Cl), that serves as a precatalyst for the oxidation of H₂, with turnover frequencies of 290 s⁻¹ in fluorobenzene, under 1 atm of H₂ using 1,4-diazabicyclo[2.2.2]octane (DABCO) as the exogenous base. The cooperative effect of the primary,more » secondary and outer coordination spheres for moving protons in this remarkably fast catalyst emphasizes the key role of pendant amines in mimicking the functionality of the proton pathway in the hydrogenase enzymes.« less

Characterization of the Inner Disk around HD 141569 A from Keck/NIRC2 L-Band Vortex Coronagraphy

NASA Astrophysics Data System (ADS)

Mawet, Dimitri; Choquet, Élodie; Absil, Olivier; Huby, Elsa; Bottom, Michael; Serabyn, Eugene; Femenia, Bruno; Lebreton, Jérémy; Matthews, Keith; Gomez Gonzalez, Carlos A.; Wertz, Olivier; Carlomagno, Brunella; Christiaens, Valentin; Defrère, Denis; Delacroix, Christian; Forsberg, Pontus; Habraken, Serge; Jolivet, Aissa; Karlsson, Mikael; Milli, Julien; Pinte, Christophe; Piron, Pierre; Reggiani, Maddalena; Surdej, Jean; Vargas Catalan, Ernesto

2017-01-01

HD 141569 A is a pre-main sequence B9.5 Ve star surrounded by a prominent and complex circumstellar disk, likely still in a transition stage from protoplanetary to debris disk phase. Here, we present a new image of the third inner disk component of HD 141569 A made in the L‧ band (3.8 μm) during the commissioning of the vector vortex coronagraph that has recently been installed in the near-infrared imager and spectrograph NIRC2 behind the W.M. Keck Observatory Keck II adaptive optics system. We used reference point-spread function subtraction, which reveals the innermost disk component from the inner working distance of ≃23 au and up to ≃70 au. The spatial scale of our detection roughly corresponds to the optical and near-infrared scattered light, thermal Q, N, and 8.6 μm PAH emission reported earlier. We also see an outward progression in dust location from the L‧ band to the H band (Very Large Telescope/SPHERE image) to the visible (Hubble Space Telescope (HST)/STIS image), which is likely indicative of dust blowout. The warm disk component is nested deep inside the two outer belts imaged by HST-NICMOS in 1999 (at 406 and 245 au, respectively). We fit our new L‧-band image and spectral energy distribution of HD 141569 A with the radiative transfer code MCFOST. Our best-fit models favor pure olivine grains and are consistent with the composition of the outer belts. While our image shows a putative very faint point-like clump or source embedded in the inner disk, we did not detect any true companion within the gap between the inner disk and the first outer ring, at a sensitivity of a few Jupiter masses.

Rational engineering of Geobacter sulfurreducens electron transfer components: A foundation for building improved Geobacter-based bioelectrochemical technologies

DOE PAGES

Dantas, Joana M.; Morgado, Leonor; Aklujkar, Muktak; ...

2015-07-30

Multiheme cytochromes have been implicated in Geobacter sulfurreducens extracellular electron transfer (EET). These proteins are potential targets to improve EET and enhance bioremediation and electrical current production by G. sulfurreducens. However, the functional characterization of multiheme cytochromes is particularly complex due to the co-existence of several microstates in solution, connecting the fully reduced and fully oxidized states. Throughout the last decade, new strategies have been developed to characterize multiheme redox proteins functionally and structurally. These strategies were used to reveal the functional mechanism of G. sulfurreducens multiheme cytochromes and also to identify key residues in these proteins for EET. Inmore » previous studies, we set the foundations for enhancement of the EET abilities of G. sulfurreducens by characterizing a family of five triheme cytochromes (PpcA-E). These periplasmic cytochromes are implicated in electron transfer between the oxidative reactions of metabolism in the cytoplasm and the reduction of extracellular terminal electron acceptors at the cell's outer surface. The results obtained suggested that PpcA can couple e -/H + transfer, a property that might contribute to the proton electrochemical gradient across the cytoplasmic membrane for metabolic energy production. The structural and functional properties of PpcA were characterized in detail and used for rational design of a family of 23 single site PpcA mutants. In this review, we summarize the functional characterization of the native and mutant proteins. Mutants that retain the mechanistic features of PpcA and adopt preferential e -/H + transfer pathways at lower reduction potential values compared to the wild-type protein were selected for in vivo studies as the best candidates to increase the electron transfer rate of G. sulfurreducens. For the first time G. sulfurreducens strains have been manipulated by the introduction of mutant forms of essential proteins with the aim to develop and improve bioelectrochemical technologies.« less

Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Juan; Lin, Dong-Yang; Yan, Xiao-Hui; Wang, Xiao-Xiang

2011-12-01

A homogeneous amorphous calcium phosphate (ACP) coating containing magnesium was achieved on titanium substrates by electrochemical deposition (ECD). Its amorphous structure is confirmed by transmission electron microscope (TEM) together with grazing reflection absorption infrared spectroscopy (IR) spectrometer. In the images of high-resolution transmission electron microscope (HRTEM), the ACP spheres are assembled by nano-particles with the diameter of 5-10 nm. In the alkaline environment, nucleation of hydroxyapatite (HAP) occurs on the surfaces of ACP spheres. By consuming the Ca and PO 4 ions inside the ACP spheres, the HAP nuclei grow outward. Confirmed by TEM, the ACP spheres converse to hollow HAP spheres composed of HAP nano-needles. The coating is finally constructed by the HAP nano-needles, which are themselves aggregated by numerous nano-particles.

The Role of Shewanella oneidensis MR-1 Outer Surface Structures in Extracellular Electron Transfer

DTIC Science & Technology

2010-01-01

Supernatants from the wells of the air-exposed VBSA that had been in operation for 220 h were harvested and planktonic cells were removed via...prepilins. In some bacteria, such as Pseudomonas aerugino- sa and Vibrio cholerae, PilD plays a dual role and processes type IVand T2SS prepilins [38 – 41... harvested from the VBSA at the times indicated by arrows in Fig. 4 (100 h data not shown). Fig. 6. Presence of riboflavin in cell-free supernatants

SPHERES-RINGS Time Lapse

NASA Image and Video Library

2014-07-10

ISS040-E-059344 (10 July 2014) --- In the International Space Station’s Kibo laboratory, NASA astronaut Reid Wiseman (left) and European Space Agency astronaut Alexander Gerst, both Expedition 40 flight engineers, conduct a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

SPHERES-RINGS Time Lapse

NASA Image and Video Library

2014-07-10

ISS040-E-059467 (10 July 2014) --- In the International Space Station's Kibo laboratory, European Space Agency astronaut Alexander Gerst and NASA astronaut Reid Wiseman (mostly obscured), both Expedition 40 flight engineers, conduct a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

SPHERES-RINGS Time Lapse

NASA Image and Video Library

2014-07-10

ISS040-E-059478 (10 July 2014) --- In the International Space Station's Kibo laboratory, European Space Agency astronaut Alexander Gerst (left) and NASA astronaut Reid Wiseman, both Expedition 40 flight engineers, conduct a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites is ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS. SPHERES-RINGS seeks to demonstrate wireless power transfer between satellites at a distance for enhanced operations.

Laminar free convection from a sphere with blowing and suction

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

Huang, Mingjer; Chen, Gahokuang

1987-05-01

The effect of mass transfer on free convection from a vertical plate has been studied by Eichhorn (1960), Sparrow and Cess (1961), Merkin (1972), and Parikh (1974). Recently, Merkin (1975) gave an asymptotic series solution for two-dimensional bodies. Minkowycz and Sparrow (1979) studied a vertical cylinder in a natural convective flow. According to their conclusions, the heat transfer rate increases with suction and decreases with blowing. The present note is concerned with the study of the influence of Prandtl number and surface mass transfer on a steady, laminar, free convective flow over a sphere with nonuniform surface temperature or heatmore » flux.« less

Optical properties and electronic energy relaxation of metallic Au144(SR)60 nanoclusters.

PubMed

Yi, Chongyue; Tofanelli, Marcus A; Ackerson, Christopher J; Knappenberger, Kenneth L

2013-12-04

Electronic energy relaxation of Au144(SR)60(q) ligand-protected nanoclusters, where SR = SC6H13 and q = -1, 0, +1, and +2, was examined using femtosecond time-resolved transient absorption spectroscopy. The observed differential transient spectra contained three distinct components: (1) transient bleaches at 525 and 600 nm, (2) broad visible excited-state absorption (ESA), and (3) stimulated emission (SE) at 670 nm. The bleach recovery kinetics depended upon the excitation pulse energy and were thus attributed to electron-phonon coupling typical of metallic nanostructures. The prominent bleach at 525 nm was assigned to a core-localized plasmon resonance (CLPR). ESA decay kinetics were oxidation-state dependent and could be described using a metal-sphere charging model. The dynamics, emission energy, and intensity of the SE peak exhibited dielectric-dependent responses indicative of Superatom charge transfer states. On the basis of these data, the Au144(SR)60 system is the smallest-known nanocluster to exhibit quantifiable electron dynamics and optical properties characteristic of metals.

Investigation into aerodynamic and heat transfer of annular channel with inner and outer surface of the shape truncated cone and swirling fluid flow

NASA Astrophysics Data System (ADS)

Leukhin, Yu L.; Pankratov, E. V.; Karpov, S. V.

2017-11-01

We have carried out Investigation into aerodynamic and convective heat transfer of the annular channel. Inner or outer surface of annular channel has shape of blunt-nosed cone tapering to outlet end. Truncated cone connects to a cyclone swirling flow generator. Asymmetric and unsteady flow from the swirling generator in the shape of periodic process gives rise to the formation of secondary flows of the type Taylor-Görtler vortices. These vortices occupy the whole space of the annular channel, with the axes, which coincide with the motion direction of the major stream. Contraction of cross-sectional area of channel (in both cases 52%) causes a marked increase in total velocity of flow, primarily due to its axial component and promotes a more intensive vortex generation. Vortex structures have a significant influence on both average heat transfer and surface distribution. At cross-sections of the annular channel we observe similarity of curves describing distribution of total velocity about wall and heat flux density on the surface. The coordinates of maximum and minimum values of velocity and heat flux coincide. At the average cross-section channel of maximum value of heat transfer is greater than minimum of about by a factor of 2.7 times for outer heat transfer surface and about by a factor of 1.7 times for inner heat transfer surface. Taper channel has a much higher influence on heat transfer of the inner surface than the outer surface and manifests itself at lower values of dimensionless axial coordinate. For the investigated taper cone geometry of the annular channel the heat transfer coefficient of inner surface increases at the outlet section and exceeds value in comparison with straight-line section by 91 … 98%. Heat transfer of the outer cylinder in the same section increases only by 5 … 11%. The increase in average heat transfer over the surfaces is 36% and 4% respectively.

Investigating inner-sphere reorganization via secondary kinetic isotope effects in the C-H cleavage reaction catalyzed by soybean lipoxygenase: tunneling in the substrate backbone as well as the transferred hydrogen.

PubMed

Meyer, Matthew P; Klinman, Judith P

2011-01-26

This work describes the application of NMR to the measurement of secondary deuterium (2° (2)H) and carbon-13 ((13)C) kinetic isotope effects (KIEs) at positions 9-13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using LA labeled with either protium (11,11-h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° (2)H and (13)C KIEs on k(cat)/K(m) directly for 11,11-d2-LA, whereas the values for the 2° (2)H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° (2)H and (13)C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of nonclassical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 1981, 85, 3763] to model the inner-sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° (2)H KIEs.

An ultrasensitive hollow-silica-based biosensor for pathogenic Escherichia coli DNA detection.

PubMed

Ariffin, Eda Yuhana; Lee, Yook Heng; Futra, Dedi; Tan, Ling Ling; Karim, Nurul Huda Abd; Ibrahim, Nik Nuraznida Nik; Ahmad, Asmat

2018-03-01

A novel electrochemical DNA biosensor for ultrasensitive and selective quantitation of Escherichia coli DNA based on aminated hollow silica spheres (HSiSs) has been successfully developed. The HSiSs were synthesized with facile sonication and heating techniques. The HSiSs have an inner and an outer surface for DNA immobilization sites after they have been functionalized with 3-aminopropyltriethoxysilane. From field emission scanning electron microscopy images, the presence of pores was confirmed in the functionalized HSiSs. Furthermore, Brunauer-Emmett-Teller (BET) analysis indicated that the HSiSs have four times more surface area than silica spheres that have no pores. These aminated HSiSs were deposited onto a screen-printed carbon paste electrode containing a layer of gold nanoparticles (AuNPs) to form a AuNP/HSiS hybrid sensor membrane matrix. Aminated DNA probes were grafted onto the AuNP/HSiS-modified screen-printed electrode via imine covalent bonds with use of glutaraldehyde cross-linker. The DNA hybridization reaction was studied by differential pulse voltammetry using an anthraquinone redox intercalator as the electroactive DNA hybridization label. The DNA biosensor demonstrated a linear response over a wide target sequence concentration range of 1.0×10 -12 -1.0×10 -2 μM, with a low detection limit of 8.17×10 -14 μM (R 2 = 0.99). The improved performance of the DNA biosensor appeared to be due to the hollow structure and rough surface morphology of the hollow silica particles, which greatly increased the total binding surface area for high DNA loading capacity. The HSiSs also facilitated molecule diffusion through the silica hollow structure, and substantially improved the overall DNA hybridization assay. Graphical abstract Step-by-step DNA biosensor fabrication based on aminated hollow silica spheres.

Axial interactions in the mixed-valent CuA active site and role of the axial methionine in electron transfer

PubMed Central

Tsai, Ming-Li; Hadt, Ryan G.; Marshall, Nicholas M.; Wilson, Tiffany D.; Lu, Yi; Solomon, Edward I.

2013-01-01

Within Cu-containing electron transfer active sites, the role of the axial ligand in type 1 sites is well defined, yet its role in the binuclear mixed-valent CuA sites is less clear. Recently, the mutation of the axial Met to Leu in a CuA site engineered into azurin (CuA Az) was found to have a limited effect on E0 relative to this mutation in blue copper (BC). Detailed low-temperature absorption and magnetic circular dichroism, resonance Raman, and electron paramagnetic resonance studies on CuA Az (WT) and its M123X (X = Q, L, H) axial ligand variants indicated stronger axial ligation in M123L/H. Spectroscopically validated density functional theory calculations show that the smaller ΔE0 is attributed to H2O coordination to the Cu center in the M123L mutant in CuA but not in the equivalent BC variant. The comparable stabilization energy of the oxidized over the reduced state in CuA and BC (CuA ∼ 180 mV; BC ∼ 250 mV) indicates that the S(Met) influences E0 similarly in both. Electron delocalization over two Cu centers in CuA was found to minimize the Jahn–Teller distortion induced by the axial Met ligand and lower the inner-sphere reorganization energy. The Cu–S(Met) bond in oxidized CuA is weak (5.2 kcal/mol) but energetically similar to that of BC, which demonstrates that the protein matrix also serves an entatic role in keeping the Met bound to the active site to tune down E0 while maintaining a low reorganization energy required for rapid electron transfer under physiological conditions. PMID:23964128

Formation of aggregated nanoparticle spheres through femtosecond laser surface processing

NASA Astrophysics Data System (ADS)

Tsubaki, Alfred T.; Koten, Mark A.; Lucis, Michael J.; Zuhlke, Craig; Ianno, Natale; Shield, Jeffrey E.; Alexander, Dennis R.

2017-10-01

A detailed structural and chemical analysis of a class of self-organized surface structures, termed aggregated nanoparticle spheres (AN-spheres), created using femtosecond laser surface processing (FLSP) on silicon, silicon carbide, and aluminum is reported in this paper. AN-spheres are spherical microstructures that are 20-100 μm in diameter and are composed entirely of nanoparticles produced during femtosecond laser ablation of material. AN-spheres have an onion-like layered morphology resulting from the build-up of nanoparticle layers over multiple passes of the laser beam. The material properties and chemical composition of the AN-spheres are presented in this paper based on scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX) analysis. There is a distinct difference in the density of nanoparticles between concentric rings of the onion-like morphology of the AN-sphere. Layers of high-density form when the laser sinters nanoparticles together and low-density layers form when nanoparticles redeposit while the laser ablates areas surrounding the AN-sphere. The dynamic nature of femtosecond laser ablation creates a variety of nanoparticles that make-up the AN-spheres including Si/C core-shell, nanoparticles that directly fragmented from the base material, nanoparticles with carbon shells that retarded oxidation, and amorphous, fully oxidized nanoparticles.

iss050e038054

NASA Image and Video Library

2017-02-03

iss050e038054 (02/03/2017) --- NASA astronaut Shane Kimbrough is seen executing the SPHERES-HALO experiment aboard the International Space Station. The investigation uses two small, self-contained satellites (SPHERES) fitted with donut-like rings to test wireless power transfer and formation flight using electromagnetic fields.

iss050e038043

NASA Image and Video Library

2017-02-03

iss050e038043 (02/03/2017) --- NASA astronaut Shane Kimbrough is seen executing the SPHERES-HALO experiment aboard the International Space Station. The investigation uses two small, self-contained satellites (SPHERES) fitted with donut-like rings to test wireless power transfer and formation flight using electromagnetic fields.

Nuclear spin relaxation in ligands outside of the first coordination sphere in a gadolinium (III) complex: Effects of intermolecular forces

NASA Astrophysics Data System (ADS)

Kruk, Danuta; Kowalewski, Jozef

2002-07-01

This article describes paramagnetic relaxation enhancement (PRE) in systems with high electron spin, S, where there is molecular interaction between a paramagnetic ion and a ligand outside of the first coordination sphere. The new feature of our treatment is an improved handling of the electron-spin relaxation, making use of the Redfield theory. Following a common approach, a well-defined second coordination sphere is assumed, and the PRE contribution from these more distant and shorter-lived ligands is treated in a way similar to that used for the first coordination sphere. This model is called "ordered second sphere," OSS. In addition, we develop here a formalism similar to that of Hwang and Freed [J. Chem. Phys. 63, 4017 (1975)], but accounting for the electron-spin relaxation effects. We denote this formalism "diffuse second sphere," DSS. The description of the dynamics of the intermolecular dipole-dipole interaction is based on the Smoluchowski equation, with a potential of mean force related to the radial distribution function. We have used a finite-difference method to calculate numerically a correlation function for translational motion, taking into account the intermolecular forces leading to an arbitrary radial distribution of the ligand protons. The OSS and DSS models, including the Redfield description of the electron-spin relaxation, were used to interpret the PRE in an aqueous solution of a slowly rotating gadolinium (III) complex (S=7/2) bound to a protein.

Method for Detecting Perlite Compaction in Large Cryogenic Tanks

NASA Technical Reports Server (NTRS)

Youngquist, Robert

2010-01-01

Perlite is the most typical insulating powder used to separate the inner and outer shells of cryogenic tanks. The inner tank holds the low-temperature commodity, while the outer shell is exposed to the ambient temperature. Perlite minimizes radiative energy transfer between the two tanks. Being a powder, perlite will settle over time, leading to the danger of transferring any loads from the inner shell to the outer shell. This can cause deformation of the outer shell, leading to damaged internal fittings. The method proposed is to place strain or displacement sensors on several locations of the outer shell. Loads induced on the shell by the expanding inner shell and perlite would be monitored, providing an indication of the location and degree of compaction.

The Proof of the ``Vortex Theory of Matter''

NASA Astrophysics Data System (ADS)

Moon, Russell

2009-11-01

According to the Vortex Theory, protons and electrons are three-dimensional holes connected by fourth-dimensional vortices. It was further theorized that when photons are absorbed then readmitted by atoms, the photon is absorbed into the proton, moves through the fourth-dimensional vortex, then reemerges back into three-dimensional space through the electron. To prove this hypothesis, an experiment was conducted using a hollow aluminum sphere containing a powerful permanent magnet suspended directly above a zinc plate. Ultraviolet light was then shined upon the zinc. The zinc emits electrons via the photoelectric effect that are attracted to the surface of the aluminum sphere. The sphere was removed from above the zinc plate and repositioned above a sensitive infrared digital camera in another room. The ball and camera were placed within a darkened box inside a Faraday cage. Light was shined upon the zinc plate and the picture taken by the camera was observed. When the light was turned on above the zinc plate in one room, the camera recorded increased light coming from the surface of the sphere within the other room; when the light was turned off, the intensity of the infrared light coming from the surface of the sphere was suddenly diminished. Five other tests were then performed to eliminate other possible explanations such as quantum-entangled electrons.

The Proof of the ``Vortex Theory of Matter''

NASA Astrophysics Data System (ADS)

Gridnev, Konstantin; Moon, Russell; Vasiliev, Victor

2009-11-01

According to the Vortex Theory, protons and electrons are three-dimensional holes connected by fourth-dimensional vortices. It was further theorized that when photons are absorbed then readmitted by atoms, the photon is absorbed into the proton, moves through the fourth-dimensional vortex, then reemerges back into three-dimensional space through the electron^2. To prove this hypothesis, an experiment was conducted using a hollow aluminum sphere containing a powerful permanent magnet suspended directly above a zinc plate. Ultraviolet light was then shined upon the zinc. The zinc emits electrons via the photoelectric effect that are attracted to the surface of the aluminum sphere. The sphere was removed from above the zinc plate and repositioned above a sensitive infrared digital camera in another room. The ball and camera were placed within a darkened box inside a Faraday cage. Light was shined upon the zinc plate and the picture taken by the camera was observed. When the light was turned on above the zinc plate in one room, the camera recorded increased light coming from the surface of the sphere within the other room; when the light was turned off, the intensity of the infrared light coming from the surface of the sphere was suddenly diminished. Five other tests were then performed to eliminate other possible explanations such as quantum-entangled electrons.

The Proof of the ``Vortex Theory of Matter''

NASA Astrophysics Data System (ADS)

Gridnev, Konstantin; Moon, Russell; Vasiliev, Victor

2009-10-01

According to the Vortex Theory, protons and electrons are three-dimensional holes connected by fourth-dimensional vortices. It was further theorized that when photons are absorbed then readmitted by atoms, the photon is absorbed into the proton, moves through the fourth-dimensional vortex, then reemerges back into three-dimensional space through the electron^2. To prove this hypothesis, an experiment was conducted using a hollow aluminum sphere containing a powerful permanent magnet suspended directly above a zinc plate. Ultraviolet light was then shined upon the zinc. The zinc emits electrons via the photoelectric effect that are attracted to the surface of the aluminum sphere. The sphere was removed from above the zinc plate and repositioned above a sensitive infrared digital camera in another room. The ball and camera were placed within a darkened box inside a Faraday cage. Light was shined upon the zinc plate and the picture taken by the camera was observed. When the light was turned on above the zinc plate in one room, the camera recorded increased light coming from the surface of the sphere within the other room; when the light was turned off, the intensity of the infrared light coming from the surface of the sphere was suddenly diminished. Five other tests were then performed to eliminate other possible explanations such as quantum-entangled electrons.

The Proof of the ``Vortex Theory of Matter''

NASA Astrophysics Data System (ADS)

Moon, Russell; Gridnev, Konstantin; Vasiliev, Victor

2010-02-01

According to the Vortex Theory, protons and electrons are three-dimensional holes connected by fourth-dimensional vortices. It was further theorized that when photons are absorbed then readmitted by atoms, the photon is absorbed into the proton, moves through the fourth-dimensional vortex, then reemerges back into three-dimensional space through the electron. To prove this hypothesis, an experiment was conducted using a hollow aluminum sphere containing a powerful permanent magnet suspended directly above a zinc plate. Ultraviolet light was then shined upon the zinc. The zinc emits electrons via the photoelectric effect that are attracted to the surface of the aluminum sphere. The sphere was removed from above the zinc plate and repositioned above a sensitive infrared digital camera in another room. The ball and camera were placed within a darkened box inside a Faraday cage. Light was shined upon the zinc plate and the picture taken by the camera was observed. When the light was turned on above the zinc plate in one room, the camera recorded increased light coming from the surface of the sphere within the other room; when the light was turned off, the intensity of the infrared light coming from the surface of the sphere was suddenly diminished. Five other tests were then performed to eliminate other possible explanations such as quantum-entangled electrons. )

Probing the dependence of electron transfer on size and coverage in carbon nanotube-quantum dot heterostructures

DOE PAGES

Wang, Lei; Wong, Stanislaus S.; Han, Jinkyu; ...

2015-11-16

As a model system for understanding charge transfer in novel architectural designs for solar cells, double-walled carbon nanotube (DWNT)–CdSe quantum dot (QD) (QDs with average diameters of 2.3, 3.0, and 4.1 nm) heterostructures have been fabricated. The individual nanoscale building blocks were successfully attached and combined using a hole-trapping thiol linker molecule, i.e., 4-mercaptophenol (MTH), through a facile, noncovalent π–π stacking attachment strategy. Transmission electron microscopy confirmed the attachment of QDs onto the external surfaces of the DWNTs. We herein demonstrate a meaningful and unique combination of near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopies bolstered by complementary electricalmore » transport measurements in order to elucidate the synergistic interactions between CdSe QDs and DWNTs, which are facilitated by the bridging MTH molecules that can scavenge photoinduced holes and potentially mediate electron redistribution between the conduction bands in CdSe QDs and the C 2p-derived states of the DWNTs. Specifically, we correlated evidence of charge transfer as manifested by (i) changes in the NEXAFS intensities of π* resonance in the C K-edge and Cd M3-edge spectra, (ii) a perceptible outer tube G-band downshift in frequency in Raman spectra, as well as (iii) alterations in the threshold characteristics present in transport data as a function of CdSe QD deposition onto the DWNT surface. Furthermore, the separate effects of (i) varying QD sizes and (ii) QD coverage densities on the electron transfer were independently studied.« less

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

PubMed Central

Bai, Da-Chang; Yu, Fei-Le; Wang, Wan-Ying; Chen, Di; Li, Hao; Liu, Qing-Rong; Ding, Chang-Hua; Chen, Bo; Hou, Xue-Long

2016-01-01

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of β-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism—nucleophilic attack of enolate oxygen on Palladium followed by C–C bond-forming [3,3']-reductive elimination. PMID:27283477

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

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

Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a ( syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanisticmore » studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

DOE PAGES

Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying; ...

2016-06-10

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a ( syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanisticmore » studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

Flavin redox bifurcation as a mechanism for controlling the direction of electron flow during extracellular electron transfer.

PubMed

Okamoto, Akihiro; Hashimoto, Kazuhito; Nealson, Kenneth H

2014-10-06

The iron-reducing bacterium Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). While the mechanism for electron export from the OM c-Cyts to an anode is well understood, how the redox centers in OM c-Cyts take electrons from a cathode has not been elucidated at the molecular level. Electrochemical analysis of live cells during switching from anodic to cathodic conditions showed that altering the direction of electron flow does not require gene expression or protein synthesis, but simply redox potential shift about 300 mV for a flavin cofactor interacting with the OM c-Cyts. That is, the redox bifurcation of the riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell-electrode interface to drive bacterial metabolism as either anode or cathode catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidovanadium(IV/V) complexes as new redox mediators in dye-sensitized solar cells: a combined experimental and theoretical study.

PubMed

Apostolopoulou, Andigoni; Vlasiou, Manolis; Tziouris, Petros A; Tsiafoulis, Constantinos; Tsipis, Athanassios C; Rehder, Dieter; Kabanos, Themistoklis A; Keramidas, Anastasios D; Stathatos, Elias

2015-04-20

Corrosiveness is one of the main drawbacks of using the iodide/triiodide redox couple in dye-sensitized solar cells (DSSCs). Alternative redox couples including transition metal complexes have been investigated where surprisingly high efficiencies for the conversion of solar to electrical energy have been achieved. In this paper, we examined the development of a DSSC using an electrolyte based on square pyramidal oxidovanadium(IV/V) complexes. The oxidovanadium(IV) complex (Ph4P)2[V(IV)O(hybeb)] was combined with its oxidized analogue (Ph4P)[V(V)O(hybeb)] {where hybeb(4-) is the tetradentate diamidodiphenolate ligand [1-(2-hydroxybenzamido)-2-(2-pyridinecarboxamido)benzenato}and applied as a redox couple in the electrolyte of DSSCs. The complexes exhibit large electron exchange and transfer rates, which are evident from electron paramagnetic resonance spectroscopy and electrochemistry, rendering the oxidovanadium(IV/V) compounds suitable for redox mediators in DSSCs. The very large self-exchange rate constant offered an insight into the mechanism of the exchange reaction most likely mediated through an outer-sphere exchange mechanism. The [V(IV)O(hybeb)](2-)/[V(V)O(hybeb)](-) redox potential and the energy of highest occupied molecular orbital (HOMO) of the sensitizing dye N719 and the HOMO of [V(IV)O(hybeb)](2-) were calculated by means of density functional theory electronic structure calculation methods. The complexes were applied as a new redox mediator in DSSCs, while the cell performance was studied in terms of the concentration of the reduced and oxidized form of the complexes. These studies were performed with the commercial Ru-based sensitizer N719 absorbed on a TiO2 semiconducting film in the DSSC. Maximum energy conversion efficiencies of 2% at simulated solar light (AM 1.5; 1000 W m(-2)) with an open circuit voltage of 660 mV, a short-circuit current of 5.2 mA cm(-2), and a fill factor of 0.58 were recorded without the presence of any additives in the electrolyte.

Finite-Element Analysis of Current-Induced Thermal Stress in a Conducting Sphere

NASA Astrophysics Data System (ADS)

Liu, Ming; Yang, Fuqian

2012-02-01

Understanding the electrothermal-mechanical behavior of electronic interconnects is of practical importance in improving the structural reliability of electronic devices. In this work, we use the finite-element method to analyze the Joule-heating-induced thermomechanical deformation of a metallic sphere that is sandwiched between two rigid plates. The deformation behavior of the sphere is elastic-perfectly plastic with Young's modulus and yield stress decreasing with temperature. The mechanical stresses created by Joule heating are found to depend on the thermal and mechanical contact conditions between the sphere and the plates. The temperature rise in the sphere for the diathermal condition between the sphere and the plates deviates from the square relation between Joule heat and electric current, due to the temperature dependence of the electrothermal properties of the material. For large electric currents, the simulations reveal the decrease of von Mises stress near the contact interfaces, which suggests that current-induced structural damage will likely occur near the contact interfaces.

Novel one-step route for synthesizing CdS/polystyrene nanocomposite hollow spheres.

PubMed

Wu, Dazhen; Ge, Xuewu; Zhang, Zhicheng; Wang, Mozhen; Zhang, Songlin

2004-06-22

CdS/polystyrene nanocomposite hollow spheres with diameters between 240 and 500 nm were synthesized under ambient conditions by a novel microemulsion method in which the polymerization of styrene and the formation of CdS nanoparticles were initiated by gamma-irradiation. The product was characterized by transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA), which show the walls of the hollow spheres are porous and composed of polystyrene containing homogeneously dispersed CdS nanoparticles. The quantum-confined effect of the CdS/polystyrene nanocomposite hollow spheres is confirmed by the ultraviolet-visible (UV-vis) and photoluminescent (PL) spectra. We propose that the walls of these nanocomposite hollow spheres originate from the simultaneous synthesis of polystyrene and CdS nanoparticles at the interface of microemulsion droplets. This novel method is expected to produce various inorganic/polymer nanocomposite hollow spheres with potential applications in the fields of materials science and biotechnology.

Heat transfer enhancement at increasing water concentration in alcohol in the process of non-stationary film boiling

NASA Astrophysics Data System (ADS)

Kanin, P. K.; Ryazantsev, V. A.; Lexin, M. A.; Zabirov, A. R.; Yagov, V. V.

2018-03-01

New experimental data on heat transfer in pool film boiling of subcooled ethanol-water mixtures at spherical surfaces are considered. The water solutions with ethanol mass fraction from 10 to 91% and temperature of liquid 50°C were examined. All the experiments were conducted under atmospheric pressure, using the stainless steel sphere of 39 mm in diameter as a cooled body. The sphere was heated up to 450-750°C, depending on ethanol concentration, and immersed into the experimental vessel with subcooled mixture. As it is expected, boiling heat transfer intensifies with ethanol concentration decrease, and duration of cooling decreases. It means that stable film boiling duration decreases, and earlier transition to intensive heat transfer regime occurs.

