Predicting Reduction Rates of Energetic Nitroaromatic Compounds Using Calculated One-Electron Reduction Potentials

DOE PAGES

Salter-Blanc, Alexandra; Bylaska, Eric J.; Johnston, Hayley; ...

2015-02-11

The evaluation of new energetic nitroaromatic compounds (NACs) for use in green munitions formulations requires models that can predict their environmental fate. The susceptibility of energetic NACs to nitro reduction might be predicted from correlations between rate constants (k) for this reaction and one-electron reduction potentials (E1NAC) / 0.059 V, but the mechanistic implications of such correlations are inconsistent with evidence from other methods. To address this inconsistency, we have reevaluated existing kinetic data using a (non-linear) free-energy relationship (FER) based on the Marcus theory of outer-sphere electron transfer. For most reductants, the results are inconsistent with rate limitation bymore » an initial, outer-sphere electron transfer, suggesting that the strong correlation between k and E1NAC is justified only as an empirical model. This empirical correlation was used to calibrate a new quantitative structure-activity relationship (QSAR) using previously reported values of k for non-energetic NAC reduction by Fe(II) porphyrin and newly reported values of E1NAC determined using density functional theory at the B3LYP/6-311++G(2d,2p) level with the COSMO solvation model. The QSAR was then validated for energetic NACs using newly measured kinetic data for 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), and 2,4-dinitroanisole (DNAN). The data show close agreement with the QSAR, supporting its applicability to energetic NACs.« less

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

Anomalously large effects of pressure on electron transfer kinetics in solution: The aqueous manganate(VI)-permanganate(VII) system

NASA Astrophysics Data System (ADS)

Swaddle, T. W.; Spiccia, L.

1986-05-01

The classical Stranks-Hush-Marcus theory of pressure effects on the rates of outer-sphere electron transfer reaction rates in solution underestimates |ΔV ∗| specifically, for the MnO 4/MnO 42- (aq) exchange, ΔV ∗=-21.2 (observed) vs. -6.6 cm3mol-1 (calculated). This discrepancy can best be resolved by conceding that the Mn-Mn separation σ in the transition state is variable and pressure-sensitive in the context of non-adiabatic electron transfer within an ellipsoidal cavity with σ ∼ 550 pm.

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.

Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer

PubMed Central

Petrenko, Alexander; Stein, Matthias

2017-01-01

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron–sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from Density Functional Theory (DFT) calculations. The distal cubane FeS-cluster has a three-cysteine and one-histidine coordination [Fe4S4](His)(Cys)3 first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and an all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe4S4](Cys)4 case. The fast and efficient electron transfer from the distal iron–sulfur cluster is realized by a fine-tuned protein environment, which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering. PMID:28067774

Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms for organometallic complexes

NASA Astrophysics Data System (ADS)

Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO(exp 2+) transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

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

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.

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.

Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation

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

Collins, Richard N.; Rosso, Kevin M.

Molecular-level pathways in the aqueous redox transformation of uranium by iron remain unclear, despite the importance of this knowledge for predicting uranium transport and distribution in natural and engineered environments. As the relative importance of homogeneous versus heterogeneous pathways is difficult to probe experimentally, here we apply computational molecular simulation to isolate rates of key one electron transfer reactions in the homogeneous pathway. By comparison to experimental observations the role of the heterogeneous pathway also becomes clear. Density functional theory (DFT) and Marcus theory calculations for all primary monomeric species at pH values ≤7 show for UO22+ and its hydrolysismore » species UO2OH+ and UO2(OH)20 that reduction by Fe2+ is thermodynamically favorable, though kinetically limited for UO22+. An inner-sphere encounter complex between UO2OH+ and Fe2+ was the most stable for the first hydrolysis species and displayed an electron transfer rate constant ket = 4.3 × 103 s-1. Three stable inner- and outer-sphere encounter complexes between UO2(OH)20 and Fe2+ were found, with electron transfer rate constants ranging from ket = 7.6 × 102 to 7.2 × 104 s-1. Homogeneous reduction of these U(VI) hydrolysis species to U(V) is, therefore, predicted to be facile. In contrast, homogeneous reduction of UO2+ by Fe2+ was found to be thermodynamically unfavorable, suggesting the possible importance of U(V)-U(V) disproportionation as a route to U(IV). Calculations on homogeneous disproportionation, however, while yielding a stable outer-sphere U(V)-U(V) encounter complex, indicate that this electron transfer reaction is not feasible at circumneutral pH. Protonation of both axial O atoms of acceptor U(V) (i.e., by H3O+) was found to be a prerequisite to stabilize U(IV), consistent with the experimental observation that the rate of this reaction is inversely correlated with pH. Thus, despite prevailing notions that U(V) is rapidly eliminated by homogeneous disproportionation, this pathway is irrelevant at environmental conditions.« 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.

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.

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.

Dioxygen in Polyoxometalate Mediated Reactions.

PubMed

Weinstock, Ira A; Schreiber, Roy E; Neumann, Ronny

2018-03-14

In this review article, we consider the use of molecular oxygen in reactions mediated by polyoxometalates. Polyoxometalates are anionic metal oxide clusters of a variety of structures that are soluble in liquid phases and therefore amenable to homogeneous catalytic transformations. Often, they are active for electron transfer oxidations of a myriad of substrates and upon reduction can be reoxidized by molecular oxygen. For example, the phosphovanadomolybdate, H 5 PV 2 Mo 10 O 40 , can oxidize Pd(0) thereby enabling aerobic reactions catalyzed by Pd and H 5 PV 2 Mo 10 O 40 . In a similar vein, polyoxometalates can stabilize metal nanoparticles, leading to additional transformations. Furthermore, electron transfer oxidation of other substrates such as halides and sulfur-containing compounds is possible. More uniquely, H 5 PV 2 Mo 10 O 40 and its analogues can mediate electron transfer-oxygen transfer reactions where oxygen atoms are transferred from the polyoxometalate to the substrate. This unique property has enabled correspondingly unique transformations involving carbon-carbon, carbon-hydrogen, and carbon-metal bond activation. The pathway for the reoxidation of vanadomolybdates with O 2 appears to be an inner-sphere reaction, but the oxidation of one-electron reduced polyoxotungstates has been shown through intensive research to be an outer-sphere reaction. Beyond electron transfer and electron transfer-oxygen transfer aerobic transformations, there a few examples of apparent dioxygenase activity where both oxygen atoms are donated to a substrate.

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.

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

A molecularly based theory for electron transfer reorganization energy.

PubMed

Zhuang, Bilin; Wang, Zhen-Gang

2015-12-14

Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule's permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory.

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.

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

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.

Reactive trajectories of the Ru2+/3+ self-exchange reaction and the connection to Marcus' theory.

PubMed

Tiwari, Ambuj; Ensing, Bernd

2016-12-22

Outer sphere electron transfer between two ions in aqueous solution is a rare event on the time scale of first principles molecular dynamics simulations. We have used transition path sampling to generate an ensemble of reactive trajectories of the self-exchange reaction between a pair of Ru 2+ and Ru 3+ ions in water. To distinguish between the reactant and product states, we use as an order parameter the position of the maximally localised Wannier center associated with the transferring electron. This allows us to align the trajectories with respect to the moment of barrier crossing and compute statistical averages over the path ensemble. We compare our order parameter with two typical reaction coordinates used in applications of Marcus theory of electron transfer: the vertical gap energy and the solvent electrostatic potential at the ions.

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.

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.

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.

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.

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.

Electrochemistry of redox-active self-assembled monolayers

PubMed Central

Eckermann, Amanda L.; Feld, Daniel J.; Shaw, Justine A.; Meade, Thomas J.

2010-01-01

Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redox-activated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C60). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs. PMID:20563297

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

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

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%.

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

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.

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.

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

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.

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

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.

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.

"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.

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.

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.

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.

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.

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.

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.

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).

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

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.

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.

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;

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.

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.

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

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

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.

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

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

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

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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. )

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

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.

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.

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].

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.

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.

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.

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

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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

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

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.

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.

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.

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

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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

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.

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.

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.

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.

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

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.

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.

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

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.

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.

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

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

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

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.

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

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.

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

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.

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.

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

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.

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

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.

The effects of magnetospheric processes on relativistic electron dynamics in the Earth's outer radiation belt

DOE PAGES

Tang, C. L.; Wang, Y. X.; Ni, B.; ...

2017-08-11

Using the electron phase space density (PSD) data measured by Van Allen Probe A from January 2013 to April 2015, we investigate the effects of magnetospheric processes on relativistic electron dynamics in the Earth's outer radiation belt during 50 geomagnetic storms. A statistical study shows that the maximum electron PSDs for various μ (μ = 630, 1096, 2290, and 3311 MeV/G) at L*~4.0 after the storm peak have good correlations with storm intensity (cc~0.70). This suggests that the occurrence and magnitude of geomagnetic storms are necessary for relativistic electron enhancements at the inner edge of the outer radiation belt (L*more » = 4.0). For moderate or weak storm events (SYM–H min > ~–100 nT) with weak substorm activity (AE max < 800 nT) and strong storm events (SYM–H min ≤ ~–100 nT) with intense substorms (AE max ≥ 800 nT) during the recovery phase, the maximum electron PSDs for various μ at different L* values (L* = 4.0, 4.5, and 5.0) are well correlated with storm intensity (cc > 0.77). For storm events with intense substorms after the storm peak, relativistic electron enhancements at L* = 4.5 and 5.0 are observed. This shows that intense substorms during the storm recovery phase are crucial to relativistic electron enhancements in the heart of the outer radiation belt. In conclusion, our statistics study suggests that magnetospheric processes during geomagnetic storms have a significant effect on relativistic electron dynamics.« less

The effects of magnetospheric processes on relativistic electron dynamics in the Earth's outer radiation belt

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

Tang, C. L.; Wang, Y. X.; Ni, B.

Using the electron phase space density (PSD) data measured by Van Allen Probe A from January 2013 to April 2015, we investigate the effects of magnetospheric processes on relativistic electron dynamics in the Earth's outer radiation belt during 50 geomagnetic storms. A statistical study shows that the maximum electron PSDs for various μ (μ = 630, 1096, 2290, and 3311 MeV/G) at L*~4.0 after the storm peak have good correlations with storm intensity (cc~0.70). This suggests that the occurrence and magnitude of geomagnetic storms are necessary for relativistic electron enhancements at the inner edge of the outer radiation belt (L*more » = 4.0). For moderate or weak storm events (SYM–H min > ~–100 nT) with weak substorm activity (AE max < 800 nT) and strong storm events (SYM–H min ≤ ~–100 nT) with intense substorms (AE max ≥ 800 nT) during the recovery phase, the maximum electron PSDs for various μ at different L* values (L* = 4.0, 4.5, and 5.0) are well correlated with storm intensity (cc > 0.77). For storm events with intense substorms after the storm peak, relativistic electron enhancements at L* = 4.5 and 5.0 are observed. This shows that intense substorms during the storm recovery phase are crucial to relativistic electron enhancements in the heart of the outer radiation belt. In conclusion, our statistics study suggests that magnetospheric processes during geomagnetic storms have a significant effect on relativistic electron dynamics.« less

Extreme enhancements and depletions of relativistic electrons in Earth's radiation belts

NASA Astrophysics Data System (ADS)

Turner, D. L.; Claudepierre, S. G.; O'Brien, T. P., III; Fennell, J. F.; Blake, J. B.; Baker, D. N.; Jaynes, A. N.; Morley, S.; Geoffrey, R.

2015-12-01

Earth's electron radiation belts consist of toroidal zones in near-Earth space characterized by intense levels of relativistic electrons with distinct energy-dependent boundaries. It has been known for decades that the outer electron radiation belt is highly variable, with electron intensities varying by orders of magnitude on timescales ranging from minutes to years. Now, we are gaining much insight into the nature of this extreme variability thanks to the unprecedented number of observatories capable of measuring radiation belt electrons, the most recent of which is NASA's Van Allen Probes mission. In this presentation, we analyze and review several of the most extreme events observed in Earth's outer radiation belt. We begin with very sudden and strong enhancements of the outer radiation belt that can result in several orders of magnitude enhancements of electron intensities up to several MeV that sometimes occur in less than one day. We compare and contrast two of the most extreme cases of sudden and strong enhancements from the Van Allen Probes era, 08-09 October 2012 and 17-18 March 2015, and review evidence of the dominant acceleration mechanism in each event. Sudden enhancements of the radiation belts can also occur from injections by interplanetary shocks impacting the magnetosphere, such as occurred on 24 March 1991. We compare shock characteristics from previous injection events to those from the Van Allen Probes era to investigate why none of the interplanetary shocks since September 2012 have caused MeV electron injections into the slot region and inner radiation belt, which has surprisingly been devoid of measurable quantities of >~1 MeV electrons throughout the Van Allen Probes era. Our last topic concerns loss processes. We discuss drastic loss events, known as "flux dropouts", and present evidence that these loss events can eliminate the vast majority of relativistic electrons in the outer radiation belt on time scales of only a few hours. We finish with cases of prolonged outer belt depletions, such as occurred throughout most of 2009 and in September 2014, and discuss how these can result from flux dropout events combined with a subsequent lack of any source of new relativistic electrons.

Hollow mesoporous TiO2 microspheres for enhanced photocatalytic degradation of acetaminophen in water.

PubMed

Lin, Chin Jung; Yang, Wen-Ta; Chou, Chen-Yi; Liou, Sofia Ya Hsuan

2016-06-01

Hollow core-shell mesoporous TiO2 microspheres were synthesized by a template-free solvothermal route for efficient photocatalytic degradation of acetaminophen. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Barrett-Joyner-Halenda data revealed a micrometer-sized mesoporous anatase TiO2 hollow sphere with large surface area and efficient light harvesting. For the photocatalytic degradation of acetaminophen in 60 min, the conversion fraction of the drug increased from 88% over commercial Degussa P25 TiO2 to 94% over hollow spheres with about 25% increase in the initial reaction rate. Even after 10 repeated runs, the recycled hollow spheres showed good photodegradation activity. The intermediates generated in the photocatalytic reactions were eventually converted into molecules that are easier to handle. The simple fabrication route would facilitate the development of photocatalysts for the decomposition of environmental contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of grain-coating mineralogy on nitrate and sulfate storage in the unsaturated zone

USGS Publications Warehouse

Reilly, T.J.; Fishman, N.S.; Baehr, A.L.