Experimentation on recurrent sphere collision with Audacity

NASA Astrophysics Data System (ADS)

Muradoglu, Murat; Ng, Enoch Ming Wei; Ng, Tuck Wah

2014-11-01

Under the theme of collisions that occur repeatedly, we conducted easy and inexpensive experiments of rebounding spheres and Newton’s cradle with two spheres to determine the coefficients of restitution using the sound record feature in modern laptops and a free and open source software called Audacity. In the rebounding sphere experiment, the coefficients of restitution of the golf and ping pong balls used were found to be 0.727 ± 0.025 and 0.816 ± 0.041 respectively. With the Netwon’s cradle experiment, the coefficient of restitution of two steel sphere balls was found to be 0.987 ± 0.003. The contrasts in the results obtained from both experiments permit the operational principles of a pendulum to be emphasized, and engagements to be made to consider the transfer of kinetic energy in the form of vibrational energy of the bodies’ constituents. Using a one-dimensional two-mass model with spring and damper linkages to account for harmonic motions that occur during impact, we found it possible to perform a simple analysis to account for this, and how it can be linked to high energy transfer modes such as the phenomenon of resonance and impedance matching.

Classical plasma dynamics of Mie-oscillations in atomic clusters

NASA Astrophysics Data System (ADS)

Kull, H.-J.; El-Khawaldeh, A.

2018-04-01

Mie plasmons are of basic importance for the absorption of laser light by atomic clusters. In this work we first review the classical Rayleigh-theory of a dielectric sphere in an external electric field and Thomson’s plum-pudding model applied to atomic clusters. Both approaches allow for elementary discussions of Mie oscillations, however, they also indicate deficiencies in describing the damping mechanisms by electrons crossing the cluster surface. Nonlinear oscillator models have been widely studied to gain an understanding of damping and absorption by outer ionization of the cluster. In the present work, we attempt to address the issue of plasmon relaxation in atomic clusters in more detail based on classical particle simulations. In particular, we wish to study the role of thermal motion on plasmon relaxation, thereby extending nonlinear models of collective single-electron motion. Our simulations are particularly adopted to the regime of classical kinetics in weakly coupled plasmas and to cluster sizes extending the Debye-screening length. It will be illustrated how surface scattering leads to the relaxation of Mie oscillations in the presence of thermal motion and of electron spill-out at the cluster surface. This work is intended to give, from a classical perspective, further insight into recent work on plasmon relaxation in quantum plasmas [1].

Toward understanding as photosynthetic biosignatures: light harvesting and energy transfer calculation

NASA Astrophysics Data System (ADS)

Komatsu, Y.; Umemura, M.; Shoji, M.; Shiraishi, K.; Kayanuma, M.; Yabana, K.

2014-03-01

Among several proposed biosignatures, red edge is a direct evidence of photosynthetic life if it is detected (Kiang et al 2007). Red edge is a sharp change in reflectance spectra of vegetation in NIR region (about 700-750 nm). The sign of red edge is observed by Earthshine or remote sensing (Wolstencroft & Raven 2002, Woolf et al 2002). But, why around 700-750 nm? The photosynthetic organisms on Earth have evolved to optimize the sunlight condition. However, if we consider about photosynthetic organism on extrasolar planets, they should have developed to utilize the spectra of its principal star. Thus, it is not strange even if it shows different vegetation spectra. In this study, we focused on the light absorption mechanism of photosynthetic organisms on Earth and investigated the fundamental properties of the light harvesting mechanisms, which is the first stage for the light absorption. Light harvesting complexes contain photosynthetic pigments like chlorophylls. Effective light absorption and the energy transfer are accomplished by the electronic excitations of collective photosynthetic pigments. In order to investigate this mechanism, we constructed an energy transfer model by using a dipole-dipole approximation for the interactions between electronic excitations. Transition moments and transition energies of each pigment are calculated at the time-dependent density functional theory (TDDFT) level (Marques & Gross 2004). Quantum dynamics simulation for the excitation energy transfer was calculated by the Liouvelle's equation. We adopted the model to purple bacteria, which has been studied experimentally and known to absorb lower energy. It is meaningful to focus on the mechanism of this bacteria, since in the future mission, M planets will become a important target. We calculated the oscillator strengths in one light harvesting complex and confirmed the validity by comparing to the experimental data. This complex is made of an inner and an outer ring. The energy transfer from the outer to the inner ring can be reproduced. To deal with a realistic system, we calculated at a macro structural model. The energy transfer between light harvesting complexes is accomplished rapidly via inner rings. By exchange the original pigment to a pigment absorb lower energy, faster energy transfer occurs and the density was trapped in pigment having lower energy. We will compare the result of purple bacteria, which is considered to show longer red edge, cyanobacteria and plants.

Synthetic vaccines.

PubMed

Lerner, R A

1983-02-01

Synthetic vaccines are designed with the help of computer-graphics programs. These displays generated by Arthur J. Olson of the Research Institute of Scripps Clinic show a method whereby parts of a viral protein that are on the surface of a virus, and therefore accessible to antibodies, can be identified. The backbone of the surface domain of the protein on the outer shell of the tomato bushy-stunt virus is displayed (1) on the basis of coordinates determined by Stephen C. Harrison of Harvard University and his colleagues. A single peptide of the protein is picked out in yellow, with the side chains of its component amino acids indicated in atomic detail (2). The peptide is enlarged and a sphere representing a water molecule is displayed (3). The sphere is rolled around the peptide to generate a map of the surface accessible to water (4); it does so, following an algorithm developed by Michael L. Connolly, by placing a dot at each point of its closest contact with the peptide, taking account of the sphere's own van der Waals radius (zone of influence, in effect) and that of each atom of the peptide and the rest of the protein. A similar-dot-surface map is generated to show what parts of the peptide are still accessible to water when three copies of the protein are associated in an array on the surface of the virus (5) and when four such arrays (out of 60) are in position on the outer surface of the virus (6).

Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions

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

Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.

Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less

The effect of the geomagnetic field on negative voltage spheres in the ionospheric plasma: Fluid simulation

NASA Astrophysics Data System (ADS)

Ma, T.-Z.; Schunk, R. W.

1994-07-01

Experiments involving the interaction of spherical conducting objects biases with hight voltages in the Low-Earth-Orbit (LEO) environment have been conducted and designed. In these experiments, both positive and negative voltages have been applied to the spheres. Previously, there have been theoretical and numerical studies of positive voltage spheres in plasmas with and without magnetic fields. There also have been studies of negative voltage objects in unmagnetized plasmas. Here, we used a fluid model to study the plasma response to a negative voltage sphere immersed in a magnetized plasma. Our main purpose was to investigate the role of the magnetic field during the early-time interaction between the negative voltage sphere and the ambient plasma in the LEO environment. In this study, different applied voltages, magnetic field strengths, and rise-times of the applied voltages were considered. It was found that with the strength of the geomagnetic field the ions are basically not affected by the magnetic field on the time scale of hundreds of plasma periods considered in this study. The ion density distribution around the sphere and the collected ion flux by the sphere are basically the same as in the case without the magnetic field. The electron motion is strongly affected by the magnetic field. One effect is to change the nature of the electron over-shoot oscillation from regular to somewhat turbulent. Although the electrons move along the magnetic field much more easily than across the magnetic field, some redirection effect causes the electron density to distribute as if the magnetic field effect is minimal. The sheath struture and the electric field around the sphere tend to be spherical. A finite rise-time of the applied voltage reduces the oscillatory activities and delays the ion acceleration. However, the effect of the rise-time depends on both the duration of the rise-time and the ion plasma period.

Enhanced adsorption of Eu(III) on mesoporous Al2O3/expanded graphite composites investigated by macroscopic and microscopic techniques.

PubMed

Sun, Yubing; Chen, Changlun; Tan, Xiaoli; Shao, Dadong; Li, Jiaxing; Zhao, Guixia; Yang, Shubin; Wang, Qi; Wang, Xiangke

2012-11-21

Mesoporous Al(2)O(3) was intercalated into an expanded graphite (EG) interlayer to prepare mesoporous Al(2)O(3)/EG composites. The basal spacing of mesoporous Al(2)O(3)/EG composites was enlarged as compared to raw graphite from the X-ray diffraction analysis. The massive surface functional groups and wedge-shaped pores were observed in terms of potentiometric acid-base titration analysis and scanning electron microscope, respectively. The pH-dependent adsorption of Eu(III) on mesoporous Al(2)O(3)/EG composites was evidently independent of ionic strength. The maximum adsorption capacity of Eu(III) on mesoporous Al(2)O(3)/EG composites at pH 6.0 and T = 293 K was calculated to be 5.14 mg g(-1). Desorption kinetics and cyclic operation results showed that mesoporous Al(2)O(3)/EG composites presented high hydrothermal stability in aqueous solution. The thermodynamic parameters suggested that Eu(III) adsorption on mesoporous Al(2)O(3)/EG composites is an endothermic and a spontaneous process. The decrease of Eu-O bond distance with the increasing pH demonstrated that the adsorption mechanism between Eu(III) and mesoporous Al(2)O(3)/EG composites would shift from outer-sphere surface complexation to inner-sphere surface complexation in terms of extended X-ray absorption fine structure spectroscopy analysis.

[Conceptual foundations of creation of branch database of technology and intellectual property rights owned by scientific institutions, organizations, higher medical educational institutions and enterprises of healthcare sphere of Ukraine].

PubMed

Horban', A Ie

2013-09-01

The question of implementation of the state policy in the field of technology transfer in the medical branch to implement the law of Ukraine of 02.10.2012 No 5407-VI "On Amendments to the law of Ukraine" "On state regulation of activity in the field of technology transfers", namely to ensure the formation of branch database on technology and intellectual property rights owned by scientific institutions, organizations, higher medical education institutions and enterprises of healthcare sphere of Ukraine and established by budget are considered. Analysis of international and domestic experience in the processing of information about intellectual property rights and systems implementation support transfer of new technologies are made. The main conceptual principles of creation of this branch database of technology transfer and branch technology transfer network are defined.

Information theoretical approach to discovering solar wind drivers of the outer radiation belt

DOE PAGES

Wing, Simon; Johnson, Jay R.; Camporeale, Enrico; ...

2016-07-29

The solar wind-magnetosphere system is nonlinear. The solar wind drivers of geosynchronous electrons with energy range of 1.8–3.5 MeV are investigated using mutual information, conditional mutual information (CMI), and transfer entropy (TE). These information theoretical tools can establish linear and nonlinear relationships as well as information transfer. The information transfer from solar wind velocity ( Vsw) to geosynchronous MeV electron flux ( Je) peaks with a lag time of 2 days. As previously reported, Je is anticorrelated with solar wind density ( nsw) with a lag of 1 day. However, this lag time and anticorrelation can be attributed at leastmore » partly to the Je( t + 2 days) correlation with Vsw( t) and nsw( t + 1 day) anticorrelation with Vsw( t). Analyses of solar wind driving of the magnetosphere need to consider the large lag times, up to 3 days, in the ( Vsw, nsw) anticorrelation. Using CMI to remove the effects of Vsw, the response of Je to nsw is 30% smaller and has a lag time < 24 h, suggesting that the MeV electron loss mechanism due to nsw or solar wind dynamic pressure has to start operating in < 24 h. nsw transfers about 36% as much information as Vsw (the primary driver) to Je. Nonstationarity in the system dynamics is investigated using windowed TE. Here, when the data are ordered according to transfer entropy value, it is possible to understand details of the triangle distribution that has been identified between Je( t + 2 days) versus Vsw( t).« less

Information theoretical approach to discovering solar wind drivers of the outer radiation belt

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

Wing, Simon; Johnson, Jay R.; Camporeale, Enrico

The solar wind-magnetosphere system is nonlinear. The solar wind drivers of geosynchronous electrons with energy range of 1.8–3.5 MeV are investigated using mutual information, conditional mutual information (CMI), and transfer entropy (TE). These information theoretical tools can establish linear and nonlinear relationships as well as information transfer. The information transfer from solar wind velocity ( Vsw) to geosynchronous MeV electron flux ( Je) peaks with a lag time of 2 days. As previously reported, Je is anticorrelated with solar wind density ( nsw) with a lag of 1 day. However, this lag time and anticorrelation can be attributed at leastmore » partly to the Je( t + 2 days) correlation with Vsw( t) and nsw( t + 1 day) anticorrelation with Vsw( t). Analyses of solar wind driving of the magnetosphere need to consider the large lag times, up to 3 days, in the ( Vsw, nsw) anticorrelation. Using CMI to remove the effects of Vsw, the response of Je to nsw is 30% smaller and has a lag time < 24 h, suggesting that the MeV electron loss mechanism due to nsw or solar wind dynamic pressure has to start operating in < 24 h. nsw transfers about 36% as much information as Vsw (the primary driver) to Je. Nonstationarity in the system dynamics is investigated using windowed TE. Here, when the data are ordered according to transfer entropy value, it is possible to understand details of the triangle distribution that has been identified between Je( t + 2 days) versus Vsw( t).« less

Dye-sensitized electron transfer from TiO2 to oxidized triphenylamines that follows first-order kinetics

PubMed Central

DiMarco, Brian N.; Troian-Gautier, Ludovic; Sampaio, Renato N.

2017-01-01

Two sensitizers, [Ru(bpy)2(dcb)]2+ (RuC) and [Ru(bpy)2(dpb)]2+ (RuP), where bpy is 2,2′-bipyridine, dcb is 4,4′-dicarboxylic acid-2,2′-bipyridine and dpb is 4,4′-diphosphonic acid-2,2′-bipyridine, were anchored to mesoporous TiO2 thin films and utilized to sensitize the reaction of TiO2 electrons with oxidized triphenylamines, TiO2(e–) + TPA+ → TiO2 + TPA, to visible light in CH3CN electrolytes. A family of four symmetrically substituted triphenylamines (TPAs) with formal Eo(TPA+/0) reduction potentials that spanned a 0.5 eV range was investigated. Surprisingly, the reaction followed first-order kinetics for two TPAs that provided the largest thermodynamic driving force. Such first-order reactivity indicates a strong Coulombic interaction between TPA+ and TiO2 that enables the injected electron to tunnel back in one concerted step. The kinetics for the other TPA derivatives were non-exponential and were modelled with the Kohlrausch–William–Watts (KWW) function. A Perrin-like reaction sphere model is proposed to rationalize the kinetic data. The activation energies were the same for all of the TPAs, within experimental error. The average rate constants were found to increase with the thermodynamic driving force, consistent with electron transfer in the Marcus normal region. PMID:29629161

Electronic structure and optical properties of Eu(III) tris-β-diketonate adducts with 1,10-phenanthroline

NASA Astrophysics Data System (ADS)

Shurygin, A. V.; Korochentsev, V. V.; Cherednichenko, A. I.; Mirochnik, A. G.; Kalinovskaya, I. V.; Vovna, V. I.

2018-03-01

Adducts of tris-β-diketonates of the rare earth metal Eu(III) with 1,10-phenanthroline are studied by photoelectron spectroscopy and quantum chemistry methods. The electronic structure, peculiarities of the nature of chemical bonds, and the geometric structure of the adducts are determined. The interpretation of UV photoelectron spectra of vapors and X-ray photoelectron spectra of solid is carried out with the chosen technique. DFT/TDDFT methods make it possible to study the 1,10-phenanthroline molecule influence on the adduct electronic structure and to analyze the electronic effects of substitution of methyl groups by trifluoromethyl groups in the ligands. At transition from the tris-β-diketonate complexes to the adducts, it is observed an increase of the absorption region and a decrease in the energy gap that contributes to the efficiency growth in electronic excitation energy transfer in the ligand-metal. Moreover, phenanthroline displaces water groups, that are luminescence quenchers, from the first coordination sphere, closes coordination in the adduct, and blocks their further attachment. Both factors contribute to an increase in the luminescence intensity.

Raman Backscatter as a Remote Laser Power Sensor in High-Energy-Density Plasmas [Stimulated Scattering as a Remote Laser Power Sensor in High-Density and Temperature Plasmas

DOE PAGES

Moody, J. D.; Strozzi, D. J.; Divol, L.; ...

2013-07-09

Stimulated Raman backscatter is used as a remote sensor to quantify the instantaneous laser power after transfer from outer to inner cones that cross in a National Ignition Facility (NIF) gas-filled hohlraum plasma. By matching stimulated Raman backscatter between a shot reducing outer versus a shot reducing inner power we infer that about half of the incident outer-cone power is transferred to inner cones, for the specific time and wavelength configuration studied. Furthermore, this is the first instantaneous nondisruptive measure of power transfer in an indirect drive NIF experiment using optical measurements.

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

Hall, J.; Richard, P.; Gray, T.J.

The systematics of single and double K-shell-vacancy production in titanium has been investigated in the limit of zero target thickness (approx.1 ..mu..g/cm/sup 2/) for incident C, N, O, F, Mg, Al, Si, S, and Cl ions over a maximum energy range of 0.5 to 6.5 MeV/amu. This corresponds to collision systems with 0.27< or =Z/sub 1//Z/sub 2/< or =0.77 and 0.24< or =v/sub 1//vK< or =0.85, where v/sub 1/ is the projectile nuclear velocity and vK is the mean velocity of an electron in the target K shell. The present work is divided into four major sections. (1) Single K-shell-vacancymore » production has been investigated by measuring K..cap alpha.. and K..beta.. p satellite x-ray-production cross sections for projectiles incident with no K-shell vacancies. For incident ions with Z/sub 1/> or =9, the contribution due to electron-transfer processes from the target K shell to outer shells of the projectile has also been noted. (2) Single K-shell--to--K-shell electron-transfer cross sections have been obtained indirectly by the measuring of the enhancement in the Ti K x-ray production cross section for bare incident projectiles over ions incident with no initial K-shell vacancies. (3) Double K-vacancy production has been investigated by measuring the K..cap alpha.. hypersatellite intensity in ratio to the total K..cap alpha.. intensity. (4) Double K-shell--to--K-shell electron-transfer cross sections have been obtained indirectly with the use of a procedure similar to that used for single K to K transfer. The measured cross sections have been compared to theoretical models for direct Coulomb ionization and inner-shell electron transfer and have been used to investigate the relative importance of these mechanisms for K-vacancy production in heavy-ion--atom collisions.« less

Site specific atomic polarizabilities in endohedral fullerenes and carbon onions

NASA Astrophysics Data System (ADS)

Zope, Rajendra R.; Bhusal, Shusil; Basurto, Luis; Baruah, Tunna; Jackson, Koblar

2015-08-01

We investigate the polarizability of trimetallic nitride endohedral fullerenes by partitioning the total polarizability into site specific components. This analysis indicates that the polarizability of the endohedral fullerene is essentially due to the outer fullerene cage and has insignificant contribution from the encapsulated unit. Thus, the outer fullerene cages effectively shield the encapsulated clusters and behave like Faraday cages. The polarizability of endohedral fullerenes is slightly smaller than the polarizability of the corresponding bare carbon fullerenes. The application of the site specific polarizabilities to C60@C240 and C60@C180 onions shows that, compared to the polarizability of isolated C60 fullerene, the encapsulation of the C60 in C240 and C180 fullerenes reduces its polarizability by 75% and 83%, respectively. The differences in the polarizability of C60 in the two onions is a result of differences in the bonding (intershell electron transfer), fullerene shell relaxations, and intershell separations. The site specific analysis further shows that the outer atoms in a fullerene shell contribute most to the fullerene polarizability.

Site specific atomic polarizabilities in endohedral fullerenes and carbon onions.

PubMed

Zope, Rajendra R; Bhusal, Shusil; Basurto, Luis; Baruah, Tunna; Jackson, Koblar

2015-08-28

We investigate the polarizability of trimetallic nitride endohedral fullerenes by partitioning the total polarizability into site specific components. This analysis indicates that the polarizability of the endohedral fullerene is essentially due to the outer fullerene cage and has insignificant contribution from the encapsulated unit. Thus, the outer fullerene cages effectively shield the encapsulated clusters and behave like Faraday cages. The polarizability of endohedral fullerenes is slightly smaller than the polarizability of the corresponding bare carbon fullerenes. The application of the site specific polarizabilities to C60@C240 and C60@C180 onions shows that, compared to the polarizability of isolated C60 fullerene, the encapsulation of the C60 in C240 and C180 fullerenes reduces its polarizability by 75% and 83%, respectively. The differences in the polarizability of C60 in the two onions is a result of differences in the bonding (intershell electron transfer), fullerene shell relaxations, and intershell separations. The site specific analysis further shows that the outer atoms in a fullerene shell contribute most to the fullerene polarizability.

Site specific atomic polarizabilities in endohedral fullerenes and carbon onions

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

Zope, Rajendra R., E-mail: rzope@utep.edu; Baruah, Tunna; Computational Science Program, The University of Texas at El Paso, El Paso, Texas 79958

2015-08-28

We investigate the polarizability of trimetallic nitride endohedral fullerenes by partitioning the total polarizability into site specific components. This analysis indicates that the polarizability of the endohedral fullerene is essentially due to the outer fullerene cage and has insignificant contribution from the encapsulated unit. Thus, the outer fullerene cages effectively shield the encapsulated clusters and behave like Faraday cages. The polarizability of endohedral fullerenes is slightly smaller than the polarizability of the corresponding bare carbon fullerenes. The application of the site specific polarizabilities to C{sub 60}@C{sub 240} and C{sub 60}@C{sub 180} onions shows that, compared to the polarizability of isolatedmore » C{sub 60} fullerene, the encapsulation of the C{sub 60} in C{sub 240} and C{sub 180} fullerenes reduces its polarizability by 75% and 83%, respectively. The differences in the polarizability of C{sub 60} in the two onions is a result of differences in the bonding (intershell electron transfer), fullerene shell relaxations, and intershell separations. The site specific analysis further shows that the outer atoms in a fullerene shell contribute most to the fullerene polarizability.« less

Encapsulation of LiFePO4 by in-situ graphitized carbon cage towards enhanced low temperature performance as cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Yao, Bin; Ding, Zhaojun; Zhang, Jianxin; Feng, Xiaoyu; Yin, Longwei

2014-08-01

The severe capacity decay of LiFePO4 at low temperatures (≤0 °C) limits its wide applications as cathode materials for energy storage batteries. Creating comprehensive carbon network between particles with improved electronic conductivity is a well known solution to this problem. Here, a novel structured LiFePO4/C composite was prepared by a facile solid state route, in which nanosized LiFePO4 spheres were encapsulated by in-situ graphitized carbon cages. With the enhancement in electronic conductivity (2.15e-1 S cm-1), the composite presented excellent rate performance at room temperature and remarkable capacity retention at -40 °C, with charge transfer resistance much lower than commercial LiFePO4.

Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

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

Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.

2014-06-24

Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses ofmore » functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.« less

Structural and spectroscopic characterizations on the charge-transfer interactions of the second generation poly(propylene amine) dendrimers with iodine and picric acid acceptors.

PubMed

El-Sayed, Mohamed Y; Refat, Moamen S

2015-02-25

Herein, this study was focused to get a knowledge about the intermolecular charge transfer complexes between the second generation of poly(propylene amine) dendrimer (PPD2) with picric acid (PA) and iodine (I2) as π and σ-acceptors. The charge-transfer interaction of the PPD2 electron donor and the PA acceptor has been studied in CHCl3. The resulted data refereed to the formation of the new CT-complex with the general formula [(PPD2)(PA)4]. The 1:4 stoichiometry of the reaction was discussed upon the on elemental analysis and photometric titration. On the other hand, the 1:3½ iodine-PPD2 heptaiodide (I7(-)) charge-transfer complex has been studied spectrophotometrically in chloroform at room temperature with general formula [(PPD2)](+)I7(-). The electronic absorption bands of 2I2·I3(-) (I7(-)) are observed at 358 and 294 nm. Raman laser spectrum of the brown solid heptaiodide complex has two clearly vibration bands at 155 and 110 cm(-1) due to symmetric stretching νs(II) outer and inner bonds, respectively. The (1)H NMR spectra and differential scanning calorimetry (DSC) data of PPD2 charge-transfer complexes were discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Enhanced photocatalytic performance and degradation pathway of Rhodamine B over hierarchical double-shelled zinc nickel oxide hollow sphere heterojunction

NASA Astrophysics Data System (ADS)

Zhang, Ying; Zhou, Jiabin; Cai, Weiquan; Zhou, Jun; Li, Zhen

2018-02-01

In this study, hierarchical double-shelled NiO/ZnO hollow spheres heterojunction were prepared by calcination of the metallic organic frameworks (MOFs) as a sacrificial template in air via a one-step solvothermal method. Additionally, the photocatalytic activity of the as-prepared samples for the degradation of Rhodamine B (RhB) under UV-vis light irradiation were also investigated. NiO/ZnO microsphere comprised a core and a shell with unique hierarchically porous structure. The photocatalytic results showed that NiO/ZnO hollow spheres exhibited excellent catalytic activity for RhB degradation, causing complete decomposition of RhB (200 mL of 10 g/L) under UV-vis light irradiation within 3 h. Furthermore, the degradation pathway was proposed on the basis of the intermediates during the photodegradation process using liquid chromatography analysis coupled with mass spectroscopy (LC-MS). The improvement in photocatalytic performance could be attributed to the p-n heterojunction in the NiO/ZnO hollow spheres with hierarchically porous structure and the strong double-shell binding interaction, which enhances adsorption of the dye molecules on the catalyst surface and facilitates the electron/hole transfer within the framework. The degradation mechanism of pollutant is ascribed to the hydroxyl radicals (rad OH), which is the main oxidative species for the photocatalytic degradation of RhB. This work provides a facile and effective approach for the fabrication of porous metal oxides heterojunction with high photocatalytic activity and thus can be potentially used in the environmental purification.

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI{sub 4}

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

Liu, H.; Tse, J. S., E-mail: john.tse@usask.ca; Hu, M. Y.

2015-10-28

The pressure-induced amorphization and subsequent recrystallization of SnI{sub 4} have been investigated using first principles molecular dynamics calculations together with high-pressure {sup 119}Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI{sub 4} under ambient conditions. Although high pressure structures of SnI{sub 4} were thought to be determined by randommore » packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.« less

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of Snl 4

DOE PAGES

Liu, Hanyu; Tse, John S.; Hu, Michael Y.; ...

2015-10-27

The pressure-induced amorphization and subsequent recrystallization of SnI 4 have been investigated using first principles molecular dynamics calculations together with high-pressure 119Sn nuclear resonant inelastic x-ray scattering measurements. Above ~8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ~64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI 4 under ambient conditions. Although high pressure structures of SnI 4 were thought to be determined by random packingmore » of equal-sized spheres, we detected electron charge transfer in each phase. As a result, this charge transfer results in a crystal structure packing determined by larger than expected iodine atoms. (C) 2015 AIP Publishing LLC.« less

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI4.

PubMed

Liu, H; Tse, J S; Hu, M Y; Bi, W; Zhao, J; Alp, E E; Pasternak, M; Taylor, R D; Lashley, J C

2015-10-28

The pressure-induced amorphization and subsequent recrystallization of SnI4 have been investigated using first principles molecular dynamics calculations together with high-pressure (119)Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4 under ambient conditions. Although high pressure structures of SnI4 were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.

Aerodynamic Characteristics of a Model of an Inflatable-Sphere Launching Vehicle under Simulated Conditions of Mach Number and Altitude

NASA Technical Reports Server (NTRS)

Robinson, Ross B.; Morris, Odell A.

1960-01-01

An investigation has been conducted in the Langley 4- by 4-foot supersonic pressure tunnel to determine the aerodynamic characteristics in pitch of a two-stage-rocket model configuration which simulated the last two stages of the launching vehicle for an inflatable sphere. Tests were made through an angle-of-attack range from -6 deg to 18 deg at dynamic pressures of 102 and 255 pounds per square foot with corresponding Mach numbers of 1.89 and 1.98 for the model both with and without a bumper arrangement designed to protect the rocket casing from the outer shell of the vehicle.

A comparative study of the electrostatic potential of fullerene-like structures of Au 32 and Au 42

NASA Astrophysics Data System (ADS)

Wang, Dong-Lai; Sun, Xiao-Ping; Shen, Hong-Tao; Hou, Dong-Yan; Zhai, Yu-Chun

2008-05-01

By using density functional theory calculations, it is found that the most negative MEP inside the gold cage occurs at the center of the sphere. The largest regions with the most negative MEP outside the sphere are localized in the neighborhood of the bridge sites and the vertex regions of the five-coordinated are more positive. The absolute values of the most negative potentials in both the inner and outer cages as well as the vertex regions of the five-coordinated of Au 32 structure are much larger than those of Au 42, which means Au 32 is preferable for electrophilic attack or nucleophilic processes.

Measuring the Density of States of the Inner and Outer Wall of Double-Walled Carbon Nanotubes.

PubMed

Chambers, Benjamin A; Shearer, Cameron J; Yu, LePing; Gibson, Christopher T; Andersson, Gunther G

2018-06-19

The combination of ultraviolet photoelectron spectroscopy and metastable helium induced electron spectroscopy is used to determine the density of states of the inner and outer coaxial carbon nanotubes. Ultraviolet photoelectron spectroscopy typically measures the density of states across the entire carbon nanotube, while metastable helium induced electron spectroscopy measures the density of states of the outermost layer alone. The use of double-walled carbon nanotubes in electronic devices allows for the outer wall to be functionalised whilst the inner wall remains defect free and the density of states is kept intact for electron transport. Separating the information of the inner and outer walls enables development of double-walled carbon nanotubes to be independent, such that the charge transport of the inner wall is maintained and confirmed whilst the outer wall is modified for functional purposes.

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals

PubMed Central

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-01-01

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV). PMID:26039669

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals.

PubMed

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-06-03

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV).

Uniform electron gases. III. Low-density gases on three-dimensional spheres.

PubMed

Agboola, Davids; Knol, Anneke L; Gill, Peter M W; Loos, Pierre-François

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGF centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids - the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) - and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.

Heterogeneous photo-Fenton processes using graphite carbon coating hollow CuFe2O4 spheres for the degradation of methylene blue

NASA Astrophysics Data System (ADS)

Guo, Xiaojun; Wang, Kebai; Li, Dai; Qin, Jiabin

2017-10-01

The novel graphite carbon coating hollow CuFe2O4 spheres were fabricated through solvothermal method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectra, etc. The catalytic performance of the graphite carbon coating hollow CuFe2O4 spheres was evaluated in photo-Fenton-like degradation of methylene blue (MB) using H2O2 as a green oxidant under light irradiation (λ > 400 nm). The results demonstrated that the hollow CuFe2O4 spheres with graphite carbon coating exhibited superior catalytic activity. In the preparation process of catalyst, the addition of glucose was very important to its catalytic performance. Photoresponse analysis of the typical samples proved that CuFe2O4@graphite carbon core-shell hollow spheres possessed excellent photocurrent response and lower electrochemical impedance. In addition, a possible mechanism for photocatalytic degradation of MB had been presumed. Moreover, after five regeneration cycles, the graphite carbon coating hollow CuFe2O4 spheres still exhibited better properties.

Catalytic behavior of ‘Pt-atomic chain encapsulated gold nanotube’: A density functional study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib

2016-05-23

With an aim to design novel material and explore its catalytic performance towards CO oxidation, Pt atomic chain was introduced inside gold nanotube (Au-NT). Theoretical calculations at the level of first principles formalism was carried out to investigate the atomic and electronic properties of the composite. Geometrically Pt atoms prefer to align in zig-zag fashion. Significant electronic charge transfer from inside Pt atoms to the outer wall Au atoms is observed. Interaction of O{sub 2} with Au-NT wall follows by injection of additional electronic charge in the anti-bonding orbital of oxygen molecule leading to activation of the O-O bond. Furthermore » interaction of CO molecule with the activated oxygen molecule leads to spontaneous oxidation reaction and formation of CO{sub 2}.« less

A survey of aerobraking orbital transfer vehicle design concepts

NASA Technical Reports Server (NTRS)

Park, Chul

1987-01-01

The five existing design concepts of the aerobraking orbital transfer vehicle (namely, the raked sphere-cone designs, conical lifting-brake, raked elliptic-cone, lifting-body, and ballute) are reviewed and critiqued. Historical backgrounds, and the geometrical, aerothermal, and operational features of these designs are reviewed first. Then, the technological requirements for the vehicle (namely, navigation, aerodynamic stability and control, afterbody flow impingement, nonequilibrium radiation, convective heat-transfer rates, mission abort and multiple atmospheric passes, transportation and construction, and the payload-to-vehicle weight requirements) are delineated by summarizing the recent advancements made on these issues. Each of the five designs are critiqued and rated on these issues. The highest and the lowest ratings are given to the raked sphere-cone and the ballute design, respectively.

Oscillation effects upon film boiling from a sphere.

NASA Technical Reports Server (NTRS)

Schmidt, W. E.; Witte, L. C.

1972-01-01

Heat transfer rates from a silver-plated copper sphere, 0.75 in. in diameter, were studied by high speed photography during oscillations of the sphere in saturated liquid nitrogen and Freon-11. The oscillation frequencies ranged from zero to 13 Hz, and the amplitude-to-diameter ratio varied from zero to 2.67. The sphere was supported by a thin-walled stainless steel tube and carried a thermocouple attached near the lower stagnation point. A Fastax WF-3 16mm movie camera was used at about 2000 frames/sec. The differences in the vapor removal process at lower and higher oscillation frequencies are discussed.

Beam conditioner for free electron lasers and synchrotrons

DOEpatents

Liu, H.; Neil, G.R.

1998-09-08

A focused optical has been used to introduce an optical pulse, or electromagnetic wave, collinear with the electron beam in a free electron laser or synchrotron thereby adding an axial field component that accelerates the electrons on the radial outside of the distribution of electrons in the electron beam. This invention consists of using the axial electrical component of a TEM{sub 10} mode Gaussian beam in vacuum to condition the electron beam and speed up the outer electrons in the beam. The conditioning beam should possess about the same diameter as the electron beam. The beam waist of the conditioning wave must be located around the entrance of the undulator longitudinally to have a net energy exchange between the electrons in the outer part of the distribution and the conditioning wave owing to the natural divergence of a Gaussian beam. By accelerating the outer electrons, the outer and core electrons are caused to stay in phase. This increases the fraction of the electron beam energy that is converted to light thereby improving the efficiency of conversion of energy to light and therefore boosting the power output of the free electron laser and synchrotron. 4 figs.

Beam conditioner for free electron lasers and synchrotrons

DOEpatents

Liu, Hongxiu; Neil, George R.

1998-01-01

A focused optical is been used to introduce an optical pulse, or electromagnetic wave, colinearly with the electron beam in a free electron laser or synchrotron thereby adding an axial field component that accelerates the electrons on the radial outside of the distribution of electrons in the electron beam. This invention consists of using the axial electrical component of a TEM.sub.10 mode Gaussian beam in vacuum to condition the electron beam and speed up the outer electrons in the beam. The conditioning beam should possess about the same diameter as the electron beam. The beam waist of the conditioning wave must be located around the entrance of the undulator longitudinally to have a net energy exchange between the electrons in the outer part of the distribution and the conditioning wave owing to the natural divergence of a Gaussian beam. By accelerating the outer electrons, the outer and core electrons are caused to stay in phase. This increases the fraction of the electron beam energy that is converted to light thereby improving the efficiency of conversion of energy to light and therefore boosting the power output of the free electron laser and synchrotron.

Locally optimal transfer trajectories between libration point orbits using invariant manifolds

NASA Astrophysics Data System (ADS)

Davis, Kathryn E.

2009-12-01

Techniques from dynamical systems theory and primer vector theory have been applied to the construction of locally optimal transfer trajectories between libration point orbits. When two libration point orbits have different energies, it has been found that the unstable manifold of the first orbit can be connected to the stable manifold of the second orbit with a bridging trajectory. A bounding sphere centered on the secondary, with a radius less than the radius of the sphere of influence of the secondary, was used to study the stable and unstable manifold trajectories. It was numerically demonstrated that within the bounding sphere, the two-body parameters of the unstable and stable manifold trajectories could be analyzed to locate low transfer costs. It was shown that as the two-body parameters of an unstable manifold trajectory more closely matched the two-body parameters of a stable manifold trajectory, the total DeltaV necessary to complete the transfer decreased. Primer vector theory was successfully applied to a transfer to determine the optimal maneuvers required to create the bridging trajectory that connected the unstable manifold of the first orbit to the stable manifold of the second orbit. Transfer trajectories were constructed between halo orbits in the Sun-Earth and Earth-Moon three-body systems. Multiple solutions were found between the same initial and final orbits, where certain solutions retraced interior portions of the trajectory. All of the trajectories created satisfied the conditions for optimality. The costs of transfers constructed using invariant manifolds were compared to the costs of transfers constructed without the use of invariant manifolds, when data was available. In all cases, the total cost of the transfers were significantly lower when invariant manifolds were used in the transfer construction. In many cases, the transfers that employed invariant manifolds were three to four times more efficient, in terms of fuel expenditure, than the transfer that did not. The decrease in transfer cost was accompanied by an increase in transfer time of flight. Transfers constructed in the Earth-Moon system were shown to be particularly viable for lunar navigation and communication constellations, as excellent coverage of the lunar surface can be achieved during the transfer.

Possible Dynamically Gated Conductance along Heme Wires in Bacterial Multiheme Cytochromes

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

Smith, Dayle MA; Rosso, Kevin M.

2014-07-24

The staggered cross decaheme configuration of electron transfer co-factors in the outer-membrane cytochrome MtrF may serve as a prototype for conformationally-gated multi-heme electron transport. Derived from the bacterium Shewanella oneidensis, the staggered cross configuration reveals intersecting c-type octaheme and tetraheme “wires” containing thermodynamic “hills” and “valleys”, suggesting that the protein structure may include a dynamical mechanism for conductance and pathway switching depending on enzymatic functional need. Recent molecular simulations have established the pair-wise electronic couplings, redox potentials, and reorganization energies to predict the maximum conductance along the various heme wire pathways by sequential hopping of a single electron (PNAS (2014)more » 11,611-616). Here, we expand this information with classical molecular and statistical mechanics calculations of large-amplitude protein dynamics in MtrF, to address its potential to modulate pathway conductance, including assessment of the effect of the total charge state. Explicit solvent molecular dynamics simulations of fully oxidized and fully reduced MtrF employing ten independent 50-ns simulations at 300 K and 1 atm showed that reduced MtrF is more expanded and explores more conformational space than oxidized MtrF, and that heme reduction leads to increased heme solvent exposure. The slowest mode of collective decaheme motion is 90% similar between the oxidized and reduced states, and consists primarily of inter-heme separation with minor rotational contributions. The frequency of this motion is 1.7×107 s 1 for fully-oxidized and fully-reduced MtrF, respectively, slower than the downhill electron transfer rates between stacked heme pairs at the octaheme termini and faster than the electron transfer rates between parallel hemes in the tetraheme chain. This implies that MtrF uses slow conformational fluctuations to modulate electron flow along the octaheme pathway, apparently for the purpose of increasing the residence time of electrons on lowest potential hemes 4 and 9. This apparent gating mechanism should increase the success rate of electron transfer from MtrF to low potential environmental acceptors via these two solvent-exposed hemes.« less

The proline-rich domain of TonB possesses an extended polyproline II-like conformation of sufficient length to span the periplasm of Gram-negative bacteria

PubMed Central

Köhler, Silvia Domingo; Weber, Annemarie; Howard, S Peter; Welte, Wolfram; Drescher, Malte

2010-01-01

TonB from Escherichia coli and its homologues are critical for the uptake of siderophores through the outer membrane of Gram-negative bacteria using chemiosmotic energy. When different models for the mechanism of TonB mediated energy transfer from the inner to the outer membrane are discussed, one of the key questions is whether TonB spans the periplasm. In this article, we use long range distance measurements by spin-label pulsed EPR (Double Electron–Electron Resonance, DEER) and CD spectroscopy to show that the proline-rich segment of TonB exists in a PPII-like conformation. The result implies that the proline-rich segment of TonB possesses a length of more than 15 nm, sufficient to span the periplasm of Gram-negative bacteria. PMID:20095050

Characterization of a transient +2 sulfur oxidation state intermediate from the oxidation of aqueous sulfide

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

Vairavmurthy, M.A.; Zhou, Weiqing

1995-04-01

The oxidation H{sub 2}S to sulfate involves a net transfer of eight electrons and occurs through the formation of several partially oxidized intermediates with oxidation states ranging from {minus}1 to +5. Known intermediates include elemental sulfur (oxidation state 0), polysulfides (outer sulfur: {minus}1, inner sulfur: 0), sulfite (+4) and thiosulfate (outer sulfur: {minus}1, inner sulfur: +5). A noticeable gap in this series of intermediates is that of a +2 sulfur oxidation state oxoacid/oxoanion species, which was never detected experimentally. Here, we present evidence of the transient existence of +2 oxidation state intermediate in the Ni(II)-catalyzed oxidation of aqueous sulfide. X-raymore » absorption near-edge structure (XANES) spectroscopy and Fourier-transform-infrared (FT-IR) spectroscopy were used to characterize this species; they suggest that it has a sulfoxylate ion (SO{sub 2}{sup 2{minus}}) structure.« less

Zonal Flow Velocimetry in Spherical Couette Flow using Acoustic Modes

NASA Astrophysics Data System (ADS)

Adams, Matthew M.; Mautino, Anthony R.; Stone, Douglas R.; Triana, Santiago A.; Lekic, Vedran; Lathrop, Daniel P.

2015-11-01

We present studies of spherical Couette flows using the technique of acoustic mode Doppler velocimetry. This technique uses rotational splittings of acoustic modes to infer the azimuthal velocity profile of a rotating flow, and is of special interest in experiments where direct flow visualization is impractical. The primary experimental system consists of a 60 cm diameter outer spherical shell concentric with a 20 cm diameter sphere, with air or nitrogen gas serving as the working fluid. The geometry of the system approximates that of the Earth's core, making these studies geophysically relevant. A turbulent shear flow is established in the system by rotating the inner sphere and outer shell at different rates. Acoustic modes of the fluid volume are excited using a speaker and measured via microphones, allowingdetermination of rotational splittings. Preliminary results comparing observed splittings with those predicted by theory are presented. While the majority of these studies were performed in the 60 cm diameter device using nitrogen gas, some work has also been done looking at acoustic modes in the 3 m diameter liquid sodium spherical Couette experiment. Prospects for measuring zonal velocity profiles in a wide variety of experiments are discussed.

Electronic transport properties of inner and outer shells in near ohmic-contacted double-walled carbon nanotube transistors

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

Zhang, Yuchun; Zhou, Liyan; Zhao, Shangqian

2014-06-14

We investigate electronic transport properties of field-effect transistors based on double-walled carbon nanotubes, of which inner shells are metallic and outer shells are semiconducting. When both shells are turned on, electron-phonon scattering is found to be the dominant phenomenon. On the other hand, when outer semiconducting shells are turned off, a zero-bias anomaly emerges in the dependence of differential conductance on the bias voltage, which is characterized according to the Tomonaga-Luttinger liquid model describing tunneling into one-dimensional materials. We attribute these behaviors to different contact conditions for outer and inner shells of the double-walled carbon nanotubes. A simple model combiningmore » Luttinger liquid model for inner metallic shells and electron-phonon scattering in outer semiconducting shells is given here to explain our transport data at different temperatures.« less

Transmission Electron Microscopy (TEM) Study of the Oxide Layers Formed on Fe-12Cr-4Al Ferritic Alloy in an Oxygenated Pb-Bi Environment at 800°C

NASA Astrophysics Data System (ADS)

Popovic, M. P.; Yang, Y.; Bolind, A. M.; Ozdol, V. B.; Olmsted, D. L.; Asta, M.; Hosemann, P.

2018-06-01

Liquid lead-bismuth eutectic (LBE) can serve as a heat transfer fluid for advanced nuclear applications as well as concentrated solar power but poses corrosion challenges for the structural materials at elevated temperatures. Oxide passivation of the surfaces of these materials during exposure to liquid LBE can inhibit such material degradation. In this study, transmission electron microscopy of oxides formed on Fe-Cr-Al alloy during exposure to low-oxygenated LBE at 800°C has been performed. A complex structure of the oxide film has been revealed, consisting of a homogeneous inner layer of mostly Al2O3 and a heterogeneous outer layer.

Radio Frequency Plasma Discharge Lamps for Use as Stable Calibration Light Sources

NASA Technical Reports Server (NTRS)

McAndrew, Brendan; Cooper, John; Arecchi, Angelo; McKee, Greg; Durell, Christopher

2012-01-01

Stable high radiance in visible and near-ultraviolet wavelengths is desirable for radiometric calibration sources. In this work, newly available electrodeless radio-frequency (RF) driven plasma light sources were combined with research grade, low-noise power supplies and coupled to an integrating sphere to produce a uniform radiance source. The stock light sources consist of a 28 VDC power supply, RF driver, and a resonant RF cavity. The RF cavity includes a small bulb with a fill gas that is ionized by the electric field and emits light. This assembly is known as the emitter. The RF driver supplies a source of RF energy to the emitter. In commercial form, embedded electronics within the RF driver perform a continual optimization routine to maximize energy transfer to the emitter. This optimization routine continually varies the light output sinusoidally by approximately 2% over a several-second period. Modifying to eliminate this optimization eliminates the sinusoidal variation but allows the output to slowly drift over time. This drift can be minimized by allowing sufficient warm-up time to achieve thermal equilibrium. It was also found that supplying the RF driver with a low-noise source of DC electrical power improves the stability of the lamp output. Finally, coupling the light into an integrating sphere reduces the effect of spatial fluctuations, and decreases noise at the output port of the sphere.

Flavin binding to the deca-heme cytochrome MtrC: Insights from computational molecular simulation

DOE PAGES

Breuer, Marian; Rosso, Kevin  M.; Blumberger, Jochen

2015-12-15

Here, certain dissimilatory bacteria have the remarkable ability to use extracellular metal oxide minerals instead of oxygen as terminal electron sinks, using a process known as “extracellular respiration”. Specialized multiheme cytochromes located on the outer membrane of the microbe were shown to be crucial for electron transfer from the cell surface to the mineral. This process is facilitated by soluble, biogenic flavins secreted by the organism for the purpose of acting as an electron shuttle. However, their interactions with the outer-membrane cytochromes are not established on a molecular scale. Here, we study the interaction between the outer-membrane deca-heme cytochrome MtrCmore » from Shewanella oneidensis and flavin mononucleotide (FMN in fully oxidized quinone form) using computational docking. We find that interaction of FMN with MtrC is significantly weaker than with known FMN-binding proteins, but identify a mildly preferred interaction site close to heme 2 with a dissociation constant (K d) = 490 μM, in good agreement with recent experimental estimates, K d = 255 μM. The weak interaction with MtrC can be qualitatively explained by the smaller number of hydrogen bonds that the planar headgroup of FMN can form with this protein compared to FMN-binding proteins. Molecular dynamics simulation gives indications for a possible conformational switch upon cleavage of the disulphide bond of MtrC, but without concomitant increase in binding affinities according to this docking study. Overall, our results suggest that binding of FMN to MtrC is reversible and not highly specific, which may be consistent with a role as redox shuttle that facilitates extracellular respiration.« less

Role of Outer Membrane C-Type Cytochromes MtrC and OmcA in Shewanella Oneidensis MR-1 Cell Production, Accumulation, and Detachment During Respiration on Hematite

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

Mitchell, Andrew C.; Peterson, L.; Reardon, Catherine L.

2012-07-01

Solid phase iron oxides are considered to be important terminal electron acceptors for microbial respiration in many anoxic environments. Besides the knowledge that cells attach to and reduce these substrates, other aspects of surface-associated cell behavior and the related cell surface components that influence cell-mineral interactions are not well understood. In the present study, wild-type cells of the dissimilatory iron-reducing bacterium Shewanella oneidensis MR-1 formed thin biofilms one-to-two cell layers in thickness when respiring on natural specular hematite under flow conditions similar to those which exist in aquatic sediments and subsurface environments. The distribution of cells within the biofilm indicatedmore » that direct contact was not required for electron transfer from cells to the mineral surface. Detached biomass in the form of single cells represented >99% of the surface-associated wild-type cell production from respiration on hematite over the biofilm life cycle. A mutant deficient in the outer membrane c35 type cytochrome OmcA, while still able to respire and replicate on hematite, established a lower steady-state cell density on the mineral surface than that of the wild-type strain. A mutant deficient in MtrC, another outer membrane c-type cytochrome, and a mutant deficient in both cytochromes were unable to reduce sufficient amounts of hematite to support detectable growth on the mineral surface. When considered in the context of previous work, the results support a growing body of evidence that the relative importance of OmcA and MtrC to cell respiration and replication depends on the form of iron oxide available as terminal electron acceptor.« less

Spectroscopic study of the reaction mechanism of buspirone interaction with iodine and tetracyanoethylene reagents and its applications.

PubMed

Zayed, M A; El-Habeeb, Abeer A

2009-06-01

The reactions between the drug buspirone (busp) in its base form and iodine amphoteric reagent (n-donor and/or sigma-acceptor) and with tetracyanoethylene as a pi-acceptor reagent (TCNE) have been studied spectrophotometrically at different reactant concentrations, time intervals, temperatures, and with different solvents and wavelengths, with the aim of selecting the conditions that give the most suitable molar extinction coefficients. This study aims chiefly to throw light on the nature of these reactions and to select the most proper conditions for spectrophotometric application of these reagents to determine this biologically active drug used in treating different diseases. The reaction mechanism involves the formation of busp-I(2) outer and inner sphere complexes. The separated busp-I(2) solid product obtained was investigated using elemental analyses, FT-IR, thermal analyses (TA) and electron ionization mass spectrometry (EI-MS) and was found to be biologically active. The reaction mechanism of busp-TCNE involves the formation of a charge transfer (CT) complex. The analytical parameters of the proposed spectrophotometric procedures were calculated. These procedures were applied in the analysis of busp in its formulations as a drug used to treat psychiatric illnesses. The values of the Sandell sensitivity, standard deviation (SD), relative standard deviation (RSD) and recovery percentage show the high sensitivity of these procedures. This study also presents a promising new busp-I(2) drug derivative that can be used more efficiently for the same purposes as its parent. It gives a clear idea about the possible metabolites and metabolic pathways of busp and its derivative that may occur in vivo. Copyright 2009 John Wiley & Sons, Ltd.

Macroscopic and molecular-scale assessment of soil lead contamination impacted by seasonal dove hunting activities

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

Arai, Y.; Tappero, R.; Rick, A.R.

Environmental contamination of lead (Pb) in soils and sediments poses serious threats to human and ecological health. The objective of this study is to investigate the effect of seasonal dove sports hunting activities on Pb contamination in acid forest soils. A grid sampling method was used to investigate the spatial distribution of Pb contamination in surface soils. Soils were analyzed for total metal(loid) concentration and characterized for physicochemical properties and mineralogy. Adsorption isotherm experiments were also conducted to understand the reactivity and retention capacity of Pb(II) in soils. Finally, synchrotron-based X-ray microprobe and X-ray absorption spectroscopy were used to understandmore » the chemical speciation of Pb that controls the retention/release mechanisms of Pb in soils. There was no excessive accumulation of Pb at the site. However, the concentration of Pb in surface soils was greater than the background level (<16 mg kg{sup -1}). The contamination level of Pb was as high as 67 mg kg{sup -1} near a patch of corn field where lime was frequently applied. A microfocused X-ray microprobe analysis showed the presence of Pb pellet fragments that predominantly contain oxidized Pb(II), suggesting that oxidative dissolution was occurring in soils. Dissolved Pb(II) can be readily retained in soils up to {approx}3,600 mg kg{sup -1} via inner-sphere and outer-sphere surface complexation on carbon and aluminol functional groups of soil components, suggesting that partitioning reactions control the concentration of Pb in soil solution. The fate of Pb is likely to be controlled by (1) oxidative dissolution process of Pb(0) pellets and (2) the release of outer-sphere and/or inner-sphere Pb surface complexes in humic substances and aluminosilicate/Al oxyhydroxides. Although no remedial actions are immediately required, the long-term accumulation of Pb in soils should be carefully monitored in protecting ecosystem and water quality at the dove hunting field.« less

Torsional Alfvén Waves in a Dipolar Magnetic Field

NASA Astrophysics Data System (ADS)

Nataf, H. C.; Tigrine, Z.; Cardin, P.; Schaeffer, N.

2017-12-01

The discovery of torsional Alfvén waves in the Earth's core (Gillet et al, 2010) is a strong motivation for investigating the properties of these waves. Here, we report on the first experimental study of such waves. Alfvén waves are difficult to excite and observe in liquid metals because of their high magnetic diffusivity. Nevertheless, we obtained clear signatures of such diffusive waves in our DTS experiment. In this setup, some 40 liters of liquid sodium are contained between a ro = 210 mm-radius stainless steel outer shell, and a ri = 74 mm-radius copper inner sphere. Both spherical boundaries can rotate independently around a common vertical axis. The inner sphere shells a strong permanent magnet, which produces a nearly dipolar magnetic field whose intensity falls from 175 mT at ri to 8 mT at ro in the equatorial plane. We excite Alfvén waves in the liquid sodium by applying a sudden jerk of the inner sphere. To study the effect of global rotation, which leads to the formation of geostrophic torsional Alfvén waves, we spin the experiment at rotation rates fo = fi up to 15 Hz. The Alfvén wave produces a clear azimuthal magnetic signal on magnetometers installed in a sleeve inside the fluid. We also probe the associated azimuthal velocity field using ultrasound Doppler velocimetry. Electric potentials at the surface of the outer sphere turn out to be very revealing as well. In parallel, we use the XSHELLS magnetohydrodynamics spherical code to model torsional Alfvén waves in the experimental conditions, and beyond. We explore both linear and non-linear regimes. We observe a strong excitation of inertial waves in the equatorial plane, where the wave transits from a region of strong magnetic field to a region dominated by rotation (see figure of meridian map of azimuthal velocity). These novel observations should help deciphering the dynamics of Alfvén waves in planetary cores.

Facial synthesis of carbon-coated ZnFe2O4/graphene and their enhanced lithium storage properties

NASA Astrophysics Data System (ADS)

Yao, Libing; Su, Qingmei; Xiao, Yanling; Huang, Min; Li, Haojie; Deng, Huihui; Du, Gaohui

2017-07-01

Carbon-coated ZnFe2O4 spheres with sizes of 110-180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g-1 and maintains a reversible capacity of 775 mAh g-1 after 150 cycles at a current density of 500 mA g-1. After being tested at 2 A g-1 for 700 cycles, the capacity still retains 617 mAh g-1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating ( 3-6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe2O4 spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries. [Figure not available: see fulltext.

Pool boiling from rotating and stationary spheres in liquid nitrogen

NASA Technical Reports Server (NTRS)

Cuan, Winston M.; Schwartz, Sidney H.

1988-01-01

Results are presented for a preliminary experiment involving saturated pool boiling at 1 atm from rotating 2 and 3 in. diameter spheres which were immersed in liquid nitrogen (LN2). Additional results are presented for a stationary, 2 inch diameter sphere, quenched in LN2, which were obtained utilizing a more versatile and complete experimental apparatus that will eventually be used for additional rotating sphere experiments. The speed for the rotational tests was varied from 0 to 10,000 rpm. The stationary experiments parametrically varied pressure and subcooling levels from 0 to 600 psig and from 0 to 50 F, respectively. During the rotational tests, a high speed photographic analysis was undertaken to measure the thickness of the vapor film surrounding the sphere. The average Nusselt number over the cooling period was plotted against the rotational Reynolds number. Stationary sphere results included local boiling heat transfer coefficients at different latitudinal locations, for various pressure and subcooling levels.

Influence of TiO2 hollow sphere size on its photo-reduction activity for toxic Cr(VI) removal.

PubMed

Cai, Jiabai; Wu, Xueqing; Zheng, Fengying; Li, Shunxing; Wu, Yaling; Lin, Yanping; Lin, Liting; Liu, Biwen; Chen, Qiaoying; Lin, Luxiu

2017-03-15

After polystyrene@titanium dioxide (PS@TiO 2 ) composite with different size was calcined at designated temperature, TiO 2 hollow sphere with controllable size was obtained for high efficient photo-reduction of Cr(VI). The feature of the TiO 2 hollow sphere was investigated by SEM, TEM, XRD, UV-Vis, and photoluminescence. The photo-reduction of Cr(VI) were measured for the performance assessment of the TiO 2 hollow sphere, Cr(VI) was used as an electron acceptor. After irradiation for 2h, the photo-reduction rate of Cr(VI) (pH=2.82) for TiO 2 (450nm) was 96%, which exhibited an increase of 5% and 8% compared with TiO 2 (370nm) and TiO 2 (600nm). The absorption edges of TiO 2 hollow sphere (450nm) was largest with the increasing of hollow sphere size from 370 to 600nm. The optimal hollow sphere size of TiO 2 was 450nm for the photo-reduction of Cr(VI), because the light-harvesting efficiency (the best of absorption edge) and photo-generated electron-hole separation rate (the best of photo-reduction rate) of TiO 2 hollow sphere were controlled by its hollow sphere size. In addition, we find that the behavior of the hydrogen production was inhibited by the coexistence Cr(VI) solution. This study can improve our understanding of the mechanism for the activity enhancement by the optimal hollow sphere size of TiO 2 . Copyright © 2016 Elsevier Inc. All rights reserved.

Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins† †Electronic supplementary information (ESI) available: Procedures for synthetic, spectroscopic, and electrochemical experiments. CCDC 1582750. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04682k

PubMed Central

Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K.; Smith, Peter T.

2018-01-01

The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input. Inspired by natural bioinorganic systems that feature precisely positioned hydrogen-bond donors in the secondary coordination sphere to direct chemical transformations occurring at redox-active metal centers, we now report the design, synthesis, and characterization of a series of iron tetraphenylporphyrin (Fe-TPP) derivatives bearing amide pendants at various positions at the periphery of the metal core. Proper positioning of the amide pendants greatly affects the electrocatalytic activity for carbon dioxide reduction to carbon monoxide. In particular, derivatives bearing proximal and distal amide pendants on the ortho position of the phenyl ring exhibit significantly larger turnover frequencies (TOF) compared to the analogous para-functionalized amide isomers or unfunctionalized Fe-TPP. Analysis of TOF as a function of catalyst standard reduction potential enables first-sphere electronic effects to be disentangled from second-sphere through-space interactions, suggesting that the ortho-functionalized porphyrins can utilize the latter second-sphere property to promote CO2 reduction. Indeed, the distally-functionalized ortho-amide isomer shows a significantly larger through-space interaction than its proximal ortho-amide analogue. These data establish that proper positioning of secondary coordination sphere groups is an effective design element for breaking electronic scaling relationships that are often observed in electrochemical CO2 reduction. PMID:29732079

General Method for the Synthesis of Hollow Mesoporous Carbon Spheres with Tunable Textural Properties.

PubMed

Mezzavilla, Stefano; Baldizzone, Claudio; Mayrhofer, Karl J J; Schüth, Ferdi

2015-06-17

A versatile synthetic procedure to prepare hollow mesoporous carbon spheres (HMCS) is presented here. This approach is based on the deposition of a homogeneous hybrid polymer/silica composite shell on the outer surface of silica spheres through the surfactant-assisted simultaneous polycondensation of silica and polymer precursors in a colloidal suspension. Such composite materials can be further processed to give hollow mesoporous carbon spheres. The flexibility of this method allows for independent control of the morphological (i.e., core diameter and shell thickness) and textural features of the carbon spheres. In particular, it is demonstrated that the size of the pores within the mesoporous shell can be precisely tailored over an extended range (2-20 nm) by simply adjusting the reaction conditions. In a similar fashion, also the specific carbon surface area as well as the total shell porosity can be tuned. Most importantly, the textural features can be adjusted without affecting the dimension or the morphology of the spheres. The possibility to directly modify the shell textural properties by varying the synthetic parameters in a scalable process represents a distinct asset over the multistep hard-templating (nanocasting) routes. As an exemplary application, Pt nanoparticles were encapsulated in the mesoporous shell of HMCS. The resulting Pt@HMCS catalyst showed an enhanced stability during the oxygen reduction reaction, one of the most important reactions in electrocatalysis. This new synthetic procedure could allow the expansion, perhaps even beyond the lab-scale, of advanced carbon nanostructured supports for applications in catalysis.

Red mud carbonation using carbon dioxide: Effects of carbonate and calcium ions on goethite surface properties and settling.

PubMed

Liang, Gaojie; Chen, Wenmi; Nguyen, Anh V; Nguyen, Tuan A H

2018-05-01

Carbonation using CO 2 appears as an attractive solution for disposing of red mud suspensions, an aluminum industry hazardous waste since it also offers an option for CO 2 sequestration. Here we report the novel findings that CO 3 2- together with Ca 2+ can significantly affect the surface properties and settling of goethite, a major component of red mud. Specifically, their effects on the goethite surface chemistry, colloidal interaction forces and settling in alkaline solutions are investigated. The surface potential becomes more negative by the formation of carbonate inner-sphere complexes on goethite surface. It is consistent with the strong repulsion, decreased particle size and settling velocity with increased carbonate concentrations as measured by atomic force microscopy, particle size analysis, and particle settling. Adding Ca 2+ that forms outer-sphere complexes with pre-adsorbed carbonate changes goethite surface charge negligibly. Changing repulsion to the attraction between goethite surfaces by increasing calcium dosage indicates the surface bridging, in accordance with the increased settling velocity. The adverse effect of carbonate on goethite flocculation is probably due to its specific chemisorption and competition with flocculants. By forming outer-sphere complexes together with the flocculant-calcium bridging effect, calcium ions can eliminate the negative influence of carbonate and improve the flocculation of goethite particles. These findings contribute to a better understanding of goethite particle interaction with salt ions and flocculants in controlling the particle behavior in the handling processes, including the red mud carbonation. Copyright © 2018 Elsevier Inc. All rights reserved.

Structural changes at the metal ion binding site during the phosphoglucomutase reaction.

PubMed

Ray, W J; Post, C B; Liu, Y; Rhyu, G I

1993-01-12

An electron density map of the reactive, Cd2+ form of crystalline phosphoglucomutase from X-ray diffraction studies shows that the enzymic phosphate donates a nonbridging oxygen to the ligand sphere of the bound metal ion, which appears to be tetracoordinate. 31P and 113Cd NMR spectroscopy are used to assess changes in the properties of bound Cd2+ produced by substrate/product and by substrate/product analog inhibitors. The approximately 50 ppm downfield shift of the 113Cd resonance on formation of the complex of dephosphoenzyme and glucose 1,6-bisphosphate is associated with the initial sugar-phosphate binding step and likely involves a change in the geometry of the coordinating ligands. This interpretation is supported by spectral studies involving various complexes of the active Co2+ and Ni(2+)-enzyme. In addition, there is a loss of the 31P-113Cd J coupling that characterizes the monophosphate complexes of the Cd2+ enzyme either during or immediately after the PO3- transfer step that produces the bisphosphate complex, indicating a further change at the metal binding site. The implications of these observations with respect to the PO3- transfer process in the phosphoglucomutase reaction are considered. The apparent plasticity of the ligand sphere of the active site metal ion in this system may allow a single metal ion to act as a chaperone for a nonbridging oxygen during PO3- transfer or to allow a change in metal ion coordination during catalysis. A general NMR line shape/chemical-exchange analysis for evaluating binding in protein-ligand systems when exchange is intermediate to fast on the NMR time scale is described. Its application to the present system involves multiple exchange sites that depend on a single binding rate, thereby adding further constraints to the analysis.

Individualized adjustments to reference phantom internal organ dosimetry—scaling factors given knowledge of patient internal anatomy

NASA Astrophysics Data System (ADS)

Wayson, Michael B.; Bolch, Wesley E.

2018-04-01

Various computational tools are currently available that facilitate patient organ dosimetry in diagnostic nuclear medicine, yet they are typically restricted to reporting organ doses to ICRP-defined reference phantoms. The present study, while remaining computational phantom based, provides straightforward tools to adjust reference phantom organ dose for both internal photon and electron sources. A wide variety of monoenergetic specific absorbed fractions were computed using radiation transport simulations for tissue spheres of varying size and separation distance. Scaling methods were then constructed for both photon and electron self-dose and cross-dose, with data validation provided from patient-specific voxel phantom simulations, as well as via comparison to the scaling methodology given in MIRD Pamphlet No. 11. Photon and electron self-dose was found to be dependent on both radiation energy and sphere size. Photon cross-dose was found to be mostly independent of sphere size. Electron cross-dose was found to be dependent on sphere size when the spheres were in close proximity, owing to differences in electron range. The validation studies showed that this dataset was more effective than the MIRD 11 method at predicting patient-specific photon doses for at both high and low energies, but gave similar results at photon energies between 100 keV and 1 MeV. The MIRD 11 method for electron self-dose scaling was accurate for lower energies but began to break down at higher energies. The photon cross-dose scaling methodology developed in this study showed gains in accuracy of up to 9% for actual patient studies, and the electron cross-dose scaling methodology showed gains in accuracy up to 9% as well when only the bremsstrahlung component of the cross-dose was scaled. These dose scaling methods are readily available for incorporation into internal dosimetry software for diagnostic phantom-based organ dosimetry.

Individualized adjustments to reference phantom internal organ dosimetry-scaling factors given knowledge of patient internal anatomy.