2009-01-01

Unsaturated-zone sediments and the chemistry of shallow groundwater underlying a small (???8-km2) watershed were studied to identify the mechanisms responsible for anion storage within the Miocene Bridgeton Formation and weathered Coastal Plain deposits in southern New Jersey. Lower unsaturated-zone sediments and shallow groundwater samples were collected and concentrations of selected ions (including NO3- and SO42-) from 11 locations were determined. Grain size, sorting, and color of the lower unsaturated-zone sediments were determined and the mineralogy of these grains and the composition of coatings were analyzed by petrographic examination, scanning electron microscopy and energy dispersive analysis of x-rays, and quantitative whole-rock x-ray diffraction. The sediment grains, largely quartz and chert (80-94% w/w), are coated with a very fine-grained (<20 ??m), complex mixture of kaolinite, halloysite, goethite, and possibly gibbsite and lepidocrocite. The mineral coatings are present as an open fabric, resulting in a large surface area in contact with pore water. Significant correlations between the amount of goethite in the grain coatings and the concentration of sediment-bound SO42- were observed, indicative of anion sorption. Other mineral-chemical relations indicate that negatively charged surfaces and competition with SO 42- results in exclusion of NO3- from inner sphere exchange sites. The observed NO3- storage may be a result of matrix forces within the grain coatings and outer sphere complexation. The results of this study indicate that the mineralogy of grain coatings can have demonstrable effects on the storage of NO 3- and SO42- in the unsaturated zone. ?? Soil Science Society of America. All rights reserved.

Synthesis and microwave absorption property of graphene oxide/carbon nanotubes modified with cauliflower-like Fe3O4 nanospheres

NASA Astrophysics Data System (ADS)

Yan, Shaojiu; Wang, Lina; Wang, Tihong; Zhang, Liqiang; Li, Yongfeng; Dai, Shenglong

2016-03-01

We report a simple procedure to fabricate graphene oxide/carbon nanotube hybrids coated with cauliflower-like Fe3O4 sphere. Characterizations have been carried out to investigate the morphology, crystalline structure of the composites by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. Fe3O4 particles have the morphologies of multi-lacuna; moreover, some spheres are hollow. As a kind of potential microwave absorption material, the composites are lightweight and exhibit excellent microwave absorbing ability in the range of 2-16 GHz.

First-principles calculation of the geometric and electronic structure of the Be(0001) surface

NASA Astrophysics Data System (ADS)

Feibelman, Peter J.

1992-07-01

Linearized-augmented-plane-wave calculations for a nine-layer Be(0001) slab agree with the unusual experimental finding of a substantial outer-layer expansion relative to the truncated bulk lattice. They imply that the separation between the outer two layers should be 3.9% larger than in the bulk, while the second- to third-layer separation should be 2.2% larger. The surface expansion is accompanied by demotion of pσ to s electrons on outer-layer Be's. The surface Be's loss of three neighbors makes the energy cost of s- to pσ-electron promotion, which is necessary for the formation of strong bonds to the next layer down, less profitable than in the bulk.

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

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

77 FR 4294 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-27

... Activities; Submission to OMB for Review and Approval; Comment Request; Air Pollution Regulations for Outer... electronic docket, go to www.regulations.gov . Title: Air Pollution Regulations for Outer Continental Shelf... Act gives EPA responsibility for regulating air pollution from outer continental shelf (OCS) sources...

Calculation of gyrosynchrotron radiation brightness temperature for outer bright loop of ICME

NASA Astrophysics Data System (ADS)

Sun, Weiying; Wu, Ji; Wang, C. B.; Wang, S.

:Solar polar orbit radio telescope (SPORT) is proposed to detect the high density plasma clouds of outer bright loop of ICMEs from solar orbit with large inclination. Of particular interest is following the propagation of the plasma clouds with remote sensor in radio wavelength band. Gyrosynchrotron emission is a main radio radiation mechanism of the plasma clouds and can provide information of interplanetary magnetic field. In this paper, we statistically analyze the electron density, electron temperature and magnetic field of background solar wind in time of quiet sun and ICMEs propagation. We also estimate the fluctuation range of the electron density, electron temperature and magnetic field of outer bright loop of ICMEs. Moreover, we calculate and analyze the emission brightness temperature and degree of polarization on the basis of the study of gyrosynchrotron emission, absorption and polarization characteristics as the optical depth is less than or equal to 1.

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

Locomotion of Amorphous Surface Robots

NASA Technical Reports Server (NTRS)

Bradley, Arthur T. (Inventor)

2018-01-01

An amorphous robot includes a compartmented bladder containing fluid, a valve assembly, and an outer layer encapsulating the bladder and valve assembly. The valve assembly draws fluid from a compartment(s) and discharges the drawn fluid into a designated compartment to displace the designated compartment with respect to the surface. Another embodiment includes elements each having a variable property, an outer layer that encapsulates the elements, and a control unit. The control unit energizes a designated element to change its variable property, thereby moving the designated element. The elements may be electromagnetic spheres with a variable polarity or shape memory polymers with changing shape and/or size. Yet another embodiment includes an elongated flexible tube filled with ferrofluid, a moveable electromagnet, an actuator, and a control unit. The control unit energizes the electromagnet and moves the electromagnet via the actuator to magnetize the ferrofluid and lengthen the flexible tube.

Locomotion of Amorphous Surface Robots

NASA Technical Reports Server (NTRS)

Bradley, Arthur T. (Inventor)

2016-01-01

An amorphous robot includes a compartmented bladder containing fluid, a valve assembly, and an outer layer encapsulating the bladder and valve assembly. The valve assembly draws fluid from a compartment(s) and discharges the drawn fluid into a designated compartment to displace the designated compartment with respect to the surface. Another embodiment includes elements each having a variable property, an outer layer that encapsulates the elements, and a control unit. The control unit energizes a designated element to change its variable property, thereby moving the designated element. The elements may be electromagnetic spheres with a variable polarity or shape memory polymers with changing shape and/or size. Yet another embodiment includes an elongated flexible tube filled with ferrofluid, a moveable electromagnet, an actuator, and a control unit. The control unit energizes the electromagnet and moves the electromagnet via the actuator to magnetize the ferrofluid and lengthen the flexible tube.

Locomotion of Amorphous Surface Robots

NASA Technical Reports Server (NTRS)

Bradley, Arthur T. (Inventor)

2014-01-01

An amorphous robot includes a compartmented bladder containing fluid, a valve assembly, and an outer layer encapsulating the bladder and valve assembly. The valve assembly draws fluid from a compartment(s) and discharges the drawn fluid into a designated compartment to displace the designated compartment with respect to the surface. Another embodiment includes elements each having a variable property, an outer layer that encapsulates the elements, and a control unit. The control unit energizes a designated element to change its variable property, thereby moving the designated element. The elements may be electromagnetic spheres with a variable polarity or shape memory polymers with changing shape and/or size. Yet another embodiment includes an elongated flexible tube filled with ferrofluid, a moveable electromagnet, an actuator, and a control unit. The control unit energizes the electromagnet and moves the electromagnet via the actuator to magnetize the ferrofluid and lengthen the flexible tube.