PubMed

Wayson, Michael B; Bolch, Wesley E

2018-04-13

Various computational tools are currently available that facilitate patient organ dosimetry in diagnostic nuclear medicine, yet they are typically restricted to reporting organ doses to ICRP-defined reference phantoms. The present study, while remaining computational phantom based, provides straightforward tools to adjust reference phantom organ dose for both internal photon and electron sources. A wide variety of monoenergetic specific absorbed fractions were computed using radiation transport simulations for tissue spheres of varying size and separation distance. Scaling methods were then constructed for both photon and electron self-dose and cross-dose, with data validation provided from patient-specific voxel phantom simulations, as well as via comparison to the scaling methodology given in MIRD Pamphlet No. 11. Photon and electron self-dose was found to be dependent on both radiation energy and sphere size. Photon cross-dose was found to be mostly independent of sphere size. Electron cross-dose was found to be dependent on sphere size when the spheres were in close proximity, owing to differences in electron range. The validation studies showed that this dataset was more effective than the MIRD 11 method at predicting patient-specific photon doses for at both high and low energies, but gave similar results at photon energies between 100 keV and 1 MeV. The MIRD 11 method for electron self-dose scaling was accurate for lower energies but began to break down at higher energies. The photon cross-dose scaling methodology developed in this study showed gains in accuracy of up to 9% for actual patient studies, and the electron cross-dose scaling methodology showed gains in accuracy up to 9% as well when only the bremsstrahlung component of the cross-dose was scaled. These dose scaling methods are readily available for incorporation into internal dosimetry software for diagnostic phantom-based organ dosimetry.

Thermo-fluid-dynamics of turbulent boundary layer over a moving continuous flat sheet in a parallel free stream

NASA Astrophysics Data System (ADS)

Afzal, Bushra; Noor Afzal Team; Bushra Afzal Team

2014-11-01

The momentum and thermal turbulent boundary layers over a continuous moving sheet subjected to a free stream have been analyzed in two layers (inner wall and outer wake) theory at large Reynolds number. The present work is based on open Reynolds equations of momentum and heat transfer without any closure model say, like eddy viscosity or mixing length etc. The matching of inner and outer layers has been carried out by Izakson-Millikan-Kolmogorov hypothesis. The matching for velocity and temperature profiles yields the logarithmic laws and power laws in overlap region of inner and outer layers, along with friction factor and heat transfer laws. The uniformly valid solution for velocity, Reynolds shear stress, temperature and thermal Reynolds heat flux have been proposed by introducing the outer wake functions due to momentum and thermal boundary layers. The comparison with experimental data for velocity profile, temperature profile, skin friction and heat transfer are presented. In outer non-linear layers, the lowest order momentum and thermal boundary layer equations have also been analyses by using eddy viscosity closure model, and results are compared with experimental data. Retired Professor, Embassy Hotel, Rasal Ganj, Aligarh 202001 India.

Three-Fluid Magnetohydrodynamic Modeling of the Solar Wind in the Outer Heliosphere

NASA Technical Reports Server (NTRS)

Usmanov, Arcadi V.; Goldstein, Melvyn L.; Matthaeus, William H.

2011-01-01

We have developed a three-fluid, fully three-dimensional magnetohydrodynamic model of the solar wind plasma in the outer heliosphere as a co-moving system of solar wind protons, electrons, and interstellar pickup protons, with separate energy equations for each species. Our approach takes into account the effects of electron heat conduction and dissipation of Alfvenic turbulence on the spatial evolution of the solar wind plasma and interplanetary magnetic fields. The turbulence transport model is based on the Reynolds decomposition of physical variables into mean and fluctuating components and uses the turbulent phenomenologies that describe the conversion of fluctuation energy into heat due to a turbulent cascade. We solve the coupled set of the three-fluid equations for the mean-field solar wind and the turbulence equations for the turbulence energy, cross helicity, and correlation length. The equations are written in the rotating frame of reference and include heating by turbulent dissipation, energy transfer from interstellar pickup protons to solar wind protons, and solar wind deceleration due to the interaction with the interstellar hydrogen. The numerical solution is constructed by the time relaxation method in the region from 0.3 to 100 AU. Initial results from the novel model are presented.

Transition from the adiabatic to the sudden limit in core-level photoemission: A model study of a localized system

NASA Astrophysics Data System (ADS)

Lee, J. D.; Gunnarsson, O.; Hedin, L.

1999-09-01

We consider core electron photoemission in a localized system, where there is a charge transfer excitation. Examples are transition metal and rare earth compounds, chemisorption systems, and high-Tc compounds. The system is modeled by three electron levels, one core level, and two outer levels. In the initital state the core level and one outer level is filled (a spinless two-electron problem). This model system is embedded in a solid state environment, and the implications of our model system results for solid state photoemission are discussed. When the core hole is created, the more localized outer level (d) is pulled below the less localized level (L). The spectrum has a leading peak corresponding to a charge transfer between L and d (``shakedown''), and a satellite corresponding to no charge transfer. The model has a Coulomb interaction between these levels and the continuum states into which the core electron is emitted. The model is simple enough to allow an exact numerical solution, and with a separable potential an analytic solution. Analytic results are also obtained in lowest order perturbation theory, and in the high-energy limit of the semiclassical approximation. We calculate the ratio r(ω) between the weights of the satellite and the main peak as a function of the photon energy ω. The transition from the adiabatic to the sudden limit is found to take place for quite small kinetic energies of the photoelectron. For such small energies, the variation of the dipole matrix elements is substantial and described by the energy scale E~d. Without the coupling to the photoelectron, the corresponding ratio r0(ω) shows a smooth turn-on of the satellite intensity, due to the turn on of the dipole matrix element. The characteristic energy scales are E~d and the satellite excitation energy δE. When the interaction potential with the continuum states is introduced an energy scale E~s=1/(2R~2s) enters, where R~s is a length scale of the interaction (scattering) potential. At threshold there is typically a (weak) constructive interference between intrinsic and extrinsic contributions, and the ratio r(ω)/r0(ω) is larger than its limiting value for large ω. The interference becomes small or weakly destructive for photoelectron energies of the order E~s. For larger photoelectron energies r(ω)/r0(ω) therefore typically has a weak undershoot. If this undershoot is neglected, r(ω)/r0(ω) reaches its limiting value on the energy scale E~s for the parameter range considered here. In a ``shake-up'' scenario, where the two outer levels do not cross as the core hole is created, we instead find that r(ω)/r0(ω) is typically reduced for small ω by interference effects, as in the case of plasmon excitation. Even for this shake-down case, however, the results are very different from those for a simple metal, where plasmons dominate the picture. In particular, the adiabatic to sudden transition takes place at much lower energies in the case of a localized excitation. The reasons for the differences are briefly discussed.

A review of iron and cobalt porphyrins, phthalocyanines, and related complexes for electrochemical and photochemical reduction of carbon dioxide

DOE PAGES

Manbeck, Gerald F.; Fujita, Etsuko

2015-03-30

This review summarizes research on the electrochemical and photochemical reduction of CO₂ using a variety of iron and cobalt porphyrins, phthalocyanines, and related complexes. Metalloporphyrins and metallophthalocyanines are visible light absorbers with extremely large extinction coefficients. However, yields of photochemically-generated active catalysts for CO₂ reduction are typically low owing to the requirement of a second photoinduced electron. This requirement is not relevant to the case of electrochemical CO₂ reduction. Recent progress on efficient and stable electrochemical systems includes the use of FeTPP catalysts that have prepositioned phenyl OH groups in their second coordination spheres. This has led to remarkable progressmore » in carrying out coupled proton-electron transfer reactions for CO₂ reduction. Such ground-breaking research has to be continued in order to produce renewable fuels in an economically feasible manner.« less

Hierarchical TiO2/C micro-nano spheres as high-performance anode materials for sodium ion batteries

NASA Astrophysics Data System (ADS)

Ma, Xiao; Zhang, Zhihui; Tian, Jianliya; Xu, Beibei; Ping, Qiushi; Wang, Baofeng

The hierarchical TiO2/C microspheres were obtained via a facile method of in-situ hydrolysis and spray drying. Antase TiO2 nanoparticles were coherent to microspheres TiO2/C due to the pyrolysis of carbon source (PVP). Besides, the favorable electron transfer from carbon to TiO2 improves the electronic conductivity of TiO2 via the presence of Ti-C bond within TiO2/C composite. Charge-discharge tests show that TiO2/C microspheres delivered a good rate capability of 106.1mAhg‑1 at the high current density of 5Ag‑1 and an enhanced cyclic capacity. The superior electrochemical performance could be ascribed to the porous micro-nano structure, smaller crystal size and increased conductivity. The synthesis of TiO2/C microspheres is easy to scale up for satisfying high-performance sodium storage.

Individually addressable vertically aligned carbon nanofiber-based electrochemical probes

NASA Astrophysics Data System (ADS)

Guillorn, M. A.; McKnight, T. E.; Melechko, A.; Merkulov, V. I.; Britt, P. F.; Austin, D. W.; Lowndes, D. H.; Simpson, M. L.

2002-03-01

In this paper we present the fabrication and initial testing results of high aspect ratio vertically aligned carbon nanofiber (VACNF)-based electrochemical probes. Electron beam lithography was used to define the catalytic growth sites of the VACNFs. Following catalyst deposition, VACNF were grown using a plasma enhanced chemical vapor deposition process. Photolithography was performed to realize interconnect structures. These probes were passivated with a thin layer of SiO2, which was then removed from the tips of the VACNF, rendering them electrochemically active. We have investigated the functionality of completed devices using cyclic voltammetry (CV) of ruthenium hexammine trichloride, a highly reversible, outer sphere redox system. The faradaic current obtained during CV potential sweeps shows clear oxidation and reduction peaks at magnitudes that correspond well with the geometry of these nanoscale electrochemical probes. Due to the size and the site-specific directed synthesis of the VACNFs, these probes are ideally suited for characterizing electrochemical phenomena with an unprecedented degree of spatial resolution.

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

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

PubMed Central

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; Sturchio, Neil C.

2017-01-01

Ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb+ species at the muscovite (001)–water interface during exchange with Na+. Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb+ desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb+ slowly transforms to a less stable outer-sphere Rb+. In contrast, Rb+ adsorption is about twice as fast, proceeding from Rb+ in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface. PMID:28598428

Regeneratively Cooled Porous Media Jacket

NASA Technical Reports Server (NTRS)

Mungas, Greg (Inventor); Fisher, David J. (Inventor); London, Adam Pollok (Inventor); Fryer, Jack Merrill (Inventor)

2013-01-01

The fluid and heat transfer theory for regenerative cooling of a rocket combustion chamber with a porous media coolant jacket is presented. This model is used to design a regeneratively cooled rocket or other high temperature engine cooling jacket. Cooling jackets comprising impermeable inner and outer walls, and porous media channels are disclosed. Also disclosed are porous media coolant jackets with additional structures designed to transfer heat directly from the inner wall to the outer wall, and structures designed to direct movement of the coolant fluid from the inner wall to the outer wall. Methods of making such jackets are also disclosed.

Comic ray flux anisotropies caused by astrospheres

NASA Astrophysics Data System (ADS)

Scherer, K.; Strauss, R. D.; Ferreira, S. E. S.; Fichtner, H.

2016-09-01

Huge astrospheres or stellar wind bubbles influence the propagation of cosmic rays at energies up to the TeV range and can act as small-scale sinks decreasing the cosmic ray flux. We model such a sink (in 2D) by a sphere of radius 10 pc embedded within a sphere of a radius of 1 kpc. The cosmic ray flux is calculated by means of backward stochastic differential equations from an observer, which is located at r0, to the outer boundary. It turns out that such small-scale sinks can influence the cosmic ray flux at the observer's location by a few permille (i.e. a few 0.1%), which is in the range of the observations by IceCube, Milagro and other large area telescopes.

SEURAT: SPH scheme extended with ultraviolet line radiative transfer

NASA Astrophysics Data System (ADS)

Abe, Makito; Suzuki, Hiroyuki; Hasegawa, Kenji; Semelin, Benoit; Yajima, Hidenobu; Umemura, Masayuki

2018-05-01

We present a novel Lyman alpha (Ly α) radiative transfer code, SEURAT (SPH scheme Extended with Ultraviolet line RAdiative Transfer), where line scatterings are solved adaptively with the resolution of the smoothed particle hydrodynamics (SPH). The radiative transfer method implemented in SEURAT is based on a Monte Carlo algorithm in which the scattering and absorption by dust are also incorporated. We perform standard test calculations to verify the validity of the code; (i) emergent spectra from a static uniform sphere, (ii) emergent spectra from an expanding uniform sphere, and (iii) escape fraction from a dusty slab. Thereby, we demonstrate that our code solves the {Ly} α radiative transfer with sufficient accuracy. We emphasize that SEURAT can treat the transfer of {Ly} α photons even in highly complex systems that have significantly inhomogeneous density fields. The high adaptivity of SEURAT is desirable to solve the propagation of {Ly} α photons in the interstellar medium of young star-forming galaxies like {Ly} α emitters (LAEs). Thus, SEURAT provides a powerful tool to model the emergent spectra of {Ly} α emission, which can be compared to the observations of LAEs.

Uniform electron gases. III. Low-density gases on three-dimensional spheres

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

Agboola, Davids; Knol, Anneke L.; Gill, Peter M. W., E-mail: peter.gill@anu.edu.au

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGFmore » centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids — the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) — and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.« less

Density and Viscosity Measurement of Liquid FeS at High Pressure and High Temperature Using Synchrotron X-ray

NASA Astrophysics Data System (ADS)

Yu, T.; Long, H.; Young, C.; Wang, L.; Chen, J.

2005-12-01

From previous experimental and theoretical studies, sulfur has been considered one of the possible light elements in the core that might be responsible for the large density deficit when compared with the theoretical pure Fe core (Ganapathy and Anders, 1974; Ahrens and Jeanloz, 1987). Therefore, understanding the physical properties of liquid FeS will help us reveal the details of the Earth?|s core. This study focused on the liquid state of sulfur in iron due to sulfur?|s lack of amount in the mantle; easiness to alloy with iron; and the predicted 5 wt% ~10 wt% amount of this light element in the core (Ahrens, 1979; Sherman, 1997). Modern development of the multi-anvil high pressure apparatus limits the pressure range of the experiments (<30 GPa). It is somewhat low if comparing with the outer core pressure condition. Therefore, extrapolation of data derived at low pressure range to the condition of the outer core (>130 GPa) has to be applied, and may produce results that are far from the true numbers. However, at the point while the techniques are limited, studying the physical properties of the liquid-phase FeS at relatively low pressures still provides us a better picture of the physical behavior of the outer core comparing with data derived from solid state FeS experiments. Pervious studies on the viscosity of the Fe-FeS system (LeBlanc and Secco, 1996; Dobson et al., 2000; Urakawa et al., 2001; Secco et al., 2002) have presented different values of viscosity numbers with a maximum difference of two orders of magnitude. We have conducted the density measurements of liquid FeS (~36 wt% of S) up to 5.6 GPa in pressure and 1673K in temperature using the in-situ synchrotron-source x-ray absorption setup at Beamline X17B2, NSLS. The viscosity measurements were conducted by the x-ray radiograph technique combined with the falling sphere method. The falling sphere method applied at the experiment is suitable for liquids with viscosities between 10-3 Pa-s and 105 Pa-s (LeBlanc et al., 1999). We used tungsten spheres in our viscosity measurement experiments. We analyzed the sphere falling motion in the sample chamber at high pressure and high temperature. And by applying our density compression curve of liquid FeS to the Stokes?| viscometry method, we were able to derive the viscosity of liquid FeS.

Experimental study of the flow in the wake of a stationary sphere immersed in a turbulent boundary layer

NASA Astrophysics Data System (ADS)

van Hout, René; Eisma, Jerke; Elsinga, Gerrit E.; Westerweel, Jerry

2018-02-01

In many applications, finite-sized particles are immersed in a turbulent boundary layer (TBL) and it is of interest to study wall effects on the instantaneous shedding of turbulence structures and associated mean velocity and Reynolds stress distributions. Here, 3D flow field dynamics in the wake of a prototypical, small sphere (D+=50 , 692

Cost-effective three dimensional Ag/polymer dyes/graphene-carbon spheres hybrids for high performance nonenzymatic sensor and its application in living cell H2O2 detection.

PubMed

Lu, Baoping; Yuan, Xuna; Ren, Yuehong; Shi, Qinghua; Wang, Song; Dong, Jinlong; Nan, Ze-Dong

2018-05-03

We describe a facile method to synthesize a new type of catalyst by electrodepositing Ag nanocrystals (AgNCs) on the different polymer dyes, Poly (methylene blue) (PMB) or Poly (4-(2-Pyridylazo)-Resorcinol) (PAR) modified graphene‑carbon spheres (GS) hybrids. The self-assembled GS take dual advantages of carbon spheres and graphene. Carbon spheres acts as nano-spacers prevent the aggregation of graphene and guarantee the fast electron transfer of GS. Secondly, polymerized dyes used here are beneficial for AgNCs growing as a linker. The effects of dyes on the growth habits, morphologies and catalytic properties for AgNCs were investigated. A novel electrochemical nonenzymatic sensor for hydrogen peroxide (H 2 O 2 ) detection is fabricated based on the Ag/Polymer dyes/GS ternary composites modified glass carbon electrode (GCE) for the first time. It was found that the proposed electrodes, especially for Ag/PMB/GS/GCE, displayed a peculiar electrocatalytic activity towards H 2 O 2 reduction synergistically as compared to Ag/PAR/GS/GCE or Ag/GS/GCE alone. Ag/PMB/GS/GCE showed a linear response over the H 2 O 2 concentration range of 0.5 to 1112 μM. The detection limit and sensitivity is 0.15 μM and 400 μA mM -1  cm -2 , respectively. These outstanding results enable the practical application of Ag/PMB/GS/GCE for the H 2 O 2 tracking released from MCF-7 (human breast cancer cells) with satisfactory results. Copyright © 2018 Elsevier B.V. All rights reserved.

Location dependent coordination chemistry and MRI relaxivity, in de novo designed lanthanide coiled coils† †Electronic supplementary information (ESI) available: Methods, peptide characterization data including mass spectrometry and analytical HPLC, sedimentation equilibrium data, circular dichroism, luminescence, and NMR data. See DOI: 10.1039/c5sc04101e

PubMed Central

Berwick, Matthew R.; Slope, Louise N.; Smith, Caitlin F.; King, Siobhan M.; Newton, Sarah L.; Gillis, Richard B.; Adams, Gary G.; Rowe, Arthur J.; Harding, Stephen E.; Britton, Melanie M.

2016-01-01

Herein, we establish for the first time the design principles for lanthanide coordination within coiled coils, and the important consequences of binding site translation. By interrogating design requirements and by systematically translating binding site residues, one can influence coiled coil stability and more importantly, the lanthanide coordination chemistry. A 10 Å binding site translation along a coiled coil, transforms a coordinatively saturated Tb(Asp)3(Asn)3 site into one in which three exogenous water molecules are coordinated, and in which the Asn layer is no longer essential for binding, Tb(Asp)3(H2O)3. This has a profound impact on the relaxivity of the analogous Gd(iii) coiled coil, with more than a four-fold increase in the transverse relaxivity (21 to 89 mM–1 s–1), by bringing into play, in addition to the outer sphere mechanism present for all Gd(iii) coiled coils, an inner sphere mechanism. Not only do these findings warrant further investigation for possible exploitation as MRI contrast agents, but understanding the impact of binding site translation on coordination chemistry has important repercussions for metal binding site design, taking us an important step closer to the predictable and truly de novo design of metal binding sites, for new functional applications. PMID:29899946

The influence of temperature on a nutty-cake structural material: LiMn1-xFexPO4 composite with LiFePO4 core and carbon outer layer for lithium-ion battery

NASA Astrophysics Data System (ADS)

Huo, Zhen-Qing; Cui, Yu-Ting; Wang, Dan; Dong, Yue; Chen, Li

2014-01-01

The extremely low electronic conductivity, slow ion diffusion kinetics, and the Jahn-Teller effect of LiMnPO4 limit its electrochemical performance. In this work, a nutty-cake structural C-LiMn1-xFexPO4-LiFePO4 cathode material is synthesized by hydrothermal method and further calcined at different temperatures. The influence of calcination temperature on the electrochemical behavior is investigated by X-ray diffractometer, scanning electron microscope, field-emission high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and charge-discharge tests. And the performance of C-LiMn1-xFexPO4-LiFePO4 materials has a relationship with its crystal structure. The well-crystallized Sample-600 calcined at 600 °C shows the smallest charge transfer resistance, the largest lithium ion diffusion coefficient (DLi) and the best cycling stability. The discharge capacity of Sample-600 holds around 112 mAh g-1 after the 3rd cycle at 0.1 C rate. The performances improvement of C-LiMn1-xFexPO4-LiFePO4 material can be mainly attributed to the iron diffusion from the LiFePO4 core to the outer LiMnPO4 layer under appropriate calcination temperature.

Electron Microscopy of Ultrathin Sections of Sporosarcina ureae

PubMed Central

Mazanec, K.; Kocur, M.; Martinec, T.

1965-01-01

Mazanec, K. (J. E. Purkyně University, Brno, Czechoslovakia), M. Kocur, and T. Martinec. Electron microscopy of ultrathin sections of Sporosarcina ureae. J. Bacteriol. 90:808–816. 1965.—Ultrathin sections of Sporosarcina ureae cells were studied by means of electron microscopy. The cell wall consists of several layers and is 340 A thick. The cytoplasm is of globular structure and includes ribosomelike structures, occasional mesosomes, and inclusions not precisely identifiable. The nuclear area has various shapes and is formed by filaments 10 to 20 A thick which proceed in various directions. Cell division occurs similarly to that of sarcinate. Both synchronic and asynchronic cell division was observed. The spores of S. ureae consist of an outer coat having several layers, a cortex, a spore wall, and cytoplasm. The results of the present investigation substantiate our previous suggestion that S. ureae should be transferred from the family Micrococcaceae to the family Bacillaceae. Images PMID:16562085

Advanced Electrochemistry of Individual Metal Clusters Electrodeposited Atom by Atom to Nanometer by Nanometer.

PubMed

Kim, Jiyeon; Dick, Jeffrey E; Bard, Allen J

2016-11-15

Metal clusters are very important as building blocks for nanoparticles (NPs) for electrocatalysis and electroanalysis in both fundamental and applied electrochemistry. Attention has been given to understanding of traditional nucleation and growth of metal clusters and to their catalytic activities for various electrochemical applications in energy harvesting as well as analytical sensing. Importantly, understanding the properties of these clusters, primarily the relationship between catalysis and morphology, is required to optimize catalytic function. This has been difficult due to the heterogeneities in the size, shape, and surface properties. Thus, methods that address these issues are necessary to begin understanding the reactivity of individual catalytic centers as opposed to ensemble measurements, where the effect of size and morphology on the catalysis is averaged out in the measurement. This Account introduces our advanced electrochemical approaches to focus on each isolated metal cluster, where we electrochemically fabricated clusters or NPs atom by atom to nanometer by nanometer and explored their electrochemistry for their kinetic and catalytic behavior. Such approaches expand the dimensions of analysis, to include the electrochemistry of (1) a discrete atomic cluster, (2) solely a single NP, or (3) individual NPs in the ensemble sample. Specifically, we studied the electrocatalysis of atomic metal clusters as a nascent electrocatalyst via direct electrodeposition on carbon ultramicroelectrode (C UME) in a femtomolar metal ion precursor. In addition, we developed tunneling ultramicroelectrodes (TUMEs) to study electron transfer (ET) kinetics of a redox probe at a single metal NP electrodeposited on this TUME. Owing to the small dimension of a NP as an active area of a TUME, extremely high mass transfer conditions yielded a remarkably high standard ET rate constant, k 0 , of 36 cm/s for outer-sphere ET reaction. Most recently, we advanced nanoscale scanning electrochemical microscopy (SECM) imaging to resolve the electrocatalytic activity of individual electrodeposited NPs within an ensemble sample yielding consistent high k 0 values of ≥2 cm/s for the hydrogen oxidation reaction (HOR) at different NPs. We envision that our advanced electrochemical approaches will enable us to systematically address structure effects on the catalytic activity, thus providing a quantitative guideline for electrocatalysts in energy-related applications.

Facilitated extracellular electron transfer of Shewanella loihica PV-4 by antimony-doped tin oxide nanoparticles as active microelectrodes.

PubMed

Zhang, Xiaojian; Liu, Huan; Wang, Jinrong; Ren, Guangyuan; Xie, Beizhen; Liu, Hong; Zhu, Ying; Jiang, Lei

2015-11-28

Dissimilatory metal reducing bacteria are capable of extracellular electron transfer (EET) to insoluble metal oxides as external electron acceptors for their anaerobic respiration, which is recognized as an important energy-conversion process in natural and engineered environments, such as in mineral cycling, bioremediation, and microbial fuel/electrolysis cells. However, the low EET efficiency remains one of the major bottlenecks for its practical application. We report firstly that the microbial current generated by Shewanella loihica PV-4 (S. loihica PV-4) could be greatly improved that is up to ca. 115 fold, by adding antimony-doped tin oxide (ATO) nanoparticles in the electrochemical reactor. The results demonstrate that the biocompatible, electrically conductive ATO nanoparticles acted as active microelectrodes could facilitate the formation of a cells/ATO composite biofilm and the reduction of the outer membrane c-type cytochromes (OM c-Cyts) that are beneficial for the electron transfer from cells to electrode. Meanwhile, a synergistic effect between the participation of OM c-Cyts and the accelerated EET mediated by cell-secreted flavins may play an important role for the enhanced current generation in the presence of ATO nanoparticles. Moreover, it is worth noting that the TCA cycle in S. loihica PV-4 cells is activated by adding ATO nanoparticles, even if the potential is poised at +0.2 V, thereby also improving the EET process. The results presented here may provide a simple and effective strategy to boost the EET of S. loihica PV-4 cells, which is conducive to providing potential applications in bioelectrochemical systems.

CHARACTERIZATION OF THE INNER DISK AROUND HD 141569 A FROM KECK/NIRC2 L-BAND VORTEX CORONAGRAPHY

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

Mawet, Dimitri; Bottom, Michael; Matthews, Keith

HD 141569 A is a pre-main sequence B9.5 Ve star surrounded by a prominent and complex circumstellar disk, likely still in a transition stage from protoplanetary to debris disk phase. Here, we present a new image of the third inner disk component of HD 141569 A made in the L ′ band (3.8 μ m) during the commissioning of the vector vortex coronagraph that has recently been installed in the near-infrared imager and spectrograph NIRC2 behind the W.M. Keck Observatory Keck II adaptive optics system. We used reference point-spread function subtraction, which reveals the innermost disk component from the innermore » working distance of ≃23 au and up to ≃70 au. The spatial scale of our detection roughly corresponds to the optical and near-infrared scattered light, thermal Q , N , and 8.6 μ m PAH emission reported earlier. We also see an outward progression in dust location from the L ′ band to the H band (Very Large Telescope/SPHERE image) to the visible ( Hubble Space Telescope ( HST )/STIS image), which is likely indicative of dust blowout. The warm disk component is nested deep inside the two outer belts imaged by HST-NICMOS in 1999 (at 406 and 245 au, respectively). We fit our new L ′-band image and spectral energy distribution of HD 141569 A with the radiative transfer code MCFOST. Our best-fit models favor pure olivine grains and are consistent with the composition of the outer belts. While our image shows a putative very faint point-like clump or source embedded in the inner disk, we did not detect any true companion within the gap between the inner disk and the first outer ring, at a sensitivity of a few Jupiter masses.« less

Triplet-triplet energy transfer between luminescent probes bound to albumins

NASA Astrophysics Data System (ADS)

Mel'Nikov, A. G.; Saletskii, A. M.; Kochubey, V. I.; Pravdin, A. B.; Kurchatov, I. S.; Mel'Nikov, G. V.

2010-08-01

The interaction of polar and nonpolar luminescent probes with human blood serum albumins is studied by absorption and luminescence spectroscopy. It is found that the probes (polar eosin and nonpolar anthracene) can efficiently bind to proteins. The radii of the quenching spheres of energy-donor (eosin) triplet states in the presence of an acceptor (anthracene) in the process of the triplet-triplet energy transfer in proteins are determined for homogeneous and inhomogeneous distributions of acceptor molecules over the solution volume. It is shown that a decrease in the radius of the quenching sphere observed upon the addition of sodium dodecylsulfate surfactant is caused by structural changes in the protein.

Enhanced heat transfer with full circumferential ribs in helical pipe

NASA Astrophysics Data System (ADS)

Chang, S. W.; Su, L. M.; Yang, T. L.

2002-08-01

This paper describes an experimental study of heat transfers in the smooth-walled and rib-roughened helical pipes with reference to the design of enhanced cooling passages in the cylinder head and liner of a marine propulsive diesel engine. The manner in which the repeated ribs modify the forced heat convection in the helical pipe is considered for the case where the flow is turbulent upon entering the coil but laminar in further downstream. A selection of experimental results illustrates the individual and interactive effects of Dean vortices and rib-flows on heat transfer along the inner and outer helixes of coils. The experimental-based observations reveal that the centrifugal force modifies the heat transfer in a manner to generate circumferential heat transfer variation with better cooling performance on the outer edge relative to its inner counterpart even with the agitated flow field caused by the repeated ribs. Heat transfer augmentation factor in the range of 1.3 - 3 times of the smooth-walled level is achieved using the present ribbing geometry. A set of empirical correlations based on the experimental data has been developed to permit the evaluation of heat transfers along the inner and outer helixes of the smooth-walled and rib-roughened helical pipes.

Sliding friction of nanocomposite WC1-x/C coatings: transfer film and its influence on tribology.

PubMed

Liu, Y; Gubisch, M; Spiess, L; Schaefer, J A

2009-06-01

The transfer film on steel spheres formed in reciprocating sliding against nanocomposite coatings based on nanocrystalline WC1-x in amorphous carbon matrix is characterized and correlated with the tribological properties measured by a precision microtribometer. With the presence of transfer film, a coefficient of friction approximately 0.13 and a depth wear rate approximately 0.35 x 10(-10) m/N.Pass were obtained. The central zone of the transfer film covering approximately 25% of the Hertz contact area is intact while cracks and wear debris are found in the vast peripheral area. It is also heavily oxidized due to the absence of carbon, which is located at the peripherals and acts as lubricants. We propose that the oxidation of WC and adhesion of the oxides to the surface of sphere is the main mechanism for the buildup of the transfer films. With the thickening of the film, the internal stress increases. Under the shear stress, spalling and cracking of the transfer film take place. The overall tribological performance of the coatings is therefore a competing process of buildup and spalling of transfer films.

Analysis and Characterization of Proteins Associated with Outer Membrane Vesicles Secreted by Cronobacter spp.

PubMed Central

Kothary, Mahendra H.; Gopinath, Gopal R.; Gangiredla, Jayanthi; Rallabhandi, Prasad V.; Harrison, Lisa M.; Yan, Qiong Q.; Chase, Hannah R.; Lee, Boram; Park, Eunbi; Yoo, YeonJoo; Chung, Taejung; Finkelstein, Samantha B.; Negrete, Flavia J.; Patel, Isha R.; Carter, Laurenda; Sathyamoorthy, Venugopal; Fanning, Séamus; Tall, Ben D.

2017-01-01

Little is known about secretion of outer membrane vesicles (OMVs) by Cronobacter. In this study, OMVs isolated from Cronobacter sakazakii, Cronobacter turicensis, and Cronobacter malonaticus were examined by electron microscopy (EM) and their associated outer membrane proteins (OMP) and genes were analyzed by SDS-PAGE, protein sequencing, BLAST, PCR, and DNA microarray. EM of stained cells revealed that the OMVs are secreted as pleomorphic micro-vesicles which cascade from the cell's surface. SDS-PAGE analysis identified protein bands with molecular weights of 18 kDa to >100 kDa which had homologies to OMPs such as GroEL; OmpA, C, E, F, and X; MipA proteins; conjugative plasmid transfer protein; and an outer membrane auto-transporter protein (OMATP). PCR analyses showed that most of the OMP genes were present in all seven Cronobacter species while a few genes (OMATP gene, groEL, ompC, mipA, ctp, and ompX) were absent in some phylogenetically-related species. Microarray analysis demonstrated sequence divergence among the OMP genes that was not captured by PCR. These results support previous findings that OmpA and OmpX may be involved in virulence of Cronobacter, and are packaged within secreted OMVs. These results also suggest that other OMV-packaged OMPs may be involved in roles such as stress response, cell wall and plasmid maintenance, and extracellular transport. PMID:28232819

Numerical experiments on charging of a spherical body in a plasma with Maxwellian distributions of charged particles

NASA Astrophysics Data System (ADS)

Krasovsky, Victor L.; Kiselyov, Alexander A.