Radial electron-beam-breakup transit-time oscillator

DOEpatents

Kwan, Thomas J. T.; Mostrom, Michael A.

1998-01-01

A radial electron-beam-breakup transit-time oscillator (RBTO) provides a compact high power microwave generator. The RBTO includes a coaxial vacuum transmission line having an outer conductor and an inner conductor. The inner conductor defines an annular cavity with dimensions effective to support an electromagnetic field in a TEM.sub.00m mode. A radial field emission cathode is formed on the outer conductor for providing an electron beam directed toward the annular cavity electrode. Microwave energy is then extracted from the annular cavity electrode.

Survey of radiation belt energetic electron pitch angle distributions based on the Van Allen Probes MagEIS measurements: Electron Pitch Angle Distributions

DOE PAGES

Shi, Run; Summers, Danny; Ni, Binbin; ...

2016-12-30

A statistical survey of electron pitch angle distributions (PADs) is performed based on the pitch angle-resolved flux observations from the Magnetic Electron Ion Spectrometer (MagEIS) instrument on board the Van Allen Probes during the period from 1 October 2012 to 1 May 2015. By fitting the measured PADs to a sin nα form, where α is the local pitch angle and n is the power law index, we investigate the dependence of PADs on electron kinetic energy, magnetic local time (MLT), the geomagnetic Kp index, and L shell. The difference in electron PADs between the inner and outer belt ismore » distinct. In the outer belt, the common averaged n values are less than 1.5, except for large values of the Kp index and high electron energies. The averaged n values vary considerably with MLT, with a peak in the afternoon sector and an increase with increasing L shell. In the inner belt, the averaged n values are much larger, with a common value greater than 2. The PADs show a slight dependence on MLT, with a weak maximum at noon. A distinct region with steep PADs lies in the outer edge of the inner belt where the electron flux is relatively low. The distance between the inner and outer belt and the intensity of the geomagnetic activity together determine the variation of PADs in the inner belt. Finally, besides being dependent on electron energy, magnetic activity, and L shell, the results show a clear dependence on MLT, with higher n values on the dayside.« less

Survey of radiation belt energetic electron pitch angle distributions based on the Van Allen Probes MagEIS measurements: Electron Pitch Angle Distributions

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

Shi, Run; Summers, Danny; Ni, Binbin

A statistical survey of electron pitch angle distributions (PADs) is performed based on the pitch angle-resolved flux observations from the Magnetic Electron Ion Spectrometer (MagEIS) instrument on board the Van Allen Probes during the period from 1 October 2012 to 1 May 2015. By fitting the measured PADs to a sin nα form, where α is the local pitch angle and n is the power law index, we investigate the dependence of PADs on electron kinetic energy, magnetic local time (MLT), the geomagnetic Kp index, and L shell. The difference in electron PADs between the inner and outer belt ismore » distinct. In the outer belt, the common averaged n values are less than 1.5, except for large values of the Kp index and high electron energies. The averaged n values vary considerably with MLT, with a peak in the afternoon sector and an increase with increasing L shell. In the inner belt, the averaged n values are much larger, with a common value greater than 2. The PADs show a slight dependence on MLT, with a weak maximum at noon. A distinct region with steep PADs lies in the outer edge of the inner belt where the electron flux is relatively low. The distance between the inner and outer belt and the intensity of the geomagnetic activity together determine the variation of PADs in the inner belt. Finally, besides being dependent on electron energy, magnetic activity, and L shell, the results show a clear dependence on MLT, with higher n values on the dayside.« less

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

High voltage coaxial switch

DOEpatents

Rink, J.P.

1983-07-19

A coaxial high voltage, high current switch having a solid cylindrical cold cathode coaxially surrounded by a thin hollow cylindrical inner electrode and a larger hollow cylindrical outer electrode. A high voltage trigger between the cathode and the inner electrode causes electrons to be emitted from the cathode and flow to the inner electrode preferably through a vacuum. Some of the electrons penetrate the inner electrode and cause a volumetric discharge in the gas (which may be merely air) between the inner and outer electrodes. The discharge provides a low impedance path between a high voltage charge placed on the outer electrode and a load (which may be a high power laser) coupled to the inner electrode. For high repetition rate the gas between the inner and outer electrodes may be continuously exchanged or refreshed under pressure. 3 figs.

High voltage coaxial switch

DOEpatents

Rink, John P.

1983-07-19

A coaxial high voltage, high current switch having a solid cylindrical cold cathode coaxially surrounded by a thin hollow cylindrical inner electrode and a larger hollow cylindrical outer electrode. A high voltage trigger between the cathode and the inner electrode causes electrons to be emitted from the cathode and flow to the inner electrode preferably through a vacuum. Some of the electrons penetrate the inner electrode and cause a volumetric discharge in the gas (which may be merely air) between the inner and outer electrodes. The discharge provides a low impedance path between a high voltage charge placed on the outer electrode and a load (which may be a high power laser) coupled to the inner electrode. For high repetition rate the gas between the inner and outer electrodes may be continuously exchanged or refreshed under pressure.

OUTER RADIATION BELT AND AURORAS

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

Gorchakov, E.V.

1961-01-01

Data obtained from Sputnik IH were used to determine the high-latitude boundary of the outer radiation belt and to interpret the nature of auroras. At the heights at which the auroras were observed, the outer boundary of the belt (69 deg north geomagnetic latitude) practically coincides with the auroral zone maximum (70 deg north geomagnetic latitude), while the maximum intensity of the outer belt near the earth lies at about 55 deg north geomagnetic latitude, i.e., at latitudes 15 deg below the auroral maximum. Consequently, auroras near the zone of maximum cannot be caused by the penetration into the atmospheremore » of electrons from the outer belt with energies on the order of 0.1 Mev (the mean energy of electrons in the outer belt). Other investigators have reported the detection of lowenergy streams at 55,000 to 75,000 km from the center of the earth in the equatorial plane. Moving toward the surface of the earth along the force lines of the magnetic field, electron streams of this type will reach the earth precisely in the region of the auroral zone maximum. It is considered possible that the electron streams are trapped at these distances from the earth and are at least partially responsible for auroras in the region of maximum. The existence of two maxima in the latitudinal distribution of auroral frequency, which attests to differert mechanisms of aurora formation, favors this hypothesis. In the region of the basic auroral maximum (70 deg north geomagnetic latitude) the auroras are the result of the invasion of belt particles, while in the region of the additional maximum (about 80 deg north geomagnetic latitude) they are caused by the direct penetration of corpuscular streams into the atmosphere. (OTS)« less

Influence of the electron density on the characteristics of terahertz waves generated under laser–cluster interaction

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

Frolov, A. A., E-mail: frolov@ihed.ras.ru

2016-12-15

A theory of generation of terahertz radiation under laser–cluster interaction, developed earlier for an overdense cluster plasma [A. A. Frolov, Plasma Phys. Rep. 42. 637 (2016)], is generalized for the case of arbitrary electron density. The spectral composition of radiation is shown to substantially depend on the density of free electrons in the cluster. For an underdense cluster plasma, there is a sharp peak in the terahertz spectrum at the frequency of the quadrupole mode of a plasma sphere. As the electron density increases to supercritical values, this spectral line vanishes and a broad maximum at the frequency comparable withmore » the reciprocal of the laser pulse duration appears in the spectrum. The dependence of the total energy of terahertz radiation on the density of free electrons is analyzed. The radiation yield is shown to increase significantly under resonance conditions, when the laser frequency is close to the eigenfrequency of the dipole or quadrupole mode of a plasma sphere.« less