2017-12-01

New results of numerical simulation of collisionless plasma perturbation caused by a sphere absorbing electrons and ions are presented. Consideration is given to nonstationary phenomena accompanying the process of charging as well as to plasma steady state reached at long times. Corresponding asymptotic values of charges of the sphere and trapped-ion cloud around it have been found along with self-consistent electric field pattern depending on parameters of the unperturbed plasma. It is established that contribution of the trapped ions to screening of the charged sphere can be quite significant, so that the screening becomes essentially nonlinear in nature. A simple interconnection between the sphere radius, electron and ion Debye lengths has been revealed as the condition for maximum trapped-ion effect. Kinetic structure of the space charge induced in the plasma is discussed with relation to the specific form of the unperturbed charged particle distribution functions.

THREE-DIMENSIONAL NON-VACUUM PULSAR OUTER-GAP MODEL: LOCALIZED ACCELERATION ELECTRIC FIELD IN THE HIGHER ALTITUDES

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

Hirotani, Kouichi

2015-01-10

We investigate the particle accelerator that arises in a rotating neutron-star magnetosphere. Simultaneously solving the Poisson equation for the electro-static potential, the Boltzmann equations for relativistic electrons and positrons, and the radiative transfer equation, we demonstrate that the electric field is substantially screened along the magnetic field lines by pairs that are created and separated within the accelerator. As a result, the magnetic-field-aligned electric field is localized in higher altitudes near the light cylinder and efficiently accelerates the positrons created in the lower altitudes outward but does not accelerate the electrons inward. The resulting photon flux becomes predominantly outward, leadingmore » to typical double-peak light curves, which are commonly observed from many high-energy pulsars.« less

The Role of the Dynamic Plasmapause on Outer Radiation Belt Electron Flux Enhancement and Three-Belt Structure Formation

NASA Astrophysics Data System (ADS)

Bruff, M.; Jaynes, A. N.; Zhao, H.; Malaspina, D.

2017-12-01

The plasmasphere is a highly dynamic toroidal region of cold, dense plasma around Earth. Plasma waves exist both inside and outside this region and can contribute to the loss and acceleration of high energy outer radiation belt electrons. Early observational studies found an apparent correlation on long time scales between the observed inner edge of the outer radiation belt and the simulated innermost plasmapause location. More recent work using high resolution Van Allen Probe satellite data has found a more complex relationship. The aim of this project was to provide a systematic study of the location and dynamics of the plasmapause compared to the MeV electrons in the outer radiation belt. We used spin-averaged electron flux data from the Relativistic Electron Proton Telescope (REPT) and density data derived from the EFW instrument on the Van Allen Probe satellites. We analyzed these data to determine the standoff distance of the location of peak electron flux of the outer belt MeV electrons from the plasmapause. We found that the location of peak flux was consistently outside but within ΔL=2.5 from the innermost location of the plasmapause at enhancement times, with an average standoff distance ΔL=1.0 +/- 0.5. This is consistent with the current model of chorus enhancement and previous observations of chorus activity. Finally, we identified "three-belt" structure events where a second outer belt formed and found a repeated pattern of plasmapause dynamics associated with specific changes in electron flux required to generate and sustain these structures. This study is significant to improving our understanding of how the plasmasphere under differing conditions can both shield Earth from or worsen the impacts of geomagnetic activity.

Mechanisms and Dynamics of Abiotic and Biotic Interactions at Environmental Interfaces

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

Roso, Kevin M.

The Stanford EMSI (SEMSI) was established in 2004 through joint funding by the National Science Foundation and the OBER-ERSD. It encompasses a number of universities and national laboratories. The PNNL component of the SEMSI is funded by ERSD and is the focus of this report. This component has the objective of providing theory support to the SEMSI by bringing computational capabilities and expertise to bear on important electron transfer problems at mineral/water and mineral/microbe interfaces. PNNL staff member Dr. Kevin Rosso, who is also ''matrixed'' into the Environmental Molecular Sciences Laboratory (EMSL) at PNNL, is a co-PI on the SEMSImore » project and the PNNL lead. The EMSL computational facilities being applied to the SEMSI project include the 11.8 teraflop massively-parallel supercomputer. Science goals of this EMSL/SEMSI partnership include advancing our understanding of: (1) The kinetics of U(VI) and Cr(VI) reduction by aqueous and solid-phase Fe(II), (2) The structure of mineral surfaces in equilibrium with solution, and (3) Mechanisms of bacterial electron transfer to iron oxide surfaces via outer-membrane cytochromes.« less

An Inner-Sphere Mechanism for Molecular Oxygen Reduction Catalyzed by Copper Amine Oxidases

PubMed Central

Mukherjee, Arnab; Smirnov, Valeriy V.; Lanci, Michael P.; Brown, Doreen E.; Shepard, Eric M.; Dooley, David M.; Roth, Justine P.

2008-01-01

Copper and topaquinone (TPQ) containing amine oxidases utilize O2 for the metabolism of biogenic amines while concomitantly generating H2O2 for use by the cell. The mechanism of O2 reduction has been the subject of long-standing debate due to the obscuring influence of a proton-coupled electron transfer between the tyrosine-derived TPQ and copper, a rapidly established equilibrium precluding assignment of the enzyme in its reactive form. Here we show that substrate-reduced pea seedling amine oxidase (PSAO) exists predominantly in the CuI, TPQ semiquinone state. A new mechanistic proposal for O2 reduction is advanced on the basis of thermodynamic considerations together with kinetic studies (at varying pH, temperature and viscosity), the identification of steady-state intermediates and the analysis of competitive oxygen kinetic isotope effects: 18O KIEs, [kcat/KM(16,16O2)]/[kcat/KM(16,18O2)]. The 18O KIE = 1.0136 ± 0.0013 at pH 7.2 is independent of temperature from 5 to 47°C and insignificantly changed to 1.0122 ± 0.0020 upon raising the pH to 9, thus indicating the absence of kinetic complexity. Using density functional methods, the effect is found to be precisely in the range expected for reversible O2 binding to CuI to afford a superoxide, [CuII(η1-O2)−I]+, intermediate. Electron transfer from the TPQ semiquinone follows in the first irreversible step to form a peroxide, CuII(η1-O2)−II, intermediate driving the reduction of O2. The similar 18O KIEs reported for copper amine oxidases from other sources raise the possibility that all enzymes react by related inner-sphere mechanisms although additional experiments are needed to test this proposal. PMID:18582059

Hierarchical Vanadium Pentoxide Spheres as High-Performance Anode Materials for Sodium-Ion Batteries.

PubMed

Su, Dawei; Dou, Shixue; Wang, Guoxiu

2015-09-07

We report the synthesis of hierarchical vanadium pentoxide (V2 O5 ) spheres as anode materials for sodium-ion batteries (Na-ion batteries). Through field emission scanning electron microscopy, X-ray diffraction, and transmission electron microscopy characterizations, it was found that the as-prepared V2 O5 spheres are composed of primary nanoparticles with pores between them. The as-prepared hierarchical V2 O5 spheres achieved a discharge capacity of 271 mA h g(-1) at a current density of 40 mA g(-1) , and 177 mA h g(-1) discharge capacity after 100 cycles. Even at high current densities, V2 O5 spheres still delivered high capacity and superior cyclability (179 and 140 mA h g(-1) discharge capacities at 640 and 1280 mA g(-1) current densities, respectively). The promising electrochemical performances of V2 O5 spheres should be ascribed to the unique architecture of hierarchical spheres and the predominant exposed (110) facets, which provides open interlayers for facile sodium ion intercalation. Each nanoparticle contains predominantly exposed (110) crystal planes. The ex situ FESEM analysis revealed that the pores formed by the primary nanocrystals effectively buffer volume changes in the electrode during cycling, contributing to the excellent cycling performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deconvolution of Raman spectroscopic signals for electrostatic, H-bonding, and inner-sphere interactions between ions and dimethyl phosphate in solution

PubMed Central

Christian, Eric L; Anderson, Vernon E.; Harris, Michael E

2011-01-01

Quantitative analysis of metal ion-phosphodiester interactions is a significant experimental challenge due to the complexities introduced by inner-sphere, outer-sphere (H-bonding with coordinated water), and electrostatic interactions that are difficult to isolate in solution studies. Here, we provide evidence that inner-sphere, H-bonding and electrostatic interactions between ions and dimethyl phosphate can be deconvoluted through peak fitting in the region of the Raman spectrum for the symmetric stretch of non-bridging phosphate oxygens (νsPO 2-). An approximation of the change in vibrational spectra due to different interaction modes is achieved using ions capable of all or a subset of the three forms of metal ion interaction. Contribution of electrostatic interactions to ion-induced changes to the Raman νsPO2- signal could be modeled by monitoring attenuation of νsPO2- in the presence of tetramethylammonium, while contribution of H-bonding and inner-sphere coordination could be approximated from the intensities of altered νsPO2- vibrational modes created by an interaction with ammonia, monovalent or divalent ions. A model is proposed in which discrete spectroscopic signals for inner-sphere, H-bonding, and electrostatic interactions are sufficient to account for the total observed change in νsPO2- signal due to interaction with a specific ion capable of all three modes of interaction. Importantly, the quantitative results are consistent with relative levels of coordination predicted from absolute electronegativity and absolute hardness of alkali and alkaline earth metals. PMID:21334281

Perfect fluid tori orbiting Kehagias-Sfetsos naked singularities

NASA Astrophysics Data System (ADS)

Stuchlík, Z.; Pugliese, D.; Schee, J.; Kučáková, H.

2015-09-01

We construct perfect fluid tori in the field of the Kehagias-Sfetsos (K-S) naked singularities. These are spherically symmetric vacuum solutions of the modified Hořava quantum gravity, characterized by a dimensionless parameter ω M^2, combining the gravitational mass parameter M of the spacetime with the Hořava parameter ω reflecting the role of the quantum corrections. In dependence on the value of ω M^2, the K-S naked singularities demonstrate a variety of qualitatively different behavior of their circular geodesics that is fully reflected in the properties of the toroidal structures, demonstrating clear distinction to the properties of the torii in the Schwarzschild spacetimes. In all of the K-S naked singularity spacetimes the tori are located above an "antigravity" sphere where matter can stay in a stable equilibrium position, which is relevant for the stability of the orbiting fluid toroidal accretion structures. The signature of the K-S naked singularity is given by the properties of marginally stable tori orbiting with the uniform distribution of the specific angular momentum of the fluid, l= const. In the K-S naked singularity spacetimes with ω M^2 > 0.2811, doubled tori with the same l= const can exist; mass transfer between the outer torus and the inner one is possible under appropriate conditions, while only outflow to the outer space is allowed in complementary conditions. In the K-S spacetimes with ω M^2 < 0.2811, accretion from cusped perfect fluid tori is not possible due to the non-existence of unstable circular geodesics.

Metastable primordial germ cell-like state induced from mouse embryonic stem cells by Akt activation

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

Yamano, Noriko; Kimura, Tohru, E-mail: tkimura@patho.med.osaka-u.ac.jp; Watanabe-Kushima, Shoko

Specification to primordial germ cells (PGCs) is mediated by mesoderm-induction signals during gastrulation. We found that Akt activation during in vitro mesodermal differentiation of embryonic stem cells (ESCs) generated self-renewing spheres with differentiation states between those of ESCs and PGCs. Essential regulators for PGC specification and their downstream germ cell-specific genes were expressed in the spheres, indicating that the sphere cells had commenced differentiation to the germ lineage. However, the spheres did not proceed to spermatogenesis after transplantation into testes. Sphere cell transfer to the original feeder-free ESC cultures resulted in chaotic differentiation. In contrast, when the spheres were culturedmore » on mouse embryonic fibroblasts or in the presence of ERK-cascade and GSK3 inhibitors, reversion to the ESC-like state was observed. These results indicate that Akt signaling promotes a novel metastable and pluripotent state that is intermediate to those of ESCs and PGCs.« less

Observational evidence of competing source, loss, and transport processes for relativistic electrons in Earth's outer radiation belt

NASA Astrophysics Data System (ADS)

Turner, Drew; Mann, Ian; Usanova, Maria; Rodriguez, Juan; Henderson, Mike; Angelopoulos, Vassilis; Morley, Steven; Claudepierre, Seth; Li, Wen; Kellerman, Adam; Boyd, Alexander; Kim, Kyung-Chan

Earth’s outer electron radiation belt is a region of extreme variability, with relativistic electron intensities changing by orders of magnitude over time scales ranging from minutes to years. Extreme variations of outer belt electrons ultimately result from the relative impacts of various competing source (and acceleration), loss, and transport processes. Most of these processes involve wave-particle interactions between outer belt electrons and different types of plasma waves in the inner magnetosphere, and in turn, the activity of these waves depends on different solar wind and magnetospheric driving conditions and thus can vary drastically from event to event. Using multipoint analysis with data from NASA’s Van Allen Probes, THEMIS, and SAMPEX missions, NOAA’s GOES and POES constellations, and ground-based observatories, we present results from case studies revealing how different source/acceleration and loss mechanisms compete during active periods to result in drastically different distributions of outer belt electrons. By using a combination of low-Earth orbiting and high-altitude-equatorial orbiting satellites, we briefly review how it is possible to get a much more complete picture of certain wave activity and electron losses over the full range of MLTs and L-shells throughout the radiation belt. We then show example cases highlighting the importance of particular mechanisms, including: substorm injections and whistler-mode chorus waves for the source and acceleration of relativistic electrons; magnetopause shadowing and wave-particle interactions with EMIC waves for sudden losses; and ULF wave activity for driving radial transport, a process which is important for redistributing relativistic electrons, contributing both to acceleration and loss processes. We show how relativistic electron enhancement events involve local acceleration that is consistent with wave-particle interactions between a seed population of 10s to 100s of keV electrons, with a source in the plasma sheet, and chorus waves. We show how sudden losses during outer belt dropout events are dominated at higher L-shells (L>~4) by magnetopause shadowing and outward radial transport, which is effective over the full ranges of energy and equatorial pitch angle of outer belt electrons, but at lower L-shells near the plasmapause, energy and pitch angle dependent losses can also occur and are consistent with rapid scattering by interactions between relativistic electrons and EMIC waves. We show cases demonstrating how these different processes occur simultaneously during active periods, with relative effects that vary as a function of L-shell and electron energy and pitch angle. Ultimately, our results highlight the complexity of competing source/acceleration, loss, and transport processes in Earth’s outer radiation belt and the necessity of using multipoint observations to disambiguate between them for future studies.

Formation of Ketenimines via the Palladium-Catalyzed Decarboxylative π-Allylic Rearrangement of N-Alloc Ynamides.

PubMed

Alexander, Juliana R; Cook, Matthew J

2017-11-03

A new approach for the formation of ketenimines via a decarboxylative allylic rearrangement pathway that does not require strong stabilizing or protecting groups has been developed. The products can be readily hydrolyzed into their corresponding secondary amides or reacted with sulfur ylides to perform an additional [2,3]-Wittig process. Mechanistic studies suggest an outer-sphere process in which reductive alkylation is rate-limiting.

NORSTAR Project: Norfolk public schools student team for acoustical research

NASA Technical Reports Server (NTRS)

Fortunato, Ronald C.

1987-01-01

Development of the NORSTAR (Norfolk Public Student Team for Acoustical Research) Project includes the definition, design, fabrication, testing, analysis, and publishing the results of an acoustical experiment. The student-run program is based on a space flight organization similar to the Viking Project. The experiment will measure the scattering transfer of momentum from a sound field to spheres in a liquid medium. It is hoped that the experimental results will shed light on a difficult physics problem - the difference in scattering cross section (the overall effect of the sound wave scattering) for solid spheres and hollow spheres of differing wall thicknesses.

Use of beam deflection to control an electron beam wire deposition process

NASA Technical Reports Server (NTRS)

Taminger, Karen M. (Inventor); Hofmeister, William H. (Inventor); Hafley, Robert A. (Inventor)

2013-01-01

A method for controlling an electron beam process wherein a wire is melted and deposited on a substrate as a molten pool comprises generating the electron beam with a complex raster pattern, and directing the beam onto an outer surface of the wire to thereby control a location of the wire with respect to the molten pool. Directing the beam selectively heats the outer surface of the wire and maintains the position of the wire with respect to the molten pool. An apparatus for controlling an electron beam process includes a beam gun adapted for generating the electron beam, and a controller adapted for providing the electron beam with a complex raster pattern and for directing the electron beam onto an outer surface of the wire to control a location of the wire with respect to the molten pool.

Multishell inertial confinement fusion target

DOEpatents

Holland, James R.; Del Vecchio, Robert M.

1984-01-01

A method of fabricating multishell fuel targets for inertial confinement fusion usage. Sacrificial hemispherical molds encapsulate a concentric fuel pellet which is positioned by fiber nets stretched tautly across each hemispherical mold section. The fiber ends of the net protrude outwardly beyond the mold surfaces. The joint between the sacrificial hemispheres is smoothed. A ceramic or glass cover is then deposited about the finished mold surfaces to produce an inner spherical surface having continuously smooth surface configuration. The sacrificial mold is removed by gaseous reaction accomplished through the porous ceramic cover prior to enclosing of the outer sphere by addition of an outer coating. The multishell target comprises the inner fuel pellet concentrically arranged within a surrounding coated cover or shell by fiber nets imbedded within the cover material.

Multishell inertial confinement fusion target

DOEpatents

Holland, James R.; Del Vecchio, Robert M.

1987-01-01

A method of fabricating multishell fuel targets for inertial confinement fusion usage. Sacrificial hemispherical molds encapsulate a concentric fuel pellet which is positioned by fiber nets stretched tautly across each hemispherical mold section. The fiber ends of the net protrude outwardly beyond the mold surfaces. The joint between the sacrificial hemispheres is smoothed. A ceramic or glass cover is then deposited about the finished mold surfaces to produce an inner spherical surface having continuously smooth surface configuration. The sacrificial mold is removed by gaseous reactions accomplished through the porous ceramic cover prior to enclosing of the outer sphere by addition of an outer coating. The multishell target comprises the inner fuel pellet concentrically arranged within a surrounding coated cover or shell by fiber nets imbedded within the cover material.

Outer Membrane Protein Folding and Topology from a Computational Transfer Free Energy Scale.

PubMed

Lin, Meishan; Gessmann, Dennis; Naveed, Hammad; Liang, Jie

2016-03-02

Knowledge of the transfer free energy of amino acids from aqueous solution to a lipid bilayer is essential for understanding membrane protein folding and for predicting membrane protein structure. Here we report a computational approach that can calculate the folding free energy of the transmembrane region of outer membrane β-barrel proteins (OMPs) by combining an empirical energy function with a reduced discrete state space model. We quantitatively analyzed the transfer free energies of 20 amino acid residues at the center of the lipid bilayer of OmpLA. Our results are in excellent agreement with the experimentally derived hydrophobicity scales. We further exhaustively calculated the transfer free energies of 20 amino acids at all positions in the TM region of OmpLA. We found that the asymmetry of the Gram-negative bacterial outer membrane as well as the TM residues of an OMP determine its functional fold in vivo. Our results suggest that the folding process of an OMP is driven by the lipid-facing residues in its hydrophobic core, and its NC-IN topology is determined by the differential stabilities of OMPs in the asymmetrical outer membrane. The folding free energy is further reduced by lipid A and assisted by general depth-dependent cooperativities that exist between polar and ionizable residues. Moreover, context-dependency of transfer free energies at specific positions in OmpLA predict regions important for protein function as well as structural anomalies. Our computational approach is fast, efficient and applicable to any OMP.

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

Initial Radiometric Calibration of the AWiFS using Vicarious Calibration Techniques

NASA Technical Reports Server (NTRS)

Pagnutti, Mary; Thome, Kurtis; Aaron, David; Leigh, Larry

2006-01-01

NASA SSC maintains four ASD FieldSpec FR spectroradiometers: 1) Laboratory transfer radiometers; 2) Ground surface reflectance for V&V field collection activities. Radiometric Calibration consists of a NIST-calibrated integrating sphere which serves as a source with known spectral radiance. Spectral Calibration consists of a laser and pen lamp illumination of integrating sphere. Environmental Testing includes temperature stability tests performed in environmental chamber.

Modelling heat transfer during flow through a random packed bed of spheres

NASA Astrophysics Data System (ADS)

Burström, Per E. C.; Frishfelds, Vilnis; Ljung, Anna-Lena; Lundström, T. Staffan; Marjavaara, B. Daniel

2018-04-01

Heat transfer in a random packed bed of monosized iron ore pellets is modelled with both a discrete three-dimensional system of spheres and a continuous Computational Fluid Dynamics (CFD) model. Results show a good agreement between the two models for average values over a cross section of the bed for an even temperature profiles at the inlet. The advantage with the discrete model is that it captures local effects such as decreased heat transfer in sections with low speed. The disadvantage is that it is computationally heavy for larger systems of pellets. If averaged values are sufficient, the CFD model is an attractive alternative that is easy to couple to the physics up- and downstream the packed bed. The good agreement between the discrete and continuous model furthermore indicates that the discrete model may be used also on non-Stokian flow in the transitional region between laminar and turbulent flow, as turbulent effects show little influence of the overall heat transfer rates in the continuous model.

Inherently-Forced Tensile Strain in Nanodiamond-Derived Onion-like Carbon: Consequences in Defect-Induced Electrochemical Activation

PubMed Central

Ko, Young-Jin; Cho, Jung-Min; Kim, Inho; Jeong, Doo Seok; Lee, Kyeong-Seok; Park, Jong-Keuk; Baik, Young-Joon; Choi, Heon-Jin; Lee, Seung-Cheol; Lee, Wook-Seong

2016-01-01

We analyzed the nanodiamond-derived onion-like carbon (OLC) as function of synthesis temperature (1000~1400 °C), by high-resolution electron microscopy, electron energy loss spectroscopy, visible-Raman spectroscopy, ultraviolet photoemission spectroscopy, impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The temperature dependences of the obtained properties (averaged particle size, tensile strain, defect density, density of states, electron transfer kinetics, and electrochemical oxidation current) unanimously coincided: they initially increased and saturated at 1200 °C. It was attributed to the inherent tensile strains arising from (1) the volume expansion associated with the layer-wise diamond-to-graphite transformation of the core, which caused forced dilation of the outer shells during their thermal synthesis; (2) the extreme curvature of the shells. The former origin was dominant over the latter at the outermost shell, of which the relevant evolution in defect density, DOS and electron transfer kinetics determined the electrochemical performances. In detection of dopamine (DA), uric acid (UA) and ascorbic acid (AA) using the OLC as electrode, their oxidation peak currents were enhanced by factors of 15~60 with annealing temperature. Their limit of detection and the linear range of detection, in the post-treatment-free condition, were as excellent as those of the nano-carbon electrodes post-treated by Pt-decoration, N-doping, plasma, or polymer. PMID:27032957

Effect of radiation and magnetohydrodynamic free convection boundary layer flow on a solid sphere with Newtonian heating in a micropolar fluid

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

Alkasasbeh, Hamzeh Taha, E-mail: zukikuj@yahoo.com; Sarif, Norhafizah Md, E-mail: zukikuj@yahoo.com; Salleh, Mohd Zuki, E-mail: zukikuj@yahoo.com

2015-02-03

In this paper, the effect of radiation on magnetohydrodynamic free convection boundary layer flow on a solid sphere with Newtonian heating in a micropolar fluid, in which the heat transfer from the surface is proportional to the local surface temperature, is considered. The transformed boundary layer equations in the form of nonlinear partial differential equations are solved numerically using an implicit finite difference scheme known as the Keller-box method. Numerical solutions are obtained for the local wall temperature and the local skin friction coefficient, as well as the velocity, angular velocity and temperature profiles. The features of the flow andmore » heat transfer characteristics for various values of the Prandtl number Pr, micropolar parameter K, magnetic parameter M, radiation parameter N{sub R}, the conjugate parameter γ and the coordinate running along the surface of the sphere, x are analyzed and discussed.« less

Density functional theory studies on the solvent effects in Al(H2O)63+ water-exchange reactions: the number and arrangement of outer-sphere water molecules.

PubMed

Liu, Li; Zhang, Jing; Dong, Shaonan; Zhang, Fuping; Wang, Ye; Bi, Shuping

2018-03-07

Density functional theory (DFT) calculations combined with cluster models are performed at the B3LYP/6-311+G(d,p) level for investigating the solvent effects in Al(H 2 O) 6 3+ water-exchange reactions. A "One-by-one" method is proposed to obtain the most representative number and arrangement of explicit H 2 Os in the second hydration sphere. First, all the possible ways to locate one explicit H 2 O in second sphere (N m ' = 1) based on the gas phase structure (N m ' = 0) are examined, and the optimal pathway (with the lowest energy barrier) for N m ' = 1 is determined. Next, more explicit H 2 Os are added one by one until the inner-sphere is fully hydrogen bonded. Finally, the optimal pathways with N m ' = 0-7 are obtained. The structural and energetic parameters as well as the lifetimes of the transition states are compared with the results obtained with the "Independent-minimum" method and the "Independent-average" method, and all three methods show that the pathway with N m ' = 6 may be representative. Our results give a new idea for finding the representative pathway for water-exchange reactions in other hydrated metal ion systems.

Hard sphere packings within cylinders.

PubMed

Fu, Lin; Steinhardt, William; Zhao, Hao; Socolar, Joshua E S; Charbonneau, Patrick

2016-03-07

Arrangements of identical hard spheres confined to a cylinder with hard walls have been used to model experimental systems, such as fullerenes in nanotubes and colloidal wire assembly. Finding the densest configurations, called close packings, of hard spheres of diameter σ in a cylinder of diameter D is a purely geometric problem that grows increasingly complex as D/σ increases, and little is thus known about the regime for D > 2.873σ. In this work, we extend the identification of close packings up to D = 4.00σ by adapting Torquato-Jiao's adaptive-shrinking-cell formulation and sequential-linear-programming (SLP) technique. We identify 17 new structures, almost all of them chiral. Beyond D ≈ 2.85σ, most of the structures consist of an outer shell and an inner core that compete for being close packed. In some cases, the shell adopts its own maximum density configuration, and the stacking of core spheres within it is quasiperiodic. In other cases, an interplay between the two components is observed, which may result in simple periodic structures. In yet other cases, the very distinction between the core and shell vanishes, resulting in more exotic packing geometries, including some that are three-dimensional extensions of structures obtained from packing hard disks in a circle.

Thermoelectric Outer Planets Spacecraft (TOPS) electronic packaging and cabling development summary report

NASA Technical Reports Server (NTRS)

Dawe, R. H.; Arnett, J. C.

1974-01-01

Electronic packaging and cabling activities performed in support of the Thermoelectric Outer Planets Spacecraft (TOPS) Advanced Systems Technology (AST) project are detailed. It describes new electronic compartment, electronic assembly, and module concepts, and a new high-density, planar interconnection technique called discrete multilayer (DML). Development and qualification of high density cabling techniques, using small gage wire and microminiature connectors, are also reported.

Electrostatic roles in electron transfer from [NiFe] hydrogenase to cytochrome c3 from Desulfovibrio vulgaris Miyazaki F.

PubMed

Sugimoto, Yu; Kitazumi, Yuki; Shirai, Osamu; Nishikawa, Koji; Higuchi, Yoshiki; Yamamoto, Masahiro; Kano, Kenji

2017-05-01

Electrostatic interactions between proteins are key factors that govern the association and reaction rate. We spectroscopically determine the second-order reaction rate constant (k) of electron transfer from [NiFe] hydrogenase (H 2 ase) to cytochrome (cyt) c 3 at various ionic strengths (I). The k value decreases with I. To analyze the results, we develop a semi-analytical formula for I dependence of k based on the assumptions that molecules are spherical and the reaction proceeds via a transition state. Fitting of the formula to the experimental data reveals that the interaction occurs in limited regions with opposite charges and with radii much smaller than those estimated from crystal structures. This suggests that local charges in H 2 ase and cyt c 3 play important roles in the reaction. Although the crystallographic data indicate a positive electrostatic potential over almost the entire surface of the proteins, there exists a small region with negative potential on H 2 ase at which the electron transfer from H 2 ase to cyt c 3 may occur. This local negative potential region is identical to the hypothetical interaction sphere predicted by the analysis. Furthermore, I dependence of k is predicted by the Adaptive Poisson-Boltzmann Solver considering all charges of the amino acids in the proteins and the configuration of H 2 ase/cyt c 3 complex. The calculation reproduces the experimental results except at extremely low I. These results indicate that the stabilization derived from the local electrostatic interaction in the H 2 ase/cyt c 3 complex overcomes the destabilization derived from the electrostatic repulsion of the overall positive charge of both proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Guiding Principles of Hydrogenase Catalysis Instigated and Clarified by Protein Film Electrochemistry.

PubMed

Armstrong, Fraser A; Evans, Rhiannon M; Hexter, Suzannah V; Murphy, Bonnie J; Roessler, Maxie M; Wulff, Philip

2016-05-17

Protein film electrochemistry (PFE) is providing cutting-edge insight into the chemical principles underpinning biological hydrogen. Attached to an electrode, many enzymes exhibit "reversible" electrocatalytic behavior, meaning that a catalyzed redox reaction appears reversible or quasi-reversible when viewed by cyclic voltammetry. This efficiency is most relevant for enzymes that are inspiring advances in renewable energy, such as hydrogen-activating and CO2-reducing enzymes. Exploiting the rich repertoire of available instrumental methods, PFE experiments yield both a general snapshot and fine detail, all from tiny samples of enzyme. The dynamic electrochemical investigations blaze new trails and add exquisite detail to the information gained from structural and spectroscopic studies. This Account describes recent investigations of hydrogenases carried out in Oxford, including ideas initiated with PFE and followed through with complementary techniques, all contributing to an eventual complete picture of fast and efficient H2 activation without Pt. By immobilization of an enzyme on an electrode, catalytic electron flow and the chemistry controlling it can be addressed at the touch of a button. The buried nature of the active site means that structures that have been determined by crystallography or spectroscopy are likely to be protected, retained, and fully relevant in a PFE experiment. An electrocatalysis model formulated for the PFE of immobilized enzymes predicts interesting behavior and gives insight into why some hydrogenases are H2 producers and others are H2 oxidizers. Immobilization also allows for easy addition and removal of inhibitors along with precise potential control, one interesting outcome being that formaldehyde forms a reversible complex with reduced [FeFe]-hydrogenases, thereby providing insight into the order of electron and proton transfers. Experiments on O2-tolerant [NiFe]-hydrogenases show that O2 behaves like a reversible inhibitor: it is also a substrate, and implicit in the description of some hydrogenases as "H2/O2 oxidoreductases" is the hypothesis that fast and efficient multielectron transfer is a key to O2 tolerance because it promotes complete reduction of O2 to harmless water. Not only is a novel [4Fe-3S] cluster (able to transfer two electrons consecutively) an important component, but connections to additional electron sources (other Fe-S clusters, an electrode, another quaternary structure unit, or the physiological membrane itself) ensure that H2 oxidation can be sustained in the presence of O2, as demonstrated with enzyme fuel cells able to operate on a H2/air mixture. Manipulating the H-H bond in the active site is the simplest proton-coupled electron-transfer reaction to be catalyzed by an enzyme. Unlike small molecular catalysts or the surfaces of materials, metalloenzymes are far better suited to engineering the all-important outer-coordination shell. Hence, recent successful site-directed mutagenesis of the conserved outer-shell "canopy" residues in a [NiFe]-hydrogenase opens up new opportunities for understanding the mechanism of H2 activation beyond the role of the inner coordination shell.

Experimental validation of tunable features in laser-induced plasma resonators

NASA Astrophysics Data System (ADS)

Colón Quiñones, Roberto A.; Cappelli, Mark A.

2017-08-01

Measurements are presented which examine the use of gaseous plasma elements as highly-tunable resonators. The resonator considered here is a laser-induced plasma kernel generated by focusing the fundamental output from a Q-switched Nd:YAG laser through a lens and into a gas at constant pressure. The near-ellipsoidal plasma element interacts with incoming microwave radiation through excitation of low-order, electric-dipole resonances similar to those seen in metallic spheres. The tunability of these elements stems from the dispersive nature of plasmas arising from their variable electron density, electron momentum transfer collision frequency, and the concomitant e↵ect of these properties on the excited surface plasmon resonance. Experiments were carried out in the Ku band of the microwave spectrum to characterize the scattering properties of these resonators for di↵erent values of electron density. The experimental results are compared with results from theoretical approximations and finite element method electromagnetic simulations. The described tunable resonators have the potential to be used as the building blocks in a new class of all-plasma metamaterials with fully three-dimensional structural flexibility.