Kinematics of mechanical and adhesional micromanipulation under a scanning electron microscope

NASA Astrophysics Data System (ADS)

Saito, Shigeki; Miyazaki, Hideki T.; Sato, Tomomasa; Takahashi, Kunio

2002-11-01

In this paper, the kinematics of mechanical and adhesional micromanipulation using a needle-shaped tool under a scanning electron microscope is analyzed. A mode diagram is derived to indicate the possible micro-object behavior for the specified operational conditions. Based on the diagram, a reasonable method for pick and place operation is proposed. The keys to successful analysis are to introduce adhesional and rolling-resistance factors into the kinematic system consisting of a sphere, a needle-shaped tool, and a substrate, and to consider the time dependence of these factors due to the electron-beam (EB) irradiation. Adhesional force and the lower limit of maximum rolling resistance are evaluated quantitatively in theoretical and experimental ways. This analysis shows that it is possible to control the fracture of either the tool-sphere or substrate-sphere interface of the system selectively by the tool-loading angle and that such a selective fracture of the interfaces enables reliable pick or place operation even under EB irradiation. Although the conventional micromanipulation was not repeatable because the technique was based on an empirically effective method, this analysis should provide us with a guideline to reliable micromanipulation.

The multiwavelength spectrum of NGC 3115: hot accretion flow properties

NASA Astrophysics Data System (ADS)

Almeida, Ivan; Nemmen, Rodrigo; Wong, Ka-Wah; Wu, Qingwen; Irwin, Jimmy A.

2018-04-01

NGC 3115 is the nearest galaxy hosting a billion solar mass black hole and is also a low-luminosity active galactic nucleus (LLAGN). X-ray observations of this LLAGN are able to spatially resolve the hot gas within the sphere of gravitational influence of the supermassive black hole. These observations make NGC 3115 an important test bed for black hole accretion theory in galactic nuclei since they constrain the outer boundary conditions of the hot accretion flow. We present a compilation of the multiwavelength spectral energy distribution (SED) of the nucleus of NGC 3115 from radio to X-rays. We report the results from modelling the observed SED with radiatively inefficient accretion flow (RIAF) models. The radio emission can be well-explained by synchrotron emission from the RIAF without the need for contribution from a relativistic jet. We obtain a tight constraint on the RIAF density profile, ρ (r) ∝ r^{-0.73 _{-0.02} ^{+0.01}}, implying that mass-loss through subrelativistic outflows from the RIAF is significant. The lower frequency radio observation requires the synchrotron emission from a non-thermal electron population in the RIAF, similarly to Sgr A*.

A novel shell-structure cell microcarrier (SSCM) for cell transplantation and bone regeneration medicine.

PubMed

Su, Kai; Gong, Yihong; Wang, Chunming; Wang, Dong-An

2011-06-01

The present study aims to develop a novel open and hollow shell-structure cell microcarrier (SSCM) to improve the anchorage-dependent cell (ADC) loading efficiency, increase the space for cell proliferation and tissue regeneration, and better propel its therapeutic effects. Gelatin particles were prepared with oil/water/oil (o/w/o) technique and modified by an adjustable surface crosslinking technique and subsequent release of uncrosslinked material. Optical microscopy and scanning electron microscopy (SEM) were utilized to observe the morphologies of the microcarriers. Cell loading tests were performed to evaluate the biocompatibilities and effect on osteogenesis of SSCM. SSCMs were successfully fabricated via the surface technique. The shell-structure could allow the cell to attach and grow on both outer and inner surface of sphere and provide adequate space for cell proliferation and extracellular matrix (ECM) secretion. The cell loading rate, proliferation rate and osteogenesis-related gene expressions on the SSCMs were higher than those on the spherical gelatin microcarriers. The outstanding performance of injectable SSCMs endowed with favorable micro-structure, desirable cytocompatibility and enhanced cell affinity makes them as a good choice as cell delivery vehicle for transplanting therapeutic cells towards the scope of tissue regeneration.

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

Borovsky, Joseph E; Cayton, Thomas E; Denton, Michael H

Electron flux measurements from 7 satellites in geosynchronous orbit from 1990-2007 are fit with relativistic bi-Maxwellians, yielding a number density n and temperature T description of the outer electron radiation belt. For 54.5 spacecraft years of measurements the median value ofn is 3.7x10-4 cm-3 and the median value ofT is 142 keY. General statistical properties of n, T, and the 1.1-1.5 MeV flux J are investigated, including local-time and solar-cycle dependencies. Using superposed-epoch analysis triggered on storm onset, the evolution of the outer electron radiation belt through high-speed-steam-driven storms is investigated. The number density decay during the calm before themore » storm is seen, relativistic-electron dropouts and recoveries from dropout are investigated, and the heating of the outer electron radiation belt during storms is examined. Using four different triggers (SSCs, southward-IMF CME sheaths, southward-IMF magnetic clouds, and minimum Dst), CME-driven storms are analyzed with superposed-epoch techniques. For CME-driven storms an absence of a density decay prior to storm onset is found, the compression of the outer electron radiation belt at time of SSC is analyzed, the number-density increase and temperature decrease during storm main phase is seen, and the increase in density and temperature during storm recovery phase is observed. Differences are found between the density-temperature and the flux descriptions, with more information for analysis being available in the density-temperature description.« less

Outer-sphere interaction of aluminum and gallium solvates with competitive anions in 1,2-propanediol solutions

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

Petrosyants, S.P.; Buslaeva, E.R.

1986-04-01

The interaction of aluminum and gallium solvates with ..pi..-acid ligand in 1,2-propanediol solutions has been investigated. The formation of associates of hexacoordinate aluminum solvates depends on the solvation of the anions in the bulk of the solution or on the faces of the solvento complexes. In the case of gallium the association of the solvates with the anions is determined by two factors: the existence of a configurational equilibrium for the solvento complexes and the preferential solvation of the competitive ..pi..-acid ligands.

The protoplanetary system HD 100546 in Hα polarized light from SPHERE/ZIMPOL. A bar-like structure across the disk gap?

NASA Astrophysics Data System (ADS)

Mendigutía, I.; Oudmaijer, R. D.; Garufi, A.; Lumsden, S. L.; Huélamo, N.; Cheetham, A.; de Wit, W. J.; Norris, B.; Olguin, F. A.; Tuthill, P.

2017-12-01

Context. HD 100546 is one of the few known pre-main-sequence stars that may host a planetary system in its disk. Aims: This work aims to contribute to our understanding of HD 100546 by analyzing new polarimetric images with high spatial resolution. Methods: Using VLT/SPHERE/ZIMPOL with two filters in Hα and the adjacent continuum, we have probed the disk gap and the surface layers of the outer disk, covering a region <500 mas (<55 au at 109 pc) from the central star, at an angular resolution of 20 mas. Results: Our data show an asymmetry: the SE and NW regions of the outer disk are more polarized than the SW and NE regions. This asymmetry can be explained from a preferential scattering angle close to 90° and is consistent with previous polarization images. The outer disk in our observations extends from 13 ± 2 to 45 ± 9 au, with a position angle and inclination of 137 ± 5° and 44 ± 8°, respectively. The comparison with previous estimates suggests that the disk inclination could increase with the stellocentric distance, although the different measurements are still consistent within the error bars. In addition, no direct signature of the innermost candidate companion is detected from the polarimetric data, confirming recent results that were based on intensity imagery. We set an upper limit to its mass accretion rate <10-8 M⊙ yr-1 for a substellar mass of 15 MJup. Finally, we report the first detection (>3σ) of a 20 au bar-like structure that crosses the gap through the central region of HD 100546. Conclusions: In the absence of additional data, it is tentatively suggested that the bar could be dust dragged by infalling gas that radially flows from the outer disk to the inner region. This could represent an exceptional case in which a small-scale radial inflow is observed in a single system. If this scenario is confirmed, it could explain the presence of atomic gas in the inner disk that would otherwise accrete on to the central star on a timescale of a few months/years, as previously indicated from spectro-interferometric data, and could be related with additional (undetected) planets.

The nylon scintillator containment vessels for the Borexino solar neutrino experiment

NASA Astrophysics Data System (ADS)

Cadonati, L.; Calaprice, F.; Galbiati, C.; Pocar, A.; Shutt, T.

2014-06-01

The neutrino event rate in the Borexino scintillator is very low ( 0.5 events per day per ton) and concentrated in an energy region well below the 2.6 MeV threshold of natural radioactivity. The intrinsic radioactive contaminants in the photomultipliers (PMTs), in the Stainless Steel Sphere, and in other detector components, play special requirements on the system required to contain the scintillator. The liquid scintillator must be shielded from the Stainless Steel Sphere and from the PMTs by a thick barrier of buffer fluid. The fluid barrier, in addition, needs to be segmented in order to contain migration of radon and daughters emanated by the Stainless Steel Sphere and by the PMTs. These requirements were met by designing and building two spherical vessel made of thin nylon film. The inner vessel contains the scintillator, separating it from the surrounding buffer. The buffer region itself is divided into two concentric shells by the second, outer nylon vessel. In addition, the two nylon vessels must satisfy stringent requirements for radioactivity and for mechanical, optical and chemical properties. This paper describes the requirements of the the nylon vessels for the Borexino experiment and offers a brief overview of the construction methods adopted to meet those requirements.

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

Zhang, R; Bai, W

Purpose: Because of statistical noise in Monte Carlo dose calculations, effective point doses may not be accurate. Volume spheres are useful for evaluating dose in Monte Carlo plans, which have an inherent statistical uncertainty.We use a user-defined sphere volume instead of a point, take sphere sampling around effective point make the dose statistics to decrease the stochastic errors. Methods: Direct dose measurements were made using a 0.125cc Semiflex ion chamber (IC) 31010 isocentrically placed in the center of a homogeneous Cylindric sliced RW3 phantom (PTW, Germany).In the scanned CT phantom series the sensitive volume length of the IC (6.5mm) weremore » delineated and defined the isocenter as the simulation effective points. All beams were simulated in Monaco in accordance to the measured model. In our simulation using 2mm voxels calculation grid spacing and choose calculate dose to medium and request the relative standard deviation ≤0.5%. Taking three different assigned IC over densities (air electron density(ED) as 0.01g/cm3 default CT scanned ED and Esophageal lumen ED 0.21g/cm3) were tested at different sampling sphere radius (2.5, 2, 1.5 and 1 mm) statistics dose were compared with the measured does. Results: The results show that in the Monaco TPS for the IC using Esophageal lumen ED 0.21g/cm3 and sampling sphere radius 1.5mm the statistical value is the best accordance with the measured value, the absolute average percentage deviation is 0.49%. And when the IC using air electron density(ED) as 0.01g/cm3 and default CT scanned EDthe recommented statistical sampling sphere radius is 2.5mm, the percentage deviation are 0.61% and 0.70%, respectivly. Conclusion: In Monaco treatment planning system for the ionization chamber 31010 recommend air cavity using ED 0.21g/cm3 and sampling 1.5mm sphere volume instead of a point dose to decrease the stochastic errors. Funding Support No.C201505006.« less

Method of synthesizing small-diameter carbon nanotubes with electron field emission properties

NASA Technical Reports Server (NTRS)

Liu, Jie (Inventor); Du, Chunsheng (Inventor); Qian, Cheng (Inventor); Gao, Bo (Inventor); Qiu, Qi (Inventor); Zhou, Otto Z. (Inventor)

2009-01-01

Carbon nanotube material having an outer diameter less than 10 nm and a number of walls less than ten are disclosed. Also disclosed are an electron field emission device including a substrate, an optionally layer of adhesion-promoting layer, and a layer of electron field emission material. The electron field emission material includes a carbon nanotube having a number of concentric graphene shells per tube of from two to ten, an outer diameter from 2 to 8 nm, and a nanotube length greater than 0.1 microns. One method to fabricate carbon nanotubes includes the steps of (a) producing a catalyst containing Fe and Mo supported on MgO powder, (b) using a mixture of hydrogen and carbon containing gas as precursors, and (c) heating the catalyst to a temperature above 950.degree. C. to produce a carbon nanotube. Another method of fabricating an electron field emission cathode includes the steps of (a) synthesizing electron field emission materials containing carbon nanotubes with a number of concentric graphene shells per tube from two to ten, an outer diameter of from 2 to 8 nm, and a length greater than 0.1 microns, (b) dispersing the electron field emission material in a suitable solvent, (c) depositing the electron field emission materials onto a substrate, and (d) annealing the substrate.

Long-Lived Glass Mirrors For Outer Space

NASA Technical Reports Server (NTRS)

Bouquet, Frank L.; Maag, Carl R.; Heggen, Philip M.

1988-01-01

Paper summarizes available knowledge about glass mirrors for use in outer space. Strengths and weaknesses of various types of first and second reflective surfaces identified. Second-surface glass mirrors used in outer space designed to different criteria more stringent for terrestrial mirrors. Protons, electrons, cosmic rays, meteorites, and orbiting space debris affect longevities of components. Contamination also factor in space.

Electrostatic-assembly three-dimensional CNTs/rGO implanted Cu2O composite spheres and its photocatalytic properties

NASA Astrophysics Data System (ADS)

Zeng, Bin; Chen, Xiaohua; Ning, Xutao; Chen, Chuansheng; Deng, Weina; Huang, Qun; Zhong, Wenbin

2013-07-01

Carbon nanotubes/reduced graphene oxides (CNTs/rGO) implanting cuprous oxide (Cu2O) composite spheres have been successfully prepared via an electrostatic self-assemble with microwave-assisted. Scanning electron microscopy and transmission electron microscopy observations confirmed that the hybrid of CNTs and rGO was implanted into Cu2O matrix and formed a three-dimensional embedded micrometer sphere structure. The possible formation mechanism of this architecture was also proposed. The photocatalytic properties were further investigated by evaluating on photo-degradation of a pollutant methyl orange (MO). The experimental results indicated that this novel architecture enhanced photocatalytic performance with 99.8% decomposition of MO after 40 min in the presence of H2O2 under visible light irradiation, which was much higher than that of pure Cu2O powders (67.9%). This study provides a convenient method for assembling various CNTs/rGO-semiconductor composites in the future applications of water purification as well as optoelectronic fields at a large scale.