Effect of Monomer Solubility on the Evolution of Copolymer Morphology during Polymerization-Induced Self-Assembly in Aqueous Solution

PubMed Central

2017-01-01

Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm–3 at 70 °C) instead of benzyl methacrylate (0.40 g dm–3 at 70 °C) for the core-forming block allows access to an unusual “monkey nut” copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering. PMID:28216792

Electronic transport properties of 4f shell elements of liquid metal using hard sphere Yukawa system

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

2018-04-01

The electronic transport properties are analyzed for 4f shell elements of liquid metals. To examine the electronic transport properties like electrical resistivity (ρ), thermal conductivity (σ) and thermo electrical power (Q), we used our own parameter free model potential with the Hard Sphere Yukawa (HSY) reference system. The screening effect on aforesaid properties has been examined by using different screening functions like Hartree (H), Taylor (T) and Sarkar (S). The correlations of our resultsand other data with available experimental values are intensely promising. Also, we conclude that our newly constructed parameter free model potential is capable of explaining the above mentioned electronic transport properties.

High Valent Manganese and Cobalt Complexes of Oxidatively Robust Nitrogen and Oxygen Donor Ligands.

NASA Astrophysics Data System (ADS)

Gordon-Wylie, Scott Wallace

1995-01-01

The focus of this thesis is to extend the range of ligands that satisfy the Collins criteria through a program of organic synthesis, and to apply the resulting high valent metal ligand complexes to the solution of current problems in structural inorganic chemistry, solid state chemistry (with a particular emphasis on magnetic interactions in solids) and to homogeneous and heterogeneous catalysis. Notable achievements along these directions to date are: (i) A streamlined synthesis of diamide dialkoxide and diamide diphenoxide acyclic ligands which allows for a wide range of both electron withdrawing and electron donating substituents to be incorporated into the ligand framework. (ii) The first example of a LMn(V)O species stable enough to be crystallographically characterized was obtained, utilizing the acyclic ligands of (i). (iii) Catalytic O-atom transfer oxidations utilizing acyclic ligands from (i) have been performed. Planar Co(III) complexes of these ligands can catalyze O-atom transfers, ^1 with 30-50 turnovers, including enantioselective ones,^2 implicating that the ligands remain at least partially intact during the catalytic process. (iv) Unusual magnetic ordering has been observed in an infinite linear chain of S = 2 LMn(III) centers, in collaboration with Edmund P. Day. (v) Ferromagnetic exchange has been obtained in a ((LCo(III)) _3Co(II)) ^{-} complex^4 Magnetic model building in collaboration with Gordon Yee and Emile Bominaar has led to an understanding of the magnetic data suitable for publication.^5 (vi) Adaptation of a range of electronic substituents (see (i)) into a macrocyclic framework^7 allows for the preparation of hydrolytically and oxidatively stable high valent metal complexes. The presence of a range of electronic substituents further allows redox potentials for a single (LM) ^{rm n+}/(LM) ^{(rm n+1)+ } oxidation process to be tuned over a range that spans ca. 1 V. (vii) Initial linear syntheses for these macrocycles involved the use of organic azide intermediates. (viii) A new macrocyclic switching ligand has been synthesized utilizing (vii), that allows H^{+} or other lewis acids to act at the secondary site as electron withdrawing groups from the metal. In the structurally characterized switching (Co(III)( kappa^4-L)) ^{ -} complex, there is a bidentate switching site consisting of a pyridine-N and an adjacent amide-O donor. It has been found that the cobalt(II) derivative (CO(II)(kappa^4-L)) ^{-} readily reduces O _2 by an outer sphere (presumably by 1 e ^{-}) process. (ix) Robust homogeneous metalloredox-active oxidants are an important strategic goal for primary pollution prevention, or what is often called "green chemistry". Use of (vii) provides access to quantities of a macrocyclic ligand, that is derivatized in such a way that it can be attached to a solid polymer support. (x) C-H bond activation has been observed in iron systems^{15} in collaboration with Mike Bartos (the principal investigator) where use of (vii) has allowed quantities of ligand to be synthesized and burned in reaction chemistry with nitriles and oxidants. (xi) Macrocyclic ligands with organic solubilizing groups have been prepared utilizing (vii) and metal complexes with substantial alkane solubility result. (Abstract shortened by UMI.).

Numerical Simulation of Heat Transfer in Porous Metals for Cooling Applications

NASA Astrophysics Data System (ADS)

Gauna, Edgar Avalos; Zhao, Yuyuan

2017-08-01

Porous metals have low densities and novel physical, mechanical, thermal, electrical, and acoustic properties. Hence, they have attracted a large amount of interest over the last few decades. One of their applications is for thermal management in the electronics industry because of their fluid permeability and thermal conductivity. The heat transfer capability is achieved by the interaction between the internal channels within the porous metal and the coolant flowing through them. This paper studies the fluid flow and heat transfer in open-cell porous metals manufactured by space holder methods by numerical simulation using software ANSYS Fluent. A 3D geometric model of the porous structure was created based on the face-centered-cubic arrangement of spheres linked by cylinders. This model allows for different combinations of pore parameters including a wide range of porosity (50 to 80 pct), pore size (400 to 1000 µm), and metal particle size (10 to 75 µm). In this study, water was used as the coolant and copper was selected as the metal matrix. The flow rate was varied in the Darcian and Forchheimer's regimes. The permeability, form drag coefficient, and heat transfer coefficient were calculated under a range of conditions. The numerical results showed that permeability increased whereas the form drag coefficient decreased with porosity. Both permeability and form drag coefficient increased with pore size. Increasing flow rate and decreasing porosity led to better heat transfer performance.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

DOE PAGES

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; ...

2017-06-09

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

On the Effect of Geomagnetic Storms on Relativistic Electrons in the Outer Radiation Belt: Van Allen Probes Observations

NASA Astrophysics Data System (ADS)

Moya, Pablo S.; Pinto, Víctor A.; Sibeck, David G.; Kanekal, Shrikanth G.; Baker, Daniel N.

2017-11-01

Using Van Allen Probes Energetic Particle, Composition, and Thermal Plasma-Relativistic Electron-Proton Telescope (ECT-REPT) observations, we performed a statistical study on the effect of geomagnetic storms on relativistic electrons fluxes in the outer radiation belt for 78 storms between September 2012 and June 2016. We found that the probability of enhancement, depletion, and no change in flux values depends strongly on L and energy. Enhancement events are more common for ˜2 MeV electrons at L ˜ 5, and the number of enhancement events decreases with increasing energy at any given L shell. However, considering the percentage of occurrence of each kind of event, enhancements are more probable at higher energies, and the probability of enhancement tends to increases with increasing L shell. Depletion are more probable for 4-5 MeV electrons at the heart of the outer radiation belt, and no-change events are more frequent at L < 3.5 for E ˜ 3 MeV particles. Moreover, for L > 4.5 the probability of enhancement, depletion, or no-change response presents little variation for all energies. Because these probabilities remain relatively constant as a function of radial distance in the outer radiation belt, measurements obtained at geosynchronous orbit may be used as a proxy to monitor E≥1.8 MeV electrons in the outer belt.

Rotation of large asymmetrical absorbing objects by Laguerre-Gauss beams.

PubMed

Herne, Catherine M; Capuzzi, Kristina M; Sobel, Emily; Kropas, Ryan T

2015-09-01

In this Letter, we show the manipulation and rotation of opaque graphite through adhesion with optically trapped polystyrene spheres. The absorbing graphite is rotated by the orbital angular momentum transfer from a Laguerre-Gauss laser mode and is trapped due to the presence of refracting spheres. This technique is effective for trapping and rotating absorbing objects of all sizes, including those larger than the laser mode.

Prompt Recovery and Enhancement of the Earth's Outer Radiation Belt due to Relativistic Electron Injections

NASA Astrophysics Data System (ADS)

Tang, C. L.; Zhang, J.; Reeves, G. D.; Baker, D. N.; Spence, H. E.; Funsten, H. O.; Blake, J. B.

2015-12-01

We present multipoint observations (RBSP, GEOS and THEMIS) of the substorm electron injections during the substorm event on 16 August 2013. RBSP-A detected the MeV electron phase space density increased by an order of magnitude in about one hour at L* > 5.0. At L* = 4.4, the injected MeV electrons were also detected. It is suggested that the magnetic field dipolarization associated with the substorm injections alone can explain that the prompt recovery and enhancements of the relativistic electron (~ MeV) fluxes in the outer radiation belt. The observations of THEMIS-A also first presented that the near-Earth magnetotail at substorm onset is important in the MeV electron injection event: the enhanced fluxes of ~200 keV electrons are the source population and intense electromagnetic pulses are the driving source of MeV injected electrons. The pulse model is used to explain the dispersionless MeV injected electrons in the outer radiation belt observed by GEOS-13 and RBSP-A.

Electromagnetic braking revisited with a magnetic point dipole model

NASA Astrophysics Data System (ADS)

Land, Sara; McGuire, Patrick; Bumb, Nikhil; Mann, Brian P.; Yellen, Benjamin B.

2016-04-01

A theoretical model is developed to predict the trajectory of magnetized spheres falling through a copper pipe. The derive magnetic point dipole model agrees well with the experimental trajectories for NdFeB spherical magnets of varying diameter, which are embedded inside 3D printed shells with fixed outer dimensions. This demonstration of electrodynamic phenomena and Lenz's law serves as a good laboratory exercise for physics, electromagnetics, and dynamics classes at the undergraduate level.

Synthesis of highly-monodisperse spherical titania particles with diameters in the submicron range.

PubMed

Tanaka, Shunsuke; Nogami, Daisuke; Tsuda, Natsuki; Miyake, Yoshikazu

2009-06-15

Monodisperse titania spheres with particle diameters in the range 380-960 nm were successfully synthesized by hydrolysis and condensation of titanium tetraisopropoxide. The preparation was performed using ammonia or dodecylamine (DDA) as a catalyst in methanol/acetonitrile co-solvent at room temperature. The samples were characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic light scattering, and nitrogen sorption measurement. The use of DDA was effective for the synthesis of monodisperse titania spheres with low coefficient of variation. When the titania spherical particles with coefficient of variation less than 4% were obtained, the colloidal crystallization easily occurred simply by centrifugation. The monodispersity was maintained even after crystallization of the particles by high temperature annealing. The titania particles prepared using DDA had mesopores near the surface of the spheres, providing high pore accessibility to the sphere from the surface-air interface. The particle size uniformity and photocatalytic reactivity of the titania prepared using DDA were higher than those of the titania prepared using ammonia.

Secondary coordination sphere interactions within the biomimetic iron azadithiolate complexes related to Fe-only hydrogenase: dynamic measure of electron density about the Fe sites.

PubMed

Liu, Yu-Chiao; Tu, Ling-Kuang; Yen, Tao-Hung; Lee, Gene-Hsiang; Yang, Shu-Ting; Chiang, Ming-Hsi

2010-07-19

A series of iron azadithiolate complexes possessing an intramolecular secondary coordination sphere interaction and an ability to reduce HOAc at the potential near the first electron-transfer process are reported. A unique structural feature in which the aza nitrogen has its lone pair point toward the apical carbonyl carbon is observed in [Fe(2)(mu-S(CH(2))(2)NR(CH(2))(2)S)(CO)(6-x)L(x)](2) (R = (n)Pr, x = 0, 1a; R = (i)Pr, x = 0, 1b; R = (n)Pr, L = PPh(3), x = 1, 2; R = (n)Pr, L = P(n)Bu(3), x = 1, 3) as biomimetic models of the active site of Fe-only hydrogenase. The presence of this weak N...C(CO(ap)) interaction provides electronic perturbation at the Fe center. The distance of the N...C(CO(ap)) contact is 3.497 A in 1a. It increases by 0.455 A in 2 when electronic density of the Fe site is slightly enriched by a weak sigma-donating ligand, PPh(3). A longer distance (4.040 A) is observed for the P(n)Bu(3) derivative, 3. This N...C(CO(ap)) distance is thus a dynamic measure of electronic nature of the Fe(2) core. Variation of electronic richness within the Fe(2) moiety among the complexes reflects on their electrochemical response. Reduction of 2 is recorded at the potential of -2.17 V, which is 270 mV more negative than that of 1. Complex 3 requires additional 150 mV for the same reduction. Such cathodic shift results from CO substitution by phosphines. Electrocatalytic hydrogen production from HOAc by both kinds of complexes (all-CO and phosphine-substituted species) requires the potential close to that for reduction of the parent molecules in the absence of acids. The catalytic mechanism of 1a is proposed to involve proton uptake at the Fe(0)Fe(I) redox level instead of the Fe(0)Fe(0) level. This result is the first observation among the all-CO complexes with respect to electrocatalysis of HOAc.

Relaxation model of radiation-induced conductivity in polymers

NASA Astrophysics Data System (ADS)

Zhutayeva, Yu. R.; Khatipov, S. A.

1999-05-01

The paper suggests a relaxation model of radiation-induced conductivity (RIC) in polymers. According to the model, the transfer of charges generated in the polymer volume by ionizing radiation takes place with the participation of molecular relaxation processes. The mechanism of electron transport consists in the transfer of the charge directly between traps when they draw close to one another due to the rotation of macromolecule segments. The numerical solutions of the corresponding kinetic equations for different distribution functions Q( τ) of the times of molecular relaxation and for different functions of the probability P( τ, τ') of charge transfer in the `overlapping' regions of the diffusion spheres of the segments are analyzed. The relaxation model provides an explanation of the non-Arrhenius behavior of the RIC temperature dependence, the power dependence of RIC on the dose rate with a power index in the interval 0.5-1.0, the appearance of maxima in the curves of the RIC temporal dependence and their irreversible character in the region of large dose rates (more than 1 Gy/s). The model can be used for interpreting polymer RIC in conditions of kinetic mobility of macromolecules.

The relationship between the plasmapause and outer belt electrons

DOE PAGES

Goldstein, J.; Baker, D. N.; Blake, J. B.; ...

2016-09-01

Here, we quantify the spatial relationship between the plasmapause and outer belt electrons for a 5 day period, 15–20 January 2013, by comparing locations of relativistic electron flux peaks to the plasmapause. A peak-finding algorithm is applied to 1.8–7.7 MeV relativistic electron flux data. A plasmapause gradient finder is applied to wave-derived electron number densities >10 cm –3. We identify two outer belts. Outer belt 1 is a stable zone of >3 MeV electrons located 1–2 R E inside the plasmapause. Outer belt 2 is a dynamic zone of <3 MeV electrons within 0.5 R E of the moving plasmapause.more » Electron fluxes earthward of each belt's peak are anticorrelated with cold plasma density. Belt 1 decayed on hiss timescales prior to a disturbance on 17 January and suffered only a modest dropout, perhaps owing to shielding by the plasmasphere. Afterward, the partially depleted belt 1 continued to decay at the initial rate. Belt 2 was emptied out by strong disturbance-time losses but restored within 24 h. For global context we use a plasmapause test particle simulation and derive a new plasmaspheric index F p, the fraction of a circular drift orbit inside the plasmapause. We find that the locally measured plasmapause is (for this event) a good proxy for the globally integrated opportunity for losses in cold plasma. Our analysis of the 15–20 January 2013 time interval confirms that high-energy electron storage rings can persist for weeks or even months if prolonged quiet conditions prevail. This case study must be followed up by more general study (not limited to a 5 day period).« less

The relationship between the plasmapause and outer belt electrons

NASA Astrophysics Data System (ADS)

Goldstein, J.; Baker, D. N.; Blake, J. B.; De Pascuale, S.; Funsten, H. O.; Jaynes, A. N.; Jahn, J.-M.; Kletzing, C. A.; Kurth, W. S.; Li, W.; Reeves, G. D.; Spence, H. E.

2016-09-01

We quantify the spatial relationship between the plasmapause and outer belt electrons for a 5 day period, 15-20 January 2013, by comparing locations of relativistic electron flux peaks to the plasmapause. A peak-finding algorithm is applied to 1.8-7.7 MeV relativistic electron flux data. A plasmapause gradient finder is applied to wave-derived electron number densities >10 cm-3. We identify two outer belts. Outer belt 1 is a stable zone of >3 MeV electrons located 1-2 RE inside the plasmapause. Outer belt 2 is a dynamic zone of <3 MeV electrons within 0.5 RE of the moving plasmapause. Electron fluxes earthward of each belt's peak are anticorrelated with cold plasma density. Belt 1 decayed on hiss timescales prior to a disturbance on 17 January and suffered only a modest dropout, perhaps owing to shielding by the plasmasphere. Afterward, the partially depleted belt 1 continued to decay at the initial rate. Belt 2 was emptied out by strong disturbance-time losses but restored within 24 h. For global context we use a plasmapause test particle simulation and derive a new plasmaspheric index Fp, the fraction of a circular drift orbit inside the plasmapause. We find that the locally measured plasmapause is (for this event) a good proxy for the globally integrated opportunity for losses in cold plasma. Our analysis of the 15-20 January 2013 time interval confirms that high-energy electron storage rings can persist for weeks or even months if prolonged quiet conditions prevail. This case study must be followed up by more general study (not limited to a 5 day period).

Contributions from inner and outer shell electron energies to reaction heats for C/sub 1/, C/sub 2/, and C/sub 3/ hydrocarbons

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

George, P.; Bock, C.W.; Trachtman, M.

1979-04-01

The expectation energy values E/sub k/, V/sub ee/, V/sub nn/, V/sub en/, and E/sub T/ have been calculated for H/sub 2/ and the C/sub 1/, C/sub 2/, and C/sub 3/ hydrocarbons using a (9,5) basis set and the experimental geometries. Treating the theoretical reaction heat, ..delta..E/sub T/, as the resultant of the nuclear repulsion term, ..delta..V/sub nn/, and the net electron energy term, ..delta..E/sub elec/ = ..delta..E/sub k/ + ..delta..V/sub ee/ + ..delta..V/sub en/, the contribution of inner and outer shell electron energies to ..delta..E/sub elec/, and hence to ..delta..E/sub T/, has been calculated for a large number of hydrocarbonmore » reactions by evaluating the Coulson--Neilson energies eta/sub i/, where eta/sub i/ = E/sub elec/. For the vast majority of reactions, 67/84, the change in inner shell electron energy, (..delta sigma..eta/sub i/)/sub inner/, accounts for more than 10% of ..delta..E/sub elec/, in many cases being as high as 20-35%. Furthermore, in addition to these cases in which the change in inner shell electron energy serves to augment (significantly) the change in outer shell electron energy, there are other cases in which the change in inner shell electron energy either exceeds in magnitude the change in outer shell energy, or is even opposite in sign, indicative of inner and outer shell electrons acting contrariwise. Inner shell electron energies contribute to the reaction heats because they are structure dependent, like the more familiar orbital energies epsilon, but the dependence is of a different kind.« less

Improved utilization of photogenerated charge using fluorine-doped TiO(2) hollow spheres scattering layer in dye-sensitized solar cells.

PubMed

Song, Junling; Yang, Hong Bin; Wang, Xiu; Khoo, Si Yun; Wong, C C; Liu, Xue-Wei; Li, Chang Ming

2012-07-25

We demonstrate a strategy to improve utilization of photogenerated charge in dye-sensitized solar cells (DSSCs) with fluorine-doped TiO2 hollow spheres as the scattering layer, which improves the fill factor from 69.4% to 74.1% and in turn results in an overall efficiency of photoanode increased by 13% (from 5.62% to 6.31%) in comparison with the control device using undoped TiO2 hollow spheres. It is proposed that the fluorine-doping improves the charge transfer and inhibition of charge recombination to enhance the utilization of the photogenerated charge in the photoanode.

SPHERES

NASA Image and Video Library

2013-08-27

ISS036-E-037288 (27 Aug. 2013) --- In the International Space Station?s Kibo laboratory, NASA astronaut Karen Nyberg, Expedition 36 flight engineer, conducts a session with a pair of bowling-ball-sized free-flying satellites known as Synchronized Position Hold, Engage, Reorient, Experimental Satellites, or SPHERES. Surrounding the two SPHERES mini-satellites with ring-shaped hardware known as the Resonant Inductive Near-field Generation System, or RINGS, Nyberg performed a demonstration of how power can be transferred between two satellites without physical contact. Station crews beginning with Expedition 8 have operated these robots to test techniques that could lead to advancements in automated dockings, satellite servicing, spacecraft assembly and emergency repairs.

Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds.

PubMed

Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

2015-05-11

A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of the outer layer of the Dictyostelium spore coat depends on the inner-layer protein SP85/PsB.

PubMed

Metcalf, Talibah; Kelley, Karen; Erdos, Gregory W; Kaplan, Lee; West, Christopher M

2003-02-01

The Dictyostelium spore is surrounded by a 220 microm thick trilaminar coat that consists of inner and outer electron-dense layers surrounding a central region of cellulose microfibrils. In previous studies, a mutant strain (TL56) lacking three proteins associated with the outer layer exhibited increased permeability to macromolecular tracers, suggesting that this layer contributes to the coat permeability barrier. Electron microscopy now shows that the outer layer is incomplete in the coats of this mutant and consists of a residual regular array of punctate electron densities. The outer layer is also incomplete in a mutant lacking a cellulose-binding protein associated with the inner layer, and these coats are deficient in an outer-layer protein and another coat protein. To examine the mechanism by which this inner-layer protein, SP85, contributes to outer-layer formation, various domain fragments were overexpressed in forming spores. Most of these exert dominant negative effects similar to the deletion of outer-layer proteins, but one construct, consisting of a fusion of the N-terminal and Cys-rich C1 domain, induces a dense mat of novel filaments at the surface of the outer layer. Biochemical studies show that the C1 domain binds cellulose, and a combination of site-directed mutations that inhibits its cellulose-binding activity suppresses outer-layer filament induction. The results suggest that, in addition to a previously described early role in regulating cellulose synthesis, SP85 subsequently contributes a cross-bridging function between cellulose and other coat proteins to organize previously unrecognized structural elements in the outer layer of the coat.

Interaction Mode and Regioselectivity in Vitamin B12-Dependent Dehalogenation of Aryl Halides by Dehalococcoides mccartyi Strain CBDB1.

PubMed

Zhang, Shangwei; Adrian, Lorenz; Schüürmann, Gerrit

2018-02-20

The bacterium Dehalococcoides, strain CBDB1, transforms aromatic halides through reductive dehalogenation. So far, however, the structures of its vitamin B 12 -containing dehalogenases are unknown, hampering clarification of the catalytic mechanism and substrate specificity as basis for targeted remediation strategies. This study employs a quantum chemical donor-acceptor approach for the Co(I)-substrate electron transfer. Computational characterization of the substrate electron affinity at carbon-halogen bonds enables discriminating aromatic halides ready for dehalogenation by strain CBDB1 (active substrates) from nondehalogenated (inactive) counterparts with 92% accuracy, covering 86 of 93 bromobenzenes, chlorobenzenes, chlorophenols, chloroanilines, polychlorinated biphenyls, and dibenzo-p-dioxins. Moreover, experimental regioselectivity is predicted with 78% accuracy by a site-specific parameter encoding the overlap potential between the Co(I) HOMO (highest occupied molecular orbital) and the lowest-energy unoccupied sigma-symmetry substrate MO (σ*), and the observed dehalogenation pathways are rationalized with a success rate of 81%. Molecular orbital analysis reveals that the most reactive unoccupied sigma-symmetry orbital of carbon-attached halogen X (σ C-X * ) mediates its reductive cleavage. The discussion includes predictions for untested substrates, thus providing opportunities for targeted experimental investigations. Overall, the presently introduced orbital interaction model supports the view that with bacterial strain CBDB1, an inner-sphere electron transfer from the supernucleophile B 12 Co(I) to the halogen substituent of the aromatic halide is likely to represent the rate-determining step of the reductive dehalogenation.

Understanding Rubredoxin Redox Sites by Density Functional Theory Studies of Analogues

PubMed Central

Luo, Yan; Niu, Shuqiang; Ichiye, Toshiko

2012-01-01

Determining the redox energetics of redox site analogues of metalloproteins is essential in unraveling the various contributions to electron transfer properties of these proteins. Since studies of the [4Fe-4S] analogues show that the energies are dependent on the ligand dihedral angles, broken symmetry density functional theory (BS-DFT) with the B3LYP functional and double-ζ basis sets calculations of optimized geometries and electron detachment energies of [1Fe] rubredoxin analogues are compared to crystal structures and gas-phase photoelectron spectroscopy data, respectively, for [Fe(SCH3)4]0/1-/2-, [Fe(S2-o-xyl2)]0/1-/2-, and Na+[Fe(S2-o-xyl)2]1-/2- in different conformations. In particular, the study of Na+[Fe(S2-o-xyl)2]1-/2- is the only direct comparison of calculated and experimental gas phase detachment energies for the 1-/2- couple found in the rubredoxins. These results show that variations in the inner sphere energetics by up to ~0.4 eV can be caused by differences in the ligand dihedral angles in either or both redox states. Moreover, these results indicate that the protein stabilizes the conformation that favors reduction. In addition, the free energies and reorganization energies of oxidation and reduction as well as electrostatic potential charges are calculated, which can be used as estimates in continuum electrostatic calculations of electron transfer properties of [1Fe] proteins. PMID:22881577

Heat insulating device for low temperature liquefied gas storage tank

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

Okamoto, T.; Nishimoto, T.; Sawada, K.

1978-05-02

Hitachi Shipbuilding and Engineering Co., Ltd.'s insulation method for spherical LNG containers solves various problems associated with insulating a sphere's three-dimensional curved surface; equalizing the thickness of the insulation, insulating the junctions between insulation blocks, and preventing seawater or LNG from penetrating the insulation barrier in the event of a rupture in the tank and ship's hull. The design incorporates a number of blocks or plates of rigid foam-insulating material bonded to the outer wall; seats for receiving pressing jigs for the bonding operation are secured to the outer wall in the joints between the insulating blocks. The joints aremore » filled with soft synthetic foam (embedding the seats), a moistureproof layer covers the insulating blocks and joints, and a waterproof material covers the moistureproof layer.« less

Heat shield characterization: Outer planet atmospheric entry probe

NASA Technical Reports Server (NTRS)

Mezines, S. A.; Rusert, E. L.; Disser, E. F.

1976-01-01

A full scale carbon phenolic heat shield was fabricated for the Outer Planet Probe in order to demonstrate the feasibility of molding large carbon phenolic parts with a new fabrication processing method (multistep). The sphere-cone heat shield was molded as an integral unit with the nose cap plies configured into a double inverse chevron shape to achieve the desired ply orientation. The fabrication activity was successful and the feasibility of the multistep processing technology was established. Delaminations or unbonded plies were visible on the heat shield and resulted from excessive loss of resin and lack of sufficient pressure applied on the part during the curing cycle. A comprehensive heat shield characterization test program was conducted, including: nondestructive tests with the full scale heat shield and thermal and mechanical property tests with small test specimen.

Theoretical analysis of the unusual temperature dependence of the kinetic isotope effect in quinol oxidation.

PubMed

Ludlow, Michelle K; Soudackov, Alexander V; Hammes-Schiffer, Sharon

2009-05-27

In this paper we present theoretical calculations on model biomimetic systems for quinol oxidation. In these model systems, an excited-state [Ru(bpy)(2)(pbim)](+) complex (bpy = 2,2'-dipyridyl, pbim = 2-(2-pyridyl)benzimidazolate) oxidizes a ubiquinol or plastoquinol analogue in acetonitrile. The charge transfer reaction occurs via a proton-coupled electron transfer (PCET) mechanism, in which an electron is transferred from the quinol to the Ru and a proton is transferred from the quinol to the pbim(-) ligand. The experimentally measured average kinetic isotope effects (KIEs) at 296 K are 1.87 and 3.45 for the ubiquinol and plastoquinol analogues, respectively, and the KIE decreases with temperature for plastoquinol but increases with temperature for ubiquinol. The present calculations provide a possible explanation for the differences in magnitudes and temperature dependences of the KIEs for the two systems and, in particular, an explanation for the unusual inverse temperature dependence of the KIE for the ubiquinol analogue. These calculations are based on a general theoretical formulation for PCET reactions that includes quantum mechanical effects of the electrons and transferring proton, as well as the solvent reorganization and proton donor-acceptor motion. The physical properties of the system that enable the inverse temperature dependence of the KIE are a stiff hydrogen bond, which corresponds to a high-frequency proton donor-acceptor motion, and small inner-sphere and solvent reorganization energies. The inverse temperature dependence of the KIE may be observed if the 0/0 pair of reactant/product vibronic states is in the inverted Marcus region, while the 0/1 pair of reactant/product vibronic states is in the normal Marcus region and is the dominant contributor to the overall rate. In this case, the free energy barrier for the dominant transition is lower for deuterium than for hydrogen because of the smaller splittings between the vibronic energy levels for deuterium, and the KIE increases with increasing temperature. The temperature dependence of the KIE is found to be very sensitive to the interplay among the driving force, the reorganization energy, and the vibronic coupling in this regime.

The acoustic radiation force on a heated (or cooled) rigid sphere - Theory

NASA Technical Reports Server (NTRS)

Lee, C. P.; Wang, T. G.

1984-01-01

A finite amplitude sound wave can exert a radiation force on an object due to second-order effect of the wave field. The radiation force on a rigid small sphere (i.e., in the long wavelength limit), which has a temperature different from that of the environment, is presently studied. This investigation assumes no thermally induced convection and is relevant to material processing in the absence of gravity. Both isotropic and nonisotropic temperature profiles are considered. In this calculation, the acoustic effect and heat transfer process are essentially decoupled because of the long wavelength limit. The heat transfer information required for determining the force is contained in the parameters, which are integrals over the temperature distribution.

Investigation of Aggregates as a Model for Titan's Aerosols Using Microwave Analog Experiments and Radiative Transfer Theory

NASA Astrophysics Data System (ADS)

Thomas-Osip, J. E.; Gustafson, B. Å. S.

1996-09-01

It has been suggested that the aerosols in the atmosphere of Titan have an aggregate morphology (Bar-Nun et al., 1988: West and Smith, 1991). Previous studies were based on formulations of the Discrete Dipole Approximation to calculate the single scattering properties of such aggregates. These studies were limited in the size of the individual spheres and total size of the aggregate. We present microwave to light analog scattering measurements and radiative transfer calculations for aggregates of 250-500 individual spheres near the Raleigh size limit in a plane parallel atmosphere. The advantages of using microwave analog experiments include the possibility of investigating a broad range of particle sizes and morphologies.

Distinct roles for key karyogamy proteins during yeast nuclear fusion.

PubMed

Melloy, Patricia; Shen, Shu; White, Erin; Rose, Mark D

2009-09-01

During yeast mating, cell fusion is followed by the congression and fusion of the two nuclei. Proteins required for nuclear fusion are found at the surface (Prm3p) and within the lumen (Kar2p, Kar5p, and Kar8p) of the nuclear envelope (NE). Electron tomography (ET) of zygotes revealed that mutations in these proteins block nuclear fusion with different morphologies, suggesting that they act in different steps of fusion. Specifically, prm3 zygotes were blocked before formation of membrane bridges, whereas kar2, kar5, and kar8 zygotes frequently contained them. Membrane bridges were significantly larger and occurred more frequently in kar2 and kar8, than in kar5 mutant zygotes. The kinetics of NE fusion in prm3, kar5, and kar8 mutants, measured by live-cell fluorescence microscopy, were well correlated with the size and frequency of bridges observed by ET. However the kar2 mutant was defective for transfer of NE lumenal GFP, but not diffusion within the lumen, suggesting that transfer was blocked at the NE fusion junction. These observations suggest that Prm3p acts before initiation of outer NE fusion, Kar5p may help dilation of the initial fusion pore, and Kar2p and Kar8p act after outer NE fusion, during inner NE fusion.

Heat transfer probe

DOEpatents

Frank, Jeffrey I.; Rosengart, Axel J.; Kasza, Ken; Yu, Wenhua; Chien, Tai-Hsin; Franklin, Jeff

2006-10-10

Apparatuses, systems, methods, and computer code for, among other things, monitoring the health of samples such as the brain while providing local cooling or heating. A representative device is a heat transfer probe, which includes an inner channel, a tip, a concentric outer channel, a first temperature sensor, and a second temperature sensor. The inner channel is configured to transport working fluid from an inner inlet to an inner outlet. The tip is configured to receive at least a portion of the working fluid from the inner outlet. The concentric outer channel is configured to transport the working fluid from the inner outlet to an outer outlet. The first temperature sensor is coupled to the tip, and the second temperature sensor spaced apart from the first temperature sensor.

NH NMR shifts of new structurally characterized fac-[Re(CO)3(polyamine)]n+ complexes probed via outer-sphere hydrogen-bonding interactions to anions, including the paramagnetic [Re(IV)Br6]2- anion.