Electrical four-point probing of spherical metallic thin films coated onto micron sized polymer particles

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

Pettersen, Sigurd R., E-mail: sigurd.r.pettersen@ntnu.no, E-mail: jianying.he@ntnu.no; Stokkeland, August Emil; Zhang, Zhiliang

Micron-sized metal-coated polymer spheres are frequently used as filler particles in conductive composites for electronic interconnects. However, the intrinsic electrical resistivity of the spherical thin films has not been attainable due to deficiency in methods that eliminate the effect of contact resistance. In this work, a four-point probing method using vacuum compatible piezo-actuated micro robots was developed to directly investigate the electric properties of individual silver-coated spheres under real-time observation in a scanning electron microscope. Poly(methyl methacrylate) spheres with a diameter of 30 μm and four different film thicknesses (270 nm, 150 nm, 100 nm, and 60 nm) were investigated. By multiplying the experimental resultsmore » with geometrical correction factors obtained using finite element models, the resistivities of the thin films were estimated for the four thicknesses. These were higher than the resistivity of bulk silver.« less

Wave number selection in the presence of noise: Experimental results

NASA Astrophysics Data System (ADS)

Zhilenko, Dmitry; Krivonosova, Olga; Gritsevich, Maria; Read, Peter

2018-05-01

In this study, we consider how the wave number selection in spherical Couette flow, in the transition to azimuthal waves after the first instability, occurs in the presence of noise. The outer sphere was held stationary, while the inner sphere rotational speed was increased linearly from a subcritical flow to a supercritical one. In a supercritical flow, one of two possible flow states, each with different azimuthal wave numbers, can appear depending upon the initial and final Reynolds numbers and the acceleration value. Noise perturbations were added by introducing small disturbances into the rotational speed signal. With an increasing noise amplitude, a change in the dominant wave number from m to m ± 1 was found to occur at the same initial and final Reynolds numbers and acceleration values. The flow velocity measurements were conducted by using laser Doppler anemometry. Using these results, the role of noise as well as the behaviour of the amplitudes of the competing modes in their stages of damping and growth were determined.

Formation of energetic electron butterfly distributions by magnetosonic waves via Landau resonance

DOE PAGES

Li, Jinxing; Ni, Binbin; Ma, Qianli; ...

2016-03-06

Radiation belt electrons can exhibit different types of pitch angle distributions in response to various magnetospheric processes. Butterfly distributions, characterized by flux minima at pitch angles around 90°, are broadly observed in both the outer and inner belts and the slot region. Butterfly distributions close to the outer magnetospheric boundary have been attributed to drift shell splitting and losses to the magnetopause. However, their occurrence in the inner belt and the slot region has hitherto not been resolved. In this study, by analyzing the particle and wave data collected by the Van Allen Probes during a geomagnetic storm, we combinemore » test particle calculations and Fokker-Planck simulations to reveal that scattering by equatorial magnetosonic waves is a significant cause for the formation of energetic electron butterfly distributions in the inner magnetosphere. Finally, another event shows that a large-amplitude magnetosonic wave in the outer belt can create electron butterfly distributions in just a few minutes.« less

3-Dimensional Colloidal Crystals From Hollow Spheres

NASA Astrophysics Data System (ADS)

Zhang, Jian; Work, William J.; Sanyal, Subrata; Lin, Keng-Hui; Yodh, A. G.

2000-03-01

We have succeeded in synthesizing submicron-sized, hollow PMMA spheres and self-assembling them into colloidal crystalline structures using the depletion force. The resulting structures can be used as templates to make high refractive-index contrast, porous, inorganic structures without the need to use calcination or chemical-etching. With the method of emulsion polymerization, we managed to coat a thin PMMA shell around a swellable P(MMA/MAA/EGDMA) core. After neutralization and heating above the glass transition temperature of PMMA, we obtained water-swollen hydrogel particles encapsulated in PMMA shells. These composite particles become hollow spheres after drying. We characterized the particles with both transmission electron microscopy (TEM) and dynamic light scattering (DLS). The TEM results confirmed that each sphere has a hollow core. The DLS results showed that our hollow spheres are submicron-sized, with a swelling ratio of at least 25%, and with a polydispersity less than 5%. We anticipate using this method in the near-future to encapsulate ferrofluid emulsion droplets and liquid crystal droplets.

Meckelin 3 Is Necessary for Photoreceptor Outer Segment Development in Rat Meckel Syndrome

PubMed Central

Tiwari, Sarika; Hudson, Scott; Gattone, Vincent H.; Miller, Caroline; Chernoff, Ellen A. G.; Belecky-Adams, Teri L.

2013-01-01

Ciliopathies lead to multiorgan pathologies that include renal cysts, deafness, obesity and retinal degeneration. Retinal photoreceptors have connecting cilia joining the inner and outer segment that are responsible for transport of molecules to develop and maintain the outer segment process. The present study evaluated meckelin (MKS3) expression during outer segment genesis and determined the consequences of mutant meckelin on photoreceptor development and survival in Wistar polycystic kidney disease Wpk/Wpk rat using immunohistochemistry, analysis of cell death and electron microscopy. MKS3 was ubiquitously expressed throughout the retina at postnatal day 10 (P10) and P21. However, in the mature retina, MKS3 expression was restricted to photoreceptors and the retinal ganglion cell layer. At P10, both the wild type and homozygous Wpk mutant retina had all retinal cell types. In contrast, by P21, cells expressing rod- and cone-specific markers were fewer in number and expression of opsins appeared to be abnormally localized to the cell body. Cell death analyses were consistent with the disappearance of photoreceptor-specific markers and showed that the cells were undergoing caspase-dependent cell death. By electron microscopy, P10 photoreceptors showed rudimentary outer segments with an axoneme, but did not develop outer segment discs that were clearly present in the wild type counterpart. At p21 the mutant outer segments appeared much the same as the P10 mutant outer segments with only a short axoneme, while the wild-type controls had developed outer segments with many well-organized discs. We conclude that MKS3 is not important for formation of connecting cilium and rudimentary outer segments, but is critical for the maturation of outer segment processes. PMID:23516626

Scanning ion-conductance and atomic force microscope with specialized sphere-shaped nanopippettes

NASA Astrophysics Data System (ADS)

Zhukov, M. V.; Sapozhnikov, I. D.; Golubok, A. O.; Chubinskiy-Nadezhdin, V. I.; Komissarenko, F. E.; Lukashenko, S. Y.

2017-11-01

A scanning ion-conductance microscope was designed on the basis of scanning probe microscope NanoTutor. The optimal parameters of nanopipettes fabrication were found according to scanning electron microscopy diagnostics, current-distance I (Z) and current-voltage characteristics. A comparison of images of test objects, including biological samples, was carried out in the modes of optical microscopy, atomic force microscopy and scanning ion-conductance microscopy. Sphere-shaped nanopippettes probes were developed and tested to increase the stability of pipettes, reduce invasiveness and improve image quality of atomic force microscopy in tapping mode. The efficiency of sphere-shaped nanopippettes is shown.