PubMed

Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

2010-06-21

fac-[Re(I)(CO)(3)L](n) complexes serve as models for short-lived fac-[(99m)Tc(I)(CO)(3)L](n) imaging tracers (L = tridentate ligands forming two five-membered chelate rings defining the L face). Dangling groups on L, needed to achieve desirable biodistribution, complicate the NMR spectra, which are not readily understood. Using less complicated L, we found that NH groups (exo-NH) projecting toward the L face sometimes showed an upfield shift attributable to steric shielding of the exo-NH group from the solvent by the chelate rings. Our goal is to advance our ability to relate these spectral features to structure and solution properties. To investigate whether exo-NH groups in six-membered rings exhibit the same effect and whether the presence of dangling groups alters the effect, we prepared new fac-[Re(CO)(3)L](n+) complexes that allow direct comparisons of exo-NH shifts for six-membered versus five-membered chelate rings. New complexes were structurally characterized with the following L: dipn [N-3-(aminopropyl)-1,3-propanediamine], N'-Medipn (3,3'-diamino-N-methyldipropylamine), N,N-Me(2)dipn (N,N-dimethyldipropylenetriamine), aepn [N-2-(aminoethyl)-1,3-propanediamine], trpn [tris-(3-aminopropyl)amine], and tren [tris-(2-aminoethyl)amine]. In DMSO-d(6), the upfield exo-NH signals were exhibited by all complexes, indicating that the rings sterically shield the exo-NH groups from bulky solvent molecules. This interpretation was supported by exo-NH signal shift changes caused by added halide and [ReBr(6)](2-) anions, consistent with outer-sphere hydrogen-bond interactions between these anions and the exo-NH groups. For fac-[Re(CO)(3)(dipn)]PF(6) in acetonitrile-d(3), the exo-NH signal shifted further downfield in the series, Cl(-) > Br(-) > I(-), and the plateau in the shift change required a lower concentration for smaller anions. These results are consistent with steric shielding of the exo-NH groups by the chelate rings. Nevertheless, despite its size, the shape and charge of [ReBr(6)](2-) allowed the dianion to induce large upfield paramagnetic shifts of the exo-NH signal of fac-[Re(CO)(3)(dipn)]PF(6). This dianion shows promise as an outer-sphere hydrogen-bonding paramagnetic shift reagent.

Insight into the core-shell structures of Cu-In-S microspheres

NASA Astrophysics Data System (ADS)

Wochnik, Angela S.; Frank, Anna; Heinzl, Christoph; Häusler, Jonas; Schneider, Julian; Hoffmann, Ramona; Matich, Sonja; Scheu, Christina

2013-12-01

In this study we report about the inner and outer structure of CuInS2 microspheres which might be used e.g. in pastes for simple, low-cost solar cell preparation, as well as in electrodes for light-driven water splitting. The microspheres are synthesized via a mild, template-free solvothermal synthesis route and characterised by electron and focused ion beam microscopy, X-ray diffraction, inductively coupled plasma atomic emission and energy dispersive X-ray spectroscopy. The investigations of cross sections prepared by focused ion beam showed that the spheres consist of compact cores and flaky surface structures. Depending on the reaction time, the core possesses a stoichiometric or Cu-rich chemical composition surrounded by an In-rich shell. The flaky surface always comprises a stoichiometric composition in tetragonal chalcopyrite crystal structure, whereas the other areas additionally show minor contributions of CuS, and CuInS2 in hexagonal wurtzite structure. The presence of different phases can be beneficial for future applications since they offer different absorption behaviour in the visible range.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

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

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab

A biomimetic nickel bis-diphosphine complex incorporating the amino-acid arginine in the outer coordination sphere, was immobilized on modified single-wall carbon nanotubes (SWCNTs) through electrostatic interactions. The sur-face-confined catalyst is characterized by a reversible 2-electron/2-proton redox process at potentials close to the equibrium potential of the H+/H2 couple. Consequently, the functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2/2H+ interconversion over a broad range of pH. This system exhibits catalytic bias, analogous to hydrogenases, resulting in high turnover frequencies at low overpotentials for electrocatalytic H2 oxida-tion between pH 0 and 7. This allowed integrating such bio-inspired nanomaterial together with amore » multicopper oxi-dase at the cathode side in a hybrid bioinspired/enzymatic hydrogen fuel cell. This device delivers ~2 mW cm–2 with an open-circuit voltage of 1.0 V at room temperature and pH 5, which sets a new efficiency record for a bio-related hydrogen fuel cell with base metal catalysts.« less

Imaging of the outer valence orbitals of CO by electron momentum spectroscopy — Comparison with high level MRSD-CI and DFT calculations

NASA Astrophysics Data System (ADS)

Fan, X. W.; Chen, X. J.; Zhou, S. J.; Zheng, Y.; Brion, C. E.; Frey, R.; Davidson, E. R.

1997-09-01

A newly constructed energy dispersive multichannel electron momentum spectrometer has been used to image the electron density of the outer valence orbitals of CO with high precision. Binding energy spectra are obtained at a coincidence energy resolution of 1.2 eV fwhm. The measured electron density profiles in momentum space for the outer valence orbitals of CO are compared with cross sections calculated using SCF wavefunctions with basis sets of varying complexity up to near-Hartree-Fock limit in quality. The effects of correlation and electronic relaxation on the calculated momentum profiles are investigated using large MRSD-CI calculations of the full ion-neutral overlap distributions, as well as large basis set DFT calculations with local and non-local (gradient corrected) functionals.

Storm-time radiation belt electron dynamics: Repeatability in the outer radiation belt

NASA Astrophysics Data System (ADS)

Murphy, K. R.; Mann, I. R.; Rae, J.; Watt, C.; Boyd, A. J.; Turner, D. L.; Claudepierre, S. G.; Baker, D. N.; Spence, H. E.; Reeves, G. D.; Blake, J. B.; Fennell, J. F.

2017-12-01

During intervals of enhanced solar wind driving the outer radiation belt becomes extremely dynamic leading to geomagnetic storms. During these storms the flux of energetic electrons can vary by over 4 orders of magnitude. Despite recent advances in understanding the nature of competing storm-time electron loss and acceleration processes the dynamic behavior of the outer radiation belt remains poorly understood; the outer radiation belt can exhibit either no change, an enhancement, or depletion in radiation belt electrons. Using a new analysis of the total radiation belt electron content, calculated from the Van Allen probes phase space density (PSD), we statistically analyze the time-dependent and global response of the outer radiation belt during storms. We demonstrate that by removing adiabatic effects there is a clear and repeatable sequence of events in storm-time radiation belt electron dynamics. Namely, the relativistic (μ=1000 MeV/G) and ultra-relativistic (μ=4000 MeV/G) electron populations can be separated into two phases; an initial phase dominated by loss followed by a second phase dominated by acceleration. At lower energies, the radiation belt seed population of electrons (μ=150 MeV/G) shows no evidence of loss but rather a net enhancement during storms. Further, we investigate the dependence of electron dynamics as a function of the second adiabatic invariant, K. These results demonstrate a global coherency in the dynamics of the source, relativistic and ultra-relativistic electron populations as function of the second adiabatic invariant K. This analysis demonstrates two key aspects of storm-time radiation belt electron dynamics. First, the radiation belt responds repeatably to solar wind driving during geomagnetic storms. Second, the response of the radiation belt is energy dependent, relativistic electrons behaving differently than lower energy seed electrons. These results have important implications in radiation belt research. In particular, the repeatability in electron dynamics coupled with observations of processes leading to electron loss (EMIC waves) and acceleration (VLF or ULF waves) can be used to diagnose the relative importance of physical processes in radiation belt dynamics during storms.

Fe2O3 hollow sphere nanocomposites for supercapacitor applications

NASA Astrophysics Data System (ADS)

Zhao, Yu; Wen, Yang; Xu, Bing; Lu, Lu; Ren, Reiming

2018-02-01

Nanomaterials have attracted increasing interest in electrochemical energy storage and conversion. Hollow sphere Fe2O3 nanocomposites were successfully prepared through facile low temperature water-bath method with carbon sphere as hard template. The morphology and microstructure of samples were characterized by X-ray diffraction (XRD) and Scanning electron microscope (SEM), respectively. Through hydrolysis mechanism, using ferric chloride direct hydrolysis, iron hydroxide coated on the surface of carbon sphere, after high temperature calcination can form the hollow spherical iron oxide materials. Electrochemical performances of the hollow sphere Fe2O3 nanocomposites electrodes were investigated by cyclic voltammery (CV) and galvanostatic charge/discharge. The Pure hollow sphere Fe2O3 nanocomposites achieves a specific capacitance of 125 F g-1 at the current density of 85 mA g-1. The results indicate that the uniform dispersion of hollow ball structure can effectively reduce the particle reunion in the process of charging and discharging.

Synthesis and transfer of galactolipids in the chloroplast envelope membranes of Arabidopsis thaliana.

PubMed

Kelly, Amélie A; Kalisch, Barbara; Hölzl, Georg; Schulze, Sandra; Thiele, Juliane; Melzer, Michael; Roston, Rebecca L; Benning, Christoph; Dörmann, Peter

2016-09-20

Galactolipids [monogalactosyldiacylglycerol (MGDG) and digalactosyldiacylglycerol (DGDG)] are the hallmark lipids of photosynthetic membranes. The galactolipid synthases MGD1 and DGD1 catalyze consecutive galactosyltransfer reactions but localize to the inner and outer chloroplast envelopes, respectively, necessitating intermembrane lipid transfer. Here we show that the N-terminal sequence of DGD1 (NDGD1) is required for galactolipid transfer between the envelopes. Different diglycosyllipid synthases (DGD1, DGD2, and Chloroflexus glucosyltransferase) were introduced into the dgd1-1 mutant of Arabidopsis in fusion with N-terminal extensions (NDGD1 and NDGD2) targeting to the outer envelope. Reconstruction of DGDG synthesis in the outer envelope membrane was observed only with diglycosyllipid synthase fusion proteins carrying NDGD1, indicating that NDGD1 enables galactolipid translocation between envelopes. NDGD1 binds to phosphatidic acid (PA) in membranes and mediates PA-dependent membrane fusion in vitro. These findings provide a mechanism for the sorting and selective channeling of lipid precursors between the galactolipid pools of the two envelope membranes.

Neutron transport analysis for nuclear reactor design

DOEpatents

Vujic, Jasmina L.

1993-01-01

Replacing regular mesh-dependent ray tracing modules in a collision/transfer probability (CTP) code with a ray tracing module based upon combinatorial geometry of a modified geometrical module (GMC) provides a general geometry transfer theory code in two dimensions (2D) for analyzing nuclear reactor design and control. The primary modification of the GMC module involves generation of a fixed inner frame and a rotating outer frame, where the inner frame contains all reactor regions of interest, e.g., part of a reactor assembly, an assembly, or several assemblies, and the outer frame, with a set of parallel equidistant rays (lines) attached to it, rotates around the inner frame. The modified GMC module allows for determining for each parallel ray (line), the intersections with zone boundaries, the path length between the intersections, the total number of zones on a track, the zone and medium numbers, and the intersections with the outer surface, which parameters may be used in the CTP code to calculate collision/transfer probability and cross-section values.

Neutron transport analysis for nuclear reactor design

DOEpatents

Vujic, J.L.

1993-11-30

Replacing regular mesh-dependent ray tracing modules in a collision/transfer probability (CTP) code with a ray tracing module based upon combinatorial geometry of a modified geometrical module (GMC) provides a general geometry transfer theory code in two dimensions (2D) for analyzing nuclear reactor design and control. The primary modification of the GMC module involves generation of a fixed inner frame and a rotating outer frame, where the inner frame contains all reactor regions of interest, e.g., part of a reactor assembly, an assembly, or several assemblies, and the outer frame, with a set of parallel equidistant rays (lines) attached to it, rotates around the inner frame. The modified GMC module allows for determining for each parallel ray (line), the intersections with zone boundaries, the path length between the intersections, the total number of zones on a track, the zone and medium numbers, and the intersections with the outer surface, which parameters may be used in the CTP code to calculate collision/transfer probability and cross-section values. 28 figures.

Superconducting coil and method of stress management in a superconducting coil

DOEpatents

McIntyre, Peter M.; Shen, Weijun; Diaczenko, Nick; Gross, Dan A.

1999-01-01

A superconducting coil (12) having a plurality of superconducting layers (18) is provided. Each superconducting layer (18) may have at least one superconducting element (20) which produces an operational load. An outer support structure (24) may be disposed outwardly from the plurality of layers (18). A load transfer system (22) may be coupled between at least one of the superconducting elements (20) and the outer support structure (24). The load transfer system (22) may include a support matrix structure (30) operable to transfer the operational load from the superconducting element (20) directly to the outer support structure (24). A shear release layer (40) may be disposed, in part, between the superconducting element (20) and the support matrix structure (30) for relieving a shear stress between the superconducting element (20) and the support matrix structure (30). A compliant layer (42) may also be disposed, in part, between the superconducting element (20) and the support matrix structure (30) for relieving a compressive stress on the superconducting element (20).

Contact and Impact Dynamic Modeling Capabilities of LS-DYNA for Fluid-Structure Interaction Problems

DTIC Science & Technology

2010-12-02

rigid sphere in a vertical water entry,” Applied Ocean Research, 13(1), pp. 43-48. Monaghan, J.J., 1994. “ Simulating free surface flows with SPH ...The kinematic free surface condition was used to determine the intersection between the free surface and the body in the outer flow domain...and the results were compared with analytical and numerical predictions. The predictive capability of ALE and SPH features of LS-DYNA for simulation

Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere

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

Jain, Avijita; Buchko, Garry W.; Reback, Matthew L.

2012-10-05

The synthesis, catalytic activity, and structural features of a rhodium-based hydrogenation catalyst containing a phosphine ligand coupled to a 14-residue peptide are reported. Both CD and NMR spectroscopy show that the peptide adopts a helical structure in 1:1:1 TFE/MeCN/H2O that is maintained when the peptide is attached to the ligand and when the ligand is attached to the metal complex. The metal complex hydrogenates aqueous solutions of 3-butenol to 1-butanol at 360 ± 50 turnovers/Rh/h at 294 K. This peptide- based catalyst represents a starting point for developing and characterizing a peptide-based outer-coordination sphere that can be used to introducemore » enzyme-like features into molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AJ, JCL and WJS), the Office of Science Early Career Research Program through the Office of Basic Energy Sciences (GWB, MLR and WJS). Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy’s Office of Biolog-ical and Environmental Research (BER) program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.« less

An Advanced Semimetal-Organic Bi Spheres-g-C3N4 Nanohybrid with SPR-Enhanced Visible-Light Photocatalytic Performance for NO Purification.

PubMed

Dong, Fan; Zhao, Zaiwang; Sun, Yanjuan; Zhang, Yuxin; Yan, Shuai; Wu, Zhongbiao

2015-10-20

To achieve efficient photocatalytic air purification, we constructed an advanced semimetal-organic Bi spheres-g-C3N4 nanohybrid through the in-situ growth of Bi nanospheres on g-C3N4 nanosheets. This Bi-g-C3N4 compound exhibited an exceptionally high and stable visible-light photocatalytic performance for NO removal due to the surface plasmon resonance (SPR) endowed by Bi metal. The SPR property of Bi could conspicuously enhance the visible-light harvesting and the charge separation. The electromagnetic field distribution of Bi spheres involving SPR effect was simulated and reaches its maximum in close proximity to the Bi particle surface. When the Bi metal content was controlled at 25%, the corresponding Bi-g-C3N4 displayed outstanding photocatalytic capability and transcended those of other visible-light photocatalysts. The Bi-g-C3N4 exhibited a high structural stability under repeated photocatalytic runs. A new visible-light-induced SPR-based photocatalysis mechanism with Bi-g-C3N4 was proposed on the basis of the DMPO-ESR spin-trapping. The photoinduced electrons could transfer from g-C3N4 to the Bi metal, as revealed with time-resolved fluorescence spectra. The function of Bi semimetal as a plasmonic cocatalyst for boosting visible light photocatalysis was similar to that of noble metals, which demonstrated a great potential of utilizing the economically feasible Bi element as a substitute for noble metals for the advancement of photocatalysis efficiency.

Remarkable activity of nitrogen-doped hollow carbon spheres encapsulated Cu on synthesis of dimethyl carbonate: Role of effective nitrogen

NASA Astrophysics Data System (ADS)

Li, Haixia; Zhao, Jinxian; Shi, Ruina; Hao, Panpan; Liu, Shusen; Li, Zhong; Ren, Jun

2018-04-01

A critical aspect in the improvement of the catalytic performance of Cu-based catalysts for the synthesis of dimethyl carbonate (DMC) is the development of an appropriate support. In this work, nitrogen-doped hollow carbon spheres (NHCSs), with 240 nm average diameter, 17 nm shell thickness, uniform mesoporous structure and a specific surface area of 611 m2 g-1, were prepared via a two-step Stӧber method. By varying the quantity of nitrogen-containing phenols used in the preparation it has been possible to control the nitrogen content and, consequently, the sphericity of the NHCSs. It was found that perfect spheres were obtained for nitrogen contents below 5.4 wt.%. The catalysts (Cu@NHCSs) were prepared by the hydrothermal impregnation method. The catalytic activity towards DMC synthesis was notably enhanced due to the immobilization effect on Cu particles and the enhanced electron transfer effect exercised by the effective nitrogen species, including pyridinic-N and graphitic-N. When the average size of the copper nanoparticles was 7.4 nm and the nitrogen content was 4.0 wt.%, the values of space-time yield of DMC and of turnover frequency (TOF) reached 1528 mg/(g h) and 11.0 h-1, respectively. The TOF value of Cu@NHCSs was 6 times higher than non-doped Cu@Carbon (2.1 h-1). The present work introduces the potential application of nitrogen-doped carbon materials and presents a novel procedure for the preparation of catalysts for DMC synthesis.

Random Walk Particle Tracking For Multiphase Heat Transfer

NASA Astrophysics Data System (ADS)

Lattanzi, Aaron; Yin, Xiaolong; Hrenya, Christine

2017-11-01

As computing capabilities have advanced, direct numerical simulation (DNS) has become a highly effective tool for quantitatively predicting the heat transfer within multiphase flows. Here we utilize a hybrid DNS framework that couples the lattice Boltzmann method (LBM) to the random walk particle tracking (RWPT) algorithm. The main challenge of such a hybrid is that discontinuous fields pose a significant challenge to the RWPT framework and special attention must be given to the handling of interfaces. We derive a method for addressing discontinuities in the diffusivity field, arising at the interface between two phases. Analytical means are utilized to develop an interfacial tracer balance and modify the RWPT algorithm. By expanding the modulus of the stochastic (diffusive) step and only allowing a subset of the tracers within the high diffusivity medium to undergo a diffusive step, the correct equilibrium state can be restored (globally homogeneous tracer distribution). The new RWPT algorithm is implemented within the SUSP3D code and verified against a variety of systems: effective diffusivity of a static gas-solids mixture, hot sphere in unbounded diffusion, cooling sphere in unbounded diffusion, and uniform flow past a hot sphere.

Obtaining the Bidirectional Transfer Distribution Function ofIsotropically Scattering Materials Using an Integrating Sphere

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

Jonsson, Jacob C.; Branden, Henrik

2006-10-19

This paper demonstrates a method to determine thebidirectional transfer distribution function (BTDF) using an integratingsphere. Information about the sample's angle dependent scattering isobtained by making transmittance measurements with the sample atdifferent distances from the integrating sphere. Knowledge about theilluminated area of the sample and the geometry of the sphere port incombination with the measured data combines to an system of equationsthat includes the angle dependent transmittance. The resulting system ofequations is an ill-posed problem which rarely gives a physical solution.A solvable system is obtained by using Tikhonov regularization on theill-posed problem. The solution to this system can then be usedmore » to obtainthe BTDF. Four bulk-scattering samples were characterised using both twogoniophotometers and the described method to verify the validity of thenew method. The agreement shown is great for the more diffuse samples.The solution to the low-scattering samples contains unphysicaloscillations, butstill gives the correct shape of the solution. Theorigin of the oscillations and why they are more prominent inlow-scattering samples are discussed.« less

Semiconductors Under Ion Radiation: Ultrafast Electron-Ion Dynamics in Perfect Crystals and the Effect of Defects

NASA Astrophysics Data System (ADS)

Lee, Cheng-Wei; Schleife, André

Stability and safety issues have been challenging difficulties for materials and devices under radiation such as solar panels in outer space. On the other hand, radiation can be utilized to modify materials and increase their performance via focused-ion beam patterning at nano-scale. In order to grasp the underlying processes, further understanding of the radiation-material and radiation-defect interactions is required and inevitably involves the electron-ion dynamics that was traditionally hard to capture. By applying Ehrenfest dynamics based on time-dependent density functional theory, we have been able to perform real-time simulation of electron-ion dynamics in MgO and InP/GaP. By simulating a high-energy proton penetrating the material, the energy gain of electronic system can be interpreted as electronic stopping power and the result is compared to existing data. We also study electronic stopping in the vicinity of defects: for both oxygen vacancy in MgO and interface of InP/GaP superlattice, electronic stopping shows strong dependence on the velocity of the proton. To study the energy transfer from electronic system to lattice, simulations of about 100 femto-seconds are performed and we analyze the difference between Ehrenfest and Born-Oppenheimer molecular dynamics.

Acoustic levitation of a large solid sphere

NASA Astrophysics Data System (ADS)

Andrade, Marco A. B.; Bernassau, Anne L.; Adamowski, Julio C.

2016-07-01

We demonstrate that acoustic levitation can levitate spherical objects much larger than the acoustic wavelength in air. The acoustic levitation of an expanded polystyrene sphere of 50 mm in diameter, corresponding to 3.6 times the wavelength, is achieved by using three 25 kHz ultrasonic transducers arranged in a tripod fashion. In this configuration, a standing wave is created between the transducers and the sphere. The axial acoustic radiation force generated by each transducer on the sphere was modeled numerically as a function of the distance between the sphere and the transducer. The theoretical acoustic radiation force was verified experimentally in a setup consisting of an electronic scale and an ultrasonic transducer mounted on a motorized linear stage. The comparison between the numerical and experimental acoustic radiation forces presents a good agreement.

30 CFR 1220.015 - Pricing of materiel purchases, transfers, and dispositions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Pricing of materiel purchases, transfers, and... PAYMENT FOR OUTER CONTINENTAL SHELF OIL AND GAS LEASES § 1220.015 Pricing of materiel purchases, transfers... accordance with § 1220.011(c)(3). (2) Transferred and disposal materiel. An item of materiel, which is...

Roles of whistler mode waves and magnetosonic waves in changing the outer radiation belt and the slot region

NASA Astrophysics Data System (ADS)

Li, L. Y.; Yu, J.; Cao, J. B.; Yang, J. Y.; Li, X.; Baker, D. N.; Reeves, G. D.; Spence, H.

2017-05-01

Using the Van Allen Probe long-term (2013-2015) observations and quasi-linear simulations of wave-particle interactions, we examine the combined or competing effects of whistler mode waves (chorus or hiss) and magnetosonic (MS) waves on energetic (<0.5 MeV) and relativistic (>0.5 MeV) electrons inside and outside the plasmasphere. Although whistler mode chorus waves and MS waves can singly or jointly accelerate electrons from the hundreds of keV energy to the MeV energy in the low-density trough, most of the relativistic electron enhancement events are best correlated with the chorus wave emissions outside the plasmapause. Inside the plasmasphere, intense plasmaspheric hiss can cause the net loss of relativistic electrons via persistent pitch angle scattering, regardless of whether MS waves were present or not. The intense hiss waves not only create the energy-dependent electron slot region but also remove a lot of the outer radiation belt electrons when the expanding dayside plasmasphere frequently covers the outer zone. Since whistler mode waves (chorus or hiss) can resonate with more electrons than MS waves, they play dominant roles in changing the outer radiation belt and the slot region. However, MS waves can accelerate the energetic electrons below 400 keV and weaken their loss inside the plasmapause. Thus, MS waves and plasmaspheric hiss generate different competing effects on energetic and relativistic electrons in the high-density plasmasphere.

Propagation of Interplanetary Disturbances in the Outer Heliosphere

NASA Technical Reports Server (NTRS)

Wang, Chi

2005-01-01

Contents include the following: 1. We have developed a one-dimensional, spherically symmetric, multi-fluid MHD model that includes solar wind protons and electrons, pickup ions, and interstellar neutral hydrogen. This model advances the existing solar wind models for the outer heliosphere in two important ways: one is that it distinguishes solar wind protons from pickup ions, and the other is that it allows for energy transfer from pickup ions to the solar wind protons. Model results compare favorably with the Voyager 2 observations. 2. 2. Solar wind slowdown and interstellar neutral density. The solar wind in the outer heliosphere is fundamentally different from that in the inner heliosphere since the effects of interstellar neutrals become significant. 3. ICME propagation from the inner to outer heliosphere. Large coronal mass ejections (CMEs) have major effects on the structure of the solar wind and the heliosphere. The plasma and magnetic field can be compressed ahead of interplanetary CMEs. 4. During the current solar cycle (Cycle 23), several major CMEs associated with solar flares produced large transient shocks which were observed by widely-separated spacecraft such as Wind at Earth and Voyager 2 beyond 60 AU. Using data from these spacecraft, we use the multi-fluid model to investigate shock propagation and interaction in the heliosphere. Specifically, we studied the Bastille Day 2000, April 2001 and Halloween 2003 events. 5. Statistical properties of the solar wind in the outer heliosphere. In a collaboration with L.F. Burlaga of GSFC, it is shown that the basic statistical properties of the solar wind in the outer heliosphere can be well produced by our model. We studied the large-scale heliospheric magnetic field strength fluctuations as a function of distance from the Sun during the declining phase of a solar cycle, using our numerical model with observations made at 1 AU during 1995 as input. 6. Radial heliospheric magnetic field events. The heliospheric magnetic field (HMF) direction, on average, conforms well to the Parker spiral.

Simulation of high-energy radiation belt electron fluxes using NARMAX-VERB coupled codes

PubMed Central

Pakhotin, I P; Drozdov, A Y; Shprits, Y Y; Boynton, R J; Subbotin, D A; Balikhin, M A

2014-01-01

This study presents a fusion of data-driven and physics-driven methodologies of energetic electron flux forecasting in the outer radiation belt. Data-driven NARMAX (Nonlinear AutoRegressive Moving Averages with eXogenous inputs) model predictions for geosynchronous orbit fluxes have been used as an outer boundary condition to drive the physics-based Versatile Electron Radiation Belt (VERB) code, to simulate energetic electron fluxes in the outer radiation belt environment. The coupled system has been tested for three extended time periods totalling several weeks of observations. The time periods involved periods of quiet, moderate, and strong geomagnetic activity and captured a range of dynamics typical of the radiation belts. The model has successfully simulated energetic electron fluxes for various magnetospheric conditions. Physical mechanisms that may be responsible for the discrepancies between the model results and observations are discussed. PMID:26167432

Heat exchanger efficiently operable alternatively as evaporator or condenser

DOEpatents

Ecker, Amir L.

1981-01-01

A heat exchanger adapted for efficient operation alternatively as evaporator or condenser and characterized by flexible outer tube having a plurality of inner conduits and check valves sealingly disposed within the outer tube and connected with respective inlet and outlet master flow conduits and configured so as to define a parallel flow path for a first fluid such as a refrigerant when flowed in one direction and to define a serpentine and series flow path for the first fluid when flowed in the opposite direction. The flexible outer tube has a heat exchange fluid, such as water, flowed therethrough by way of suitable inlet and outlet connections. The inner conduits and check valves form a package that is twistable so as to define a spiral annular flow path within the flexible outer tube for the heat exchange fluid. The inner conduits have thin walls of highly efficient heat transfer material for transferring heat between the first and second fluids. Also disclosed are specific materials and configurations.

The fabrication and electrochemical properties of electrospun nanofibers of a multiwalled carbon nanotube grafted by chitosan

NASA Astrophysics Data System (ADS)

Feng, Wei; Wu, Zigang; Li, Yu; Feng, Yiyu; Yuan, Xiaoyan

2008-03-01

Multiwalled carbon nanotubes (MWCNTs) were grafted by chitosan (CS); the product could disperse well in poly(vinyl alcohol) (PVA) aqueous solution with 2% (v/v) acetic acid solution. Because this product has potential in several biological fields, it was electrospun so as to enlarge the surface area. Raman spectra indicated that the electrospinning process did not severely alter the electron hybridization of carbon atoms within the nanotube framework. Moreover and interestingly, these nanofibers showed a novel sheath-core structure; the outer and inner diameters of these sheath-core nanofibers were about 200 nm and 100 nm, respectively. These nanofibers' electrochemical properties were characterized by detection of hydrogen peroxide and voltammetric responses of potassium ferricyanide. The electrospun fibers' web displayed faster electron transfer kinetics and better electrochemical properties than its cast film, which justified further applications in biological areas.

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

Melo, Ronaldo P. de; Colégio Militar do Recife, Exército Brasileiro, Recife PE 50730-120; Oliveira, Nathalia Talita C.

A novel procedure based on a two-step method was developed to obtain β-Ga{sub 2}O{sub 3} nanowires by the chemical vapor deposition (CVD) method. The first step consists in the gallium micro-spheres growth inside a metal-organic chemical vapor deposition environment, using an organometallic precursor. Nanoscale spheres covering the microspheres were obtained. The second step involves the CVD oxidization of the gallium micro-spheres, which allow the formation of β-Ga{sub 2}O{sub 3} nanowires on the micro-sphere surface, with the final result being a nanostructure mimicking nature's sea urchin morphology. The grown nanomaterial is characterized by several techniques, including X-ray diffraction, scanning electron microscopy,more » energy-dispersive X-ray, transmission electron microscopy, and photoluminescence. A discussion about the growth mechanism and the optical properties of the β-Ga{sub 2}O{sub 3} material is presented considering its unknown true bandgap value (extending from 4.4 to 5.68 eV). As an application, the scattering properties of the nanomaterial are exploited to demonstrate random laser emission (around 570 nm) when it is permeated with a laser dye liquid solution.« less

The Role of 4-Hydroxyphenylpyruvate Dioxygenase in Enhancement of Solid-Phase Electron Transfer by Shewanella oneidensis MR-1

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

Turick, Charles E.; Beliaev, Alex S.; Zakrajsek, Brian A.

2009-05-01

ABSTRACT - While mechanistic details of dissimilatory metal reduction are far from being understood, it is postulated that the electron transfer to solid metal oxides is mediated by outer membrane associated c-type cytochromes and electron shuttling compounds. This study focuses on the production of homogensitate in Shewanella oneidensis MR-1, an intermediate of the tyrosine degradation pathway, which is a precursor of a redox cycling metabolite, pyomelanin. We determined that two enzymes involved in this pathway, 4-hydroxyphenylpyruvate dioxygenase (4HPPD) and homogentisate 1,2-dioxygenase are responsible for homogentisate production and oxidation, respectively. Inhibition of 4-HPPD activity with the specific inhibitor sulcotrione ([2-(2- chloro-more » 4- methane sulfonylbenzoyl)-1,3-cyclohexanedione), and deletion of melA, a gene encoding 4-HPPD, resulted in no pyomelanin production by S. oneidensis MR-1. Conversely, deletion of hmgA, which encodes the putative homogentisate 1,2-dioxygenase, resulted in pyomelanin overproduction. The efficiency and rates at which MR-1 reduces hydrous ferric oxide were directly linked to the ability of mutant strains to produce pyomelanin. Electrochemical studies with whole cells demonstrated that pyomelanin substantially increases the formal potential (E°') of S. oneidensis MR-1. Based on our findings, environmental production of pyomelanin likely contributes to an increased solid-phase metal reduction capacity in S. oneidensis MR-1.« less

THE ROLE OF 4-HYDROXYPHENYLPYRUVATE DIOXYGENASE IN ENHANCEMENT OF SOLID-PHASE ELECTRON TRANSFER BY SHEWANELLA ONEIDENSIS MR-1

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

Turick, C; Amy Ekechukwu, A

2007-06-01

While mechanistic details of dissimilatory metal reduction are far from being understood, it is postulated that the electron transfer to solid metal oxides is mediated by outer membrane-associated c-type cytochromes and redox active electron shuttling compounds. This study focuses on the production of homogensitate in Shewanella oneidensis MR-1, an intermediate of tyrosine degradation pathway, which is a precursor of a redox cycling metabolite, pyomelanin. In this study, we determined that two enzymes involved in this pathway, 4-hydroxyphenylpyruvate dioxygenase (4HPPD) and homogentisate 1,2-dioxygenase are responsible for homogentisate production and oxidation, respectively. Inhibition of 4-HPPD activity with the specific inhibitor sulcotrione (2-(2-chloro-4-methanemore » sulfonylbenzoyl)-1,3-cyclohexanedione), and deletion of melA, a gene encoding 4-HPPD, resulted in no pyomelanin production by S. oneidensis MR-1. Conversely, deletion of hmgA which encodes the putative homogentisate 1,2-dioxygenase, resulted in pyomelanin overproduction. The efficiency and rates, with which MR-1 reduces hydrous ferric oxide, were directly linked to the ability of mutant strains to produce pyomelanin. Electrochemical studies with whole cells demonstrated that pyomelanin substantially increases the formal potential (E{sup o}{prime}) of S. oneidensis MR-1. Based on this work, environmental production of pyomelanin likely contributes to an increased solid-phase metal reduction capacity in Shewanella oneidensis.« less

Target electron ionization in Li2+-Li collisions: A multi-electron perspective

NASA Astrophysics Data System (ADS)

Śpiewanowski, M. D.; Gulyás, L.; Horbatsch, M.; Kirchner, T.

2015-05-01

The recent development of the magneto-optical trap reaction-microscope has opened a new chapter for detailed investigations of charged-particle collisions from alkali atoms. It was shown that energy-differential cross sections for ionization from the outer-shell in O8+-Li collisions at 1500 keV/amu can be readily explained with the single-active-electron approximation. Understanding of K-shell ionization, however, requires incorporating many-electron effects. An ionization-excitation process was found to play an important role. We present a theoretical study of target electron removal in Li2+-Li collisions at 2290 keV/amu. The results indicate that in outer-shell ionization a single-electron process plays the dominant part. However, the K-shell ionization results are more difficult to interpret. On one hand, we find only weak contributions from multi-electron processes. On the other hand, a large discrepancy between experimental and single-particle theoretical results indicate that multi-electron processes involving ionization from the outer shell may be important for a complete understanding of the process. Work supported by NSERC, Canada and the Hungarian Scientific Research Fund.

Contactless ultrasonic energy transfer for wireless systems: acoustic-piezoelectric structure interaction modeling and performance enhancement

NASA Astrophysics Data System (ADS)

Shahab, S.; Erturk, A.

2014-12-01

There are several applications of wireless electronic components with little or no ambient energy available to harvest, yet wireless battery charging for such systems is still of great interest. Example applications range from biomedical implants to sensors located in hazardous environments. Energy transfer based on the propagation of acoustic waves at ultrasonic frequencies is a recently explored alternative that offers increased transmitter-receiver distance, reduced loss and the elimination of electromagnetic fields. As this research area receives growing attention, there is an increased need for fully coupled model development to quantify the energy transfer characteristics, with a focus on the transmitter, receiver, medium, geometric and material parameters. We present multiphysics modeling and case studies of the contactless ultrasonic energy transfer for wireless electronic components submerged in fluid. The source is a pulsating sphere, and the receiver is a piezoelectric bar operating in the 33-mode of piezoelectricity with a fundamental resonance frequency above the audible frequency range. The goal is to quantify the electrical power delivered to the load (connected to the receiver) in terms of the source strength. Both the analytical and finite element models have been developed for the resulting acoustic-piezoelectric structure interaction problem. Resistive and resistive-inductive electrical loading cases are presented, and optimality conditions are discussed. Broadband power transfer is achieved by optimal resistive-reactive load tuning for performance enhancement and frequency-wise robustness. Significant enhancement of the power output is reported due to the use of a hard piezoelectric receiver (PZT-8) instead of a soft counterpart (PZT-5H) as a result of reduced material damping. The analytical multiphysics modeling approach given in this work can be used to predict and optimize the coupled system dynamics with very good accuracy and dramatically improved computational efficiency compared to the use of commercial finite element packages.

Synthetic-Focusing Strategies for Real-Time Annular-Array Imaging

PubMed Central

Ketterling, Jeffrey A.; Filoux, Erwan

2012-01-01

Annular arrays provide a means to achieve enhanced image quality with a limited number of elements. Synthetic-focusing (SF) strategies that rely on beamforming data from individual transmit-to-receive (TR) element pairs provide a means to improve image quality without specialized TR delay electronics. Here, SF strategies are examined in the context of high-frequency ultrasound (>15 MHz) annular arrays composed of five elements, operating at 18 and 38 MHz. Acoustic field simulations are compared with experimental data acquired from wire and anechoic-sphere phantoms, and the values of lateral beamwidth, SNR, contrast-to-noise ratio (CNR), and depth of field (DOF) are compared as a function of depth. In each case, data were acquired for all TR combinations (25 in total) and processed with SF using all 25 TR pairs and SF with the outer receive channels removed one by one. The results show that removing the outer receive channels led to an overall degradation of lateral resolution, an overall decrease in SNR, and did not reduce the DOF, although the DOF profile decreased in amplitude. The CNR was >1 and remained fairly constant as a function of depth, with a slight decrease in CNR for the case with just the central element receiving. The relative changes between the calculated and measured quantities were nearly identical for the 18- and 38-MHz arrays. B-mode images of the anechoic phantom and an in vivo mouse embryo using full SF with 25 TR pairs or reduced TR-pair approaches showed minimal qualitative difference. PMID:22899130

Development of soft-sphere contact models for thermal heat conduction in granular flows

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

Morris, A. B.; Pannala, S.; Ma, Z.

2016-06-08

Conductive heat transfer to flowing particles occurs when two particles (or a particle and wall) come into contact. The direct conduction between the two bodies depends on the collision dynamics, namely the size of the contact area and the duration of contact. For soft-sphere discrete-particle simulations, it is computationally expensive to resolve the true collision time because doing so would require a restrictively small numerical time step. To improve the computational speed, it is common to increase the 'softness' of the material to artificially increase the collision time, but doing so affects the heat transfer. In this work, two physically-basedmore » correction terms are derived to compensate for the increased contact area and time stemming from artificial particle softening. By including both correction terms, the impact that artificial softening has on the conductive heat transfer is removed, thus enabling simulations at greatly reduced computational times without sacrificing physical accuracy.« less

VLF Wave Local Acceleration & ULF Wave Radial Diffusion: The Importance of K-Dependent PSD Analysis for Diagnosing the cause of Radiation Belt Acceleration.

NASA Astrophysics Data System (ADS)

Ozeke, L.; Mann, I. R.; Claudepierre, S. G.; Morley, S.; Henderson, M. G.; Baker, D. N.; Kletzing, C.; Spence, H. E.

2017-12-01

We present results showing the temporal evolution of electron Phase Space Density (PSD) in the outer radiation belt during the most intense geomagnetic storm of the last decade which occurred on March 17th 2015. Based on observations of growing local PSD peaks at fixed first and second adiabatic invariants of M=1000 MeV/G and K=0.18 G1/2Re respectively, previous studies argued that the outer radiation belt flux enhancement that occurred during this storm resulted from local acceleration driven by VLF waves. Here we show that the vast majority of the outer radiation belt consisted of electrons with much lower K-values than 0.18 G1/2Re, and that at these lower K-values there is no clear evidence of growing local PSD peaks consistent with that expected from local acceleration. Contrary to prior studies we show that the outer radiation belt flux enhancement is consistent with inward radial diffusion driven by ULF waves and present evidence that the growing local PSD peaks at K=0.18 G1/2Re and M=1000 MeV/G result from pitch-angle scattering of lower-K electrons to K=0.18 G1/2Re. In addition, we also show that the observed outer radiation belt flux enhancement during this geomagnetic storm can be reproduced using a radial diffusion model driven by measured ULF waves without including any local acceleration. These results highlight the importance of careful analysis of the electron PSD profiles as a function of L* over a range of fixed first, M and second K, adiabatic invariants to correctly determine the mechanism responsible for the electron flux enhancements observed in the outer radiation belt.

A new Predictive Model for Relativistic Electrons in Outer Radiation Belt

NASA Astrophysics Data System (ADS)

Chen, Y.

2017-12-01

Relativistic electrons trapped in the Earth's outer radiation belt present a highly hazardous radiation environment for spaceborne electronics. These energetic electrons, with kinetic energies up to several megaelectron-volt (MeV), manifest a highly dynamic and event-specific nature due to the delicate interplay of competing transport, acceleration and loss processes. Therefore, developing a forecasting capability for outer belt MeV electrons has long been a critical and challenging task for the space weather community. Recently, the vital roles of electron resonance with waves (including such as chorus and electromagnetic ion cyclotron) have been widely recognized; however, it is still difficult for current diffusion radiation belt models to reproduce the behavior of MeV electrons during individual geomagnetic storms, mainly because of the large uncertainties existing in input parameters. In this work, we expanded our previous cross-energy cross-pitch-angle coherence study and developed a new predictive model for MeV electrons over a wide range of L-shells inside the outer radiation belt. This new model uses NOAA POES observations from low-Earth-orbits (LEOs) as inputs to provide high-fidelity nowcast (multiple hour prediction) and forecast (> 1 day prediction) of the energization of MeV electrons as well as the evolving MeV electron distributions afterwards during storms. Performance of the predictive model is quantified by long-term in situ data from Van Allen Probes and LANL GEO satellites. This study adds new science significance to an existing LEO space infrastructure, and provides reliable and powerful tools to the whole space community.

10 CFR 32.19 - Same: Conditions of licenses.

Code of Federal Regulations, 2010 CFR

2010-01-01

... NUCLEAR REGULATORY COMMISSION SPECIFIC DOMESTIC LICENSES TO MANUFACTURE OR TRANSFER CERTAIN ITEMS... set forth in § 30.71, Schedule B of this chapter shall be sold or transferred in any single... packaged exempt quantities shall be contained in any outer package for transfer to persons exempt pursuant...

10 CFR 32.19 - Same: Conditions of licenses.

Code of Federal Regulations, 2011 CFR

2011-01-01

... NUCLEAR REGULATORY COMMISSION SPECIFIC DOMESTIC LICENSES TO MANUFACTURE OR TRANSFER CERTAIN ITEMS... set forth in § 30.71, Schedule B of this chapter shall be sold or transferred in any single... packaged exempt quantities shall be contained in any outer package for transfer to persons exempt pursuant...

On the anomalous adsorption of [Pd(edta)]2- at the water/Goethite interface: spectroscopic evidence for two types of surface complexes.

PubMed

Kaplun, Marina; Nordin, Agneta; Persson, Per

2008-01-15

The structure of palladium(II) ethylenediaminetetraacetate (edta) in aqueous solutions and its adsorption on the surface of goethite (alpha-FeOOH) were studied using extended X-ray absorption fine structure spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. The obtained results show that in aqueous solutions, Pd-edta exists as a 1:1 complex, [Pd(edta)]2-, with edta acting as a quadridentate ligand. On the surface of goethite, [Pd(edta)]2- forms two different types of complexes over a pH range of 3.40-8.12. At pH < 5, [Pd(edta)]2- adsorbs as an outer-sphere species with possible hydrogen bonding. At higher pH values, the formation of inner-sphere complexes of the cation-type sets in after a cleavage of one glycinate ring and the formation of an (edta)Pd-O-Fe linkage.

Pulsation of black holes

NASA Astrophysics Data System (ADS)

Gao, Changjun; Lu, Youjun; Shen, You-Gen; Faraoni, Valerio

2018-01-01

The Hawking-Penrose singularity theorem states that a singularity forms inside a black hole in general relativity. To remove this singularity one must resort to a more fundamental theory. Using a corrected dynamical equation arising in loop quantum cosmology and braneworld models, we study the gravitational collapse of a perfect fluid sphere with a rather general equation of state. In the frame of an observer comoving with this fluid, the sphere pulsates between a maximum and a minimum size, avoiding the singularity. The exterior geometry is also constructed. There are usually an outer and an inner apparent horizon, resembling the Reissner-Nordström situation. For a distant observer the horizon crossing occurs in an infinite time and the pulsations of the black hole quantum "beating heart" are completely unobservable. However, it may be observable if the black hole is not spherical symmetric and radiates gravitational wave due to the quadrupole moment, if any.

Selenium adsorption to aluminum-based water treatment residuals

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

Ippolito, James A.; Scheckel, Kirk G.; Barbarick, Ken A.

2009-09-02

Aluminum-based water treatment residuals (WTR) can adsorb water- and soil-borne P, As(V), As(III), and perchlorate, and may be able to adsorb excess environmental selenium. WTR, clay minerals, and amorphous aluminum hydroxide were shaken for 24 h in selenate or selenite solutions at pH values of 5-9, and then analyzed for selenium content. Selenate and selenite adsorption edges were unaffected across the pH range studied. Selenate adsorbed on to WTR, reference mineral phases, and amorphous aluminum hydroxide occurred as outer sphere complexes (relatively loosely bound), while selenite adsorption was identified as inner-sphere complexation (relatively tightly bound). Selenite sorption to WTR inmore » an anoxic environment reduced Se(IV) to Se(0), and oxidation of Se(0) or Se(IV) appeared irreversible once sorbed to WTR. Al-based WTR could play a favorable role in sequestering excess Se in affected water sources.« less

Turbulent convective heat transfer of methane at supercritical pressure in a helical coiled tube

NASA Astrophysics Data System (ADS)

Wang, Chenggang; Sun, Baokun; Lin, Wei; He, Fan; You, Yingqiang; Yu, Jiuyang

2018-02-01

The heat transfer of methane at supercritical pressure in a helically coiled tube was numerically investigated using the Reynolds Stress Model under constant wall temperature. The effects of mass flux ( G), inlet pressure ( P in) and buoyancy force on the heat transfer behaviors were discussed in detail. Results show that the light fluid with higher temperature appears near the inner wall of the helically coiled tube. When the bulk temperature is less than or approach to the pseudocritical temperature ( T pc ), the combined effects of buoyancy force and centrifugal force make heavy fluid with lower temperature appear near the outer-right of the helically coiled tube. Beyond the T pc , the heavy fluid with lower temperature moves from the outer-right region to the outer region owing to the centrifugal force. The buoyancy force caused by density variation, which can be characterized by Gr/ Re 2 and Gr/ Re 2.7, enhances the heat transfer coefficient ( h) when the bulk temperature is less than or near the T pc , and the h experiences oscillation due to the buoyancy force. The oscillation is reduced progressively with the increase of G. Moreover, h reaches its peak value near the T pc . Higher G could improve the heat transfer performance in the whole temperature range. The peak value of h depends on P in. A new correlation was proposed for methane at supercritical pressure convective heat transfer in the helical tube, which shows a good agreement with the present simulated results.

Directional moisture transfer through a wild silkworm cocoon wall.

PubMed

Jin, Xing; Zhang, Jin; Gao, Weimin; Du, Shan; Li, Jingliang; Wang, Xungai

2016-06-25

A silkworm cocoon is a porous biological structure with multiple protective functions. In the current work, the authors have used both experimental and numerical methods to reveal the unique moisture transfer characteristics through a wild Antheraea pernyi silkworm cocoon wall, in comparison with the long-domesticated Bombyx mori silkworm cocoon walls. The water vapor transmission and water vapor permeability (WVP) properties show that the A. pernyi cocoons exhibit directional moisture transfer behavior, with easier moisture transfer from inside out than outside in [e.g., the average WVP is 0.057 g/(h m bar) from inside out and is 0.034 g/(h m bar) from outside in]. Numerical analysis shows that the cubic mineral crystals in the outer section of the A. pernyi cocoon wall create a rough surface that facilitates air turbulence and promotes disturbance amplitude of the flow field, leading to lengthened water vapor transfer path and increased tortuosity of the moist air. It also indicates the vortex of water vapor can be generated in the outer section of cocoon wall, which increases the diffusion distance of water vapor and enhances the turbulence kinetic energy and turbulence eddy dissipation, signifying higher moisture resistance in the outer section. The difference in moisture resistance of the multiple A. pernyi cocoon layers is largely responsible for the unique directional moisture transfer behavior of this wild silkworm cocoon. These findings may inspire a biomimicry approach to develop novel lightweight moisture management materials and structures.

A Study for the Restoration of Hong Dae-Yong Honsangui - Focusing on the structure and operating mechanism

NASA Astrophysics Data System (ADS)

Lee, Yong Sam; Kim, Sang Hyuk; Park, Je Hoon

2013-09-01

Honsangui (celestial globe) which is a water-hammering method astronomical clock is recorded in "Juhaesuyong" which is Volume VI of supplement from "Damheonseo", written by Hong Dae-Yong (1731~1783). We made out the conceptual design of Hong Dae-Yong's Honsangui through the study on its structure and working mechanism. Honsangui consist of three rings and two layers, the structure of rings which correspond to outer layer is similar to his own Tongcheonui (armillary sphere) which is a kind of armillary sphere. Honsang sphere which correspond to inner layer depicts constellations and milky way and two beads hang on it as Sun and Moon respectively for realize the celestial motion. Tongcheonui is operated by the pendulum power but Honsangui is operated by water-hammering method mechanism. This Honsangui's working mechanism is the traditional way of Joseon and it was simplified the working mechanism of Shui y'n i hsiang t'ai which is a representative astronomical clock of China. This record of Honsangui is the only historical record about the water-hammering method working mechanism of Joseon Era and it provide the study of water-hammering method mechanism with a vital clue.

Compaction of granular materials: numerical simulation of "elastic" compression and pressure solution creep

NASA Astrophysics Data System (ADS)

Bernabe, Y.; Evans, J.

2012-12-01

In a previous work we investigated stress transfer in a pair of grain contacts undergoing pressure solution (PS) creep, showed that stress transfer resulted in a significant decrease in overall strain rate, and concluded that PS creep rates of a randomly packed granular aggregate should be affected by packing evolution and the formation of new contacts during creep. To test these conclusions further, we are numerically simulating the "elastic" hydrostatic compression of a random pack of spheres, using a numerical method similar to that of Cundall and Strack [1979]. We assumed that the spheres were frictionless (i.e., spheres in contact only interacted through normal forces) and that the contact forces obeyed the non-linear Digby [1981] model. In order to determine the PS creep compression of the sphere pack subjected to a constant confining pressure pc, we calculated the thicknesses of the dissolved layers at each individual grain contact during a small time increment and, from these, the overall deformation of the sphere pack. We used an analytical expression discussed in our previous paper and originating from Lehner and Leroy [2004]. During these simulations, we also computed the mean coordination number of the grain contact z, the effective bulk modulus K of the sphere pack and others parameters characterizing the topological and mechanical properties of the sphere assembly. Our results show strong non-linear increase of z and K with pc during "elastic" compression and, with time, during PS creep. The packing rearrangements associated with PS creep produce complex time dependence of the overall deformation ɛ(t). We observed a regular transition from ɛ∝t^3/4 at early times (i.e., less than 0.1 years) and ɛ∝t^1/3 at late times (i.e., more than 1000 years). Cundall, P.A., and O.D.L. Strack (1979), A discrete numerical model for granular assemblies, Geotech., 29, 47-65. Digby, P.J. (1981), The effective elastic moduli of porous rocks, J. Appl. Mech., 48, 803-808. Lehner, F.K., and Y. Leroy (2004), Sandstone compaction by intergranular pressure solution, In Mech. Fluid Saturated Rocks (eds. Y. Guéguen and M. Boutéca), Elsevier.

Sputtering of ices in the outer solar system

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

Johnson, R.E.

1996-01-01

Exploration of the outer solar system has led to studies in a new area of physics: electronically induced sputtering of low-temperature, condensed-gas solids (ices). Many of the icy bodies in the outer solar system were found to be bombarded by relatively intense fluxes of ions and electrons, causing both changes in their optical reflectance and ejection (sputtering) of molecules from their surfaces. The small cohesive energies of the condensed-gas solids afford relatively large sputtering rates from the electronic excitations produced in the solid by fast ions and electrons. Such sputtering produces an ambient gas about an icy body, often themore » source of the local plasma. This colloquium outlines the physics of the sputtering of ices and its relevance to several outer-solar-system phenomena: the sputter-produced plasma trapped in Saturn{close_quote}s magnetosphere; the O{sub 2} atmosphere on Europa; and optical absorption features such as SO{sub 2} in the surface of Europa and O{sub 2} and, possibly, O{sub 3} in the surface of Ganymede. {copyright} {ital 1996 The American Physical Society.}« less

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

Versino, Daniele; Brock, Jerry Steven

In this manuscript we describe test cases for the dynamic sphere problem in presence of finite deformations. The spherical shell in exam is made of a homogeneous, isotropic or transverse isotropic material and elastic and elastic-plastic material behaviors are considered. Twenty cases, (a) to (t), are thus defined combining material types and boundary conditions. The inner surface radius, the outer surface radius and the material's density are kept constant for all the considered test cases and their values are r i = 10mm, r o = 20mm and p = 1000Kg/m 3 respectively.

One-step facile hydrothermal synthesis of Fe2O3@LiCoO2 composite as excellent supercapacitor electrode materials

NASA Astrophysics Data System (ADS)

Gopi, Chandu V. V. Muralee; Somasekha, A.; Reddy, Araveeti Eswar; Kim, Soo-Kyoung; Kim, Hee-Je

2018-03-01

Herein, for the first time, we demonstrate the fabrication of Fe2O3@LiCoO2 hybrid nanostructures on Ni foam substrate by facile one-step hydrothermal technique. Morphological studies reveal that aggregated Fe2O3 nanoflakes anchored on the surface of sphere-like LiCoO2 nanoflakes. Electrochemical studies are used to examine the performance of the supercapacitor electrodes. The composite Fe2O3@LiCoO2 electrode exhibited excellent electrochemical performance than Fe2O3 and LiCoO2 electrodes, such as a low charge transfer resistance, a high specific capacitance of 489 F g-1 at 5 mA cm-2 and an enhanced capacity retention of 108% over 3000 cycles at 15 mA cm-2. The composite Fe2O3@LiCoO2 holds great promise for electrochemical applications due to well-defined hierarchical morphology, synergetic effect of Fe2O3 and LiCoO2, enhanced electrical conductivity, efficient electrolyte penetration and fast electron transfer.

A likely planet-induced gap in the disc around T Cha

NASA Astrophysics Data System (ADS)

Hendler, Nathanial P.; Pinilla, Paola; Pascucci, Ilaria; Pohl, Adriana; Mulders, Gijs; Henning, Thomas; Dong, Ruobing; Clarke, Cathie; Owen, James; Hollenbach, David

2018-03-01

We present high-resolution (0.11 × 0.06 arcsec2) 3 mm ALMA observations of the highly inclined transition disc around the star T Cha. Our continuum image reveals multiple dust structures: an inner disc, a spatially resolved dust gap, and an outer ring. When fitting sky-brightness models to the real component of the 3 mm visibilities, we infer that the inner emission is compact (≤1 au in radius), the gap width is between 18 and 28 au, and the emission from the outer ring peaks at ˜36 au. We compare our ALMA image with previously published 1.6 μm VLT/SPHERE imagery. This comparison reveals that the location of the outer ring is wavelength dependent. More specifically, the peak emission of the 3 mm ring is at a larger radial distance than that of the 1.6 μm ring, suggesting that millimeter-sized grains in the outer disc are located farther away from the central star than micron-sized grains. We discuss different scenarios to explain our findings, including dead zones, star-driven photoevaporation, and planet-disc interactions. We find that the most likely origin of the dust gap is from an embedded planet, and estimate - for a single planet scenario - that T Cha's gap is carved by a 1.2MJup planet.

Acoustic levitation of a large solid sphere

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

Andrade, Marco A. B., E-mail: marcobrizzotti@gmail.com; Bernassau, Anne L.; Adamowski, Julio C.

2016-07-25

We demonstrate that acoustic levitation can levitate spherical objects much larger than the acoustic wavelength in air. The acoustic levitation of an expanded polystyrene sphere of 50 mm in diameter, corresponding to 3.6 times the wavelength, is achieved by using three 25 kHz ultrasonic transducers arranged in a tripod fashion. In this configuration, a standing wave is created between the transducers and the sphere. The axial acoustic radiation force generated by each transducer on the sphere was modeled numerically as a function of the distance between the sphere and the transducer. The theoretical acoustic radiation force was verified experimentally in a setupmore » consisting of an electronic scale and an ultrasonic transducer mounted on a motorized linear stage. The comparison between the numerical and experimental acoustic radiation forces presents a good agreement.« less

Versatile Photocatalytic Systems for H2 Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst

PubMed Central

2013-01-01

The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2R′N2R″)2]2+ core (P2R′N2R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system. PMID:24320740

Effects of Complex Interplanetary Structures on the Dynamics of the Earth's Outer Radiation Belt During the 16-30 September 2014 Period: II) Corotating Solar Wind Stream

NASA Astrophysics Data System (ADS)

Souza, V. M. C. E. S.; Da Silva, L. A.; Sibeck, D. G.; Alves, L. R.; Jauer, P. R.; Dias Silveira, M. V.; Medeiros, C.; Marchezi, J.; Rockenbach, M.; Baker, D. N.; Kletzing, C.; Kanekal, S. G.; Georgiou, M.; Mendes, O., Jr.; Dal Lago, A.; Vieira, L. E. A.

2015-12-01

We present a case study describing the dynamics of the outer radiation belt for two different solar wind conditions. First, we discuss a dropout of outer belt energetic electron fluxes corresponding to the arrival of an interplanetary coronal mass ejection (ICME) followed by a corotating stream in September 2014. Second, we discuss the reformation of the outer radiation belt that began on September 22nd. We find that the arrival of the ICME and the corotating interaction region that preceded the stream cause a long-duration (many day) dropout of high-energy electrons. The recovery in radiation belt fluxes only begins when the high-speed stream begins to develop IMF Bz fluctuations and auroral activity resumes. Furthermore, during periods in which several consecutive solar wind structures appear, the first structure primes the outer radiation belt prior to the interaction of the subsequent solar wind structures with the magnetosphere. Consequently, the evolution of the outer radiation belt through the solar cycle is significantly affected by the dominant structure of each phase of the cycle. We use energetic electron and magnetic field observations provided by the Van Allen Probes, THEMIS, and GOES missions.

RAFT Aqueous Dispersion Polymerization Yields Poly(ethylene glycol)-Based Diblock Copolymer Nano-Objects with Predictable Single Phase Morphologies

PubMed Central

2013-01-01

A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by 1H NMR spectroscopy and relatively low diblock copolymer polydispersities (Mw/Mn < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMAx diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG113-PHPMAx phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications. PMID:24400622

Theoretical understanding on the v(1)-SO4(2-) band perturbed by the formation of magnesium sulfate ion pairs.

PubMed

Zhang, Hao; Zhang, Yun-Hong; Wang, Feng

2009-02-01

The factors determining the spectroscopic characteristics of the v(1)-SO4(2-) band of the MgSO4 ion pairs are discussed via ab initio calculation, including coupling effect, hydrogen bonding effect, and direct contact effect of Mg2+ with SO4(2-). With the calculation of the heavy water hydrated contact ion pairs (CIP), the overlap between the librations of water and the v(1)-SO4(2-) band can be separated, and thus the coupling effect is abstracted, and this coupling effect leads to a blue shift for the v(1)-SO4(2-) band of 5.6 cm(-1) in the monodentate CIP and 3.6 cm(-1) in the bidentate CIP. The hydrogen bonding between each water molecule without relation to Mg2+ and the sulfate ion makes the v(1)-SO4(2-) band blue shift of 3.7 cm(-1). When the outer-sphere water around Mg2+ are hydrogen bonded between SO4(2-) and Mg2+, it will make the largest disturbance to the v(1)-SO4(2-) band. Moreover, the inner-sphere water can affect the v(1)-SO4(2-) band conjunct with the direct contact of Mg2+ with SO4(2-), showing a blue shift of 14.4 cm(-1) in the solvent-shared ion pair, 22.6 cm(-1) in the monodentate CIP, 4.3 cm(-1) in the bidentate CIP, and 21.4 cm(-1) in the tridentate CIP. At last, the Raman spectral evolution in the efflorescence production process is tried to be rationalized. The shoulder at 995 cm(-1) is attributed to the monodentate CIP with 2-3 outer-sphere water molecules, whereas the new peak at 1021 cm(-1) at high concentration is assigned to the formation of aqueous triple ion.

Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

PubMed Central

Kubicki, James D; Halada, Gary P; Jha, Prashant; Phillips, Brian L

2009-01-01

Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids. PMID:19689800

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

PubMed Central

2014-01-01

Density functional theory with optimally tuned range-separated hybrid (OT-RSH) functionals has been recently suggested [Refaely-Abramson et al. Phys. Rev. Lett.2012, 109, 226405] as a nonempirical approach to predict the outer-valence electronic structure of molecules with the same accuracy as many-body perturbation theory. Here, we provide a quantitative evaluation of the OT-RSH approach by examining its performance in predicting the outer-valence electron spectra of several prototypical gas-phase molecules, from aromatic rings (benzene, pyridine, and pyrimidine) to more complex organic systems (terpyrimidinethiol and copper phthalocyanine). For a range up to several electronvolts away from the frontier orbital energies, we find that the outer-valence electronic structure obtained from the OT-RSH method agrees very well (typically within ∼0.1–0.2 eV) with both experimental photoemission and theoretical many-body perturbation theory data in the GW approximation. In particular, we find that with new strategies for an optimal choice of the short-range fraction of Fock exchange, the OT-RSH approach offers a balanced description of localized and delocalized states. We discuss in detail the sole exception found—a high-symmetry orbital, particular to small aromatic rings, which is relatively deep inside the valence state manifold. Overall, the OT-RSH method is an accurate DFT-based method for outer-valence electronic structure prediction for such systems and is of essentially the same level of accuracy as contemporary GW approaches, at a reduced computational cost. PMID:24839410

Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

PubMed

Chen, Yiling; Zhang, Huichun

2013-10-01

Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

Six-coordinate manganese(3+) in catalysis by yeast manganese superoxide dismutase

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

Sheng, Yuewei; Gralla, Edith Butler; Schumacher, Mikhail

Reduction of superoxide (O{sub 2}{sup -}) by manganese-containing superoxide dismutase occurs through either a 'prompt protonation' pathway, or an 'inner-sphere' pathway, with the latter leading to formation of an observable Mn-peroxo complex. We recently reported that wild-type (WT) manganese superoxide dismutases (MnSODs) from Saccharomyces cerevisiae and Candida albicans are more gated toward the 'prompt protonation' pathway than human and bacterial MnSODs and suggested that this could result from small structural changes in the second coordination sphere of manganese. We report here that substitution of a second-sphere residue, Tyr34, by phenylalanine (Y34F) causes the MnSOD from S. cerevisiae to react exclusivelymore » through the 'inner-sphere' pathway. At neutral pH, we have a surprising observation that protonation of the Mn-peroxo complex in the mutant yeast enzyme occurs through a fast pathway, leading to a putative six-coordinate Mn3+ species, which actively oxidizes O{sub 2}{sup -} in the catalytic cycle. Upon increasing pH, the fast pathway is gradually replaced by a slow proton-transfer pathway, leading to the well-characterized five-coordinate Mn{sup 3+}. We here propose and compare two hypothetical mechanisms for the mutant yeast enzyme, diffeeing in the structure of the Mn-peroxo complex yet both involving formation of the active six-coordinate Mn{sup 3+} and proton transfer from a second-sphere water molecule, which has substituted for the -OH of Tyr34, to the Mn-peroxo complex. Because WT and the mutant yeast MnSOD both rest in the 2+ state and become six-coordinate when oxidized up from Mn{sup 2+}, six-coordinate Mn{sup 3+} species could also actively function in the mechanism of WT yeast MnSODs.« less

Representing Precipitation Ice Species With Both Spherical and Nonspherical Particles for Radiative Transfer Modeling of Microphysics-Consistent Cloud Microwave Scattering Properties

NASA Astrophysics Data System (ADS)

Sieron, Scott B.; Zhang, Fuqing; Clothiaux, Eugene E.; Zhang, Lily N.; Lu, Yinghui

2018-04-01

Cloud microwave scattering properties for the Community Radiative Transfer Model (CRTM) have previously been created to be consistent with the particle size distributions specified by the WSM6 single-moment microphysics scheme. Here substitution of soft sphere scattering properties with nonspherical particle scattering properties is explored in studies of Hurricane Karl (2010). A nonsphere replaces a sphere of the same maximum dimension, and the number of particles of a given size is scaled by the ratio of the sphere to nonsphere mass to keep the total mass of a given particle size unchanged. The replacement of homogeneous soft sphere snow particles is necessary to resolve a highly evident issue in CRTM simulations: precipitation-affected brightness temperatures are generally warmer at 183 GHz than at 91.7 GHz, whereas the reverse is seen in observations. Using sector snowflakes resolve this issue better than using columns/plates, bullet rosettes, or dendrites. With sector snowflakes, both of these high frequencies have low simulated brightness temperatures compared to observations, providing a clear and consistent suggestion that snow is being overproduced in the examined simulation using WSM6 microphysics. Graupel causes cold biases at lower frequencies which can be reduced by either reducing graupel water contents or replacing the microphysics-consistent spherical graupel particles with sector snowflakes. However, soft spheres are likely the better physical representation of graupel particles. The hypotheses that snow and graupel are overproduced in simulations using WSM6 microphysics shall be examined more systematically in future studies through additional cases and ensemble data assimilation of all-sky microwave radiance observations.