Porous cobalt spheres for high temperature gradient magnetically assisted fluidized beds

NASA Technical Reports Server (NTRS)

Atwater, James E.; Akse, James R.; Jovanovic, Goran N.; Wheeler, Richard R Jr; Sornchamni, Thana

2003-01-01

Porous metallic cobalt spheres have been prepared as high temperature capable media for employment in gradient magnetically assisted fluidization and filtration technologies. Cobalt impregnated alginate beads are first formed by extrusion of an aqueous suspension of Co3O4 into a Co(II) chloride solution. The organic polymer is thermally decomposed yielding cobalt oxide spheres, followed by reduction to the metallic state, and densification. Cobalt beads have been produced with porosities ranging between 10 and 50%, depending upon sintering conditions. The product media have been characterized by scanning electron microscopy (SEM), nitrogen adsorption porosimetry, and vibrating sample magnetometry. c2003 Elsevier Science Ltd. All rights reserved.

Coherent Extreme Ultraviolet Generation and Surface Studies Using Ultraviolet Excimer Lasers.

DTIC Science & Technology

1986-02-10

of Outer-Shell Electrons" 7. "A Theoretical Model of Inner-Shell ......................... 30 A Excitation by Outer-Snell Electrons" E. "Anomalous...rays are feasible. Our work involves a program of activities, involving both experimental and theoretical components, to explore the physical... theoretical effort con- centrating on the character of high order multiquantum coupling in the inten- sity regime above 1017 WcM2 . In addition

Acquisition of Long-Duration, Low-Gravity Slosh Data Utilizing Existing ISS Equipment (SPHERES) for Calibration of CFD Models of Coupled Fluid-Vehicle Behavior

NASA Technical Reports Server (NTRS)

Schallhorn, Paul; Roth, Jacob; Marsell, Brandon; Kirk, Daniel; Gutierrez, Hector; Saenz-Otero, Alvar; Dorney, Daniel; Moder, Jeffrey

2013-01-01

Accurate prediction of coupled fluid slosh and launch vehicle or spacecraft dynamics (e.g., nutation/precessional movement about various axes, attitude changes, ect.) requires Computational Fluid Dynamics (CFD) models calibrated with low-gravity, long duration slosh data. Recently completed investigations of reduced gravity slosh behavior have demonstrated the limitations of utilizing parabolic flights on specialized aircraft with respect to the specific objectives of the experiments. Although valuable data was collected, the benefits of longer duration low-gravity environments were clearly established. The proposed research provides the first data set from long duration tests in zero gravity that can be directly used to benchmark CFD models, including the interaction between the sloshing fluid and the tank/vehicle dynamics. To explore the coupling of liquid slosh with the motion of an unconstrained tank in microgravity, NASA's Kennedy Space Center, Launch Services Program has teamed up with the Florida Institute of Technology (FIT), Massachusetts Institute of Technology (MIT) and the NASA Game Changing Development Program (GCD) to perform a series of slosh dynamics experiments on the International Space Station using the SPHERES platform. The Synchronized Position Hold Engage Reorient Experimental Satellites (SPHERES) testbed provides a unique, free-floating instrumented platform on ISS that can be utilized in a manner that would solve many of the limitations of the current knowledge related to propellant slosh dynamics on launch vehicle and spacecraft fuel tanks. The six degree of freedom (6-DOF) motion of the SPHERES free-flyer is controlled by an array of cold-flow C02 thrusters, supplied from a built-in liquid C02 tank. These SPHERES can independently navigate and re-orient themselves within the ISS. The intent of this project is to design an externally mounted tank to be driven inside the ISS by a set of two SPHERES devices (Figure 1). The tank geometry simulates a launch vehicle upper stage propellant tank and the maneuvers replicate those of real vehicles. The design includes inertial sensors, data acquisition, image capture and data storage interfaces to the SPHERES VERTIGO computer system on board the flight article assembly. The design also includes mechanical and electronic interfaces to the existing SPHERES hardware, which include self-contained packages that can operate in conjunction with the existing SPHERES electronics

Acquisition of Long-Duration, Low-Gravity Slosh Data Utilizing Existing ISS Equipment (SPHERES) for Calibration of CFD Models of Coupled Fluid-Vehicle Behavior

NASA Technical Reports Server (NTRS)

Schallhorn, Paul; Roth, Jacob; Marsell, Brandon; Kirk, Daniel; Gutierrez, Hector; Saenz-Otero, Alvar; Dorney, Daniel; Moder, Jeffrey

2012-01-01

Accurate prediction of coupled fluid slosh and launch vehicle or spacecraft dynamics (e.g., nutation/precessional movement about various axes, attitude changes, ect.) requires Computational Fluid Dynamics (CFD) models calibrated with low-gravity, long duration slosh data. Recently completed investigations of reduced gravity slosh behavior have demonstrated the limitations of utilizing parabolic flights on specialized aircraft with respect to the specific objectives of the experiments. Although valuable data was collected, the benefits of longer duration low-gravity environments were clearly established. The proposed research provides the first data set from long duration tests in zero gravity that can be directly used to benchmark CFD models, including the interaction between the sloshing fluid and the tank/vehicle dynamics. To explore the coupling of liquid slosh with the motion of an unconstrained tank in microgravity, NASA's Kennedy Space Center, Launch Services Program has teamed up with the Florida Institute of Technology (FIT), Massachusetts Institute of Technology (MIT) and the Office of the Chief Technologist (OCT) to perform a series of slosh dynamics experiments on the International Space Station using the SPHERES platform. The Synchronized Position Hold Engage Reorient Experimental Satellites (SPHERES) testbed provides a unique, free-floating instrumented platform on ISS that can be utilized in a manner that would solve many of the limitations of the current knowledge related to propellant slosh dynamics on launch vehicle and spacecraft fuel tanks. The six degree of freedom (6-DOF) motion of the SPHERES free-flyer is controlled by an array of cold-flow C02 thrusters, supplied from a built-in liquid C02 tank. These SPHERES can independently navigate and re-orient themselves within the ISS. The intent of this project is to design an externally mounted tank to be driven inside the ISS by a set of two SPHERES devices (Figure 1 ). The tank geometry simulates a launch vehicle upper stage propellant tank and the maneuvers replicate those of real vehicles. The design includes inertial sensors, data acquisition, image capture and data storage interfaces to the SPHERES VERTIGO computer system on board the flight article assembly. The design also includes mechanical and electronic interfaces to the existing SPHERES hardware, which include self-contained packages that can operate in conjunction with the existing SPHERES electronics.

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

Computational study of the electronic structure and magnetic properties of the Ni-C state in [NiFe] hydrogenases including the second coordination sphere.

PubMed

Kampa, Mario; Lubitz, Wolfgang; van Gastel, Maurice; Neese, Frank

2012-12-01

[NiFe] hydrogenases catalyze the reversible formation of H(2). The [NiFe] heterobimetallic active site is rich in redox states. Here, we investigate the key catalytic state Ni-C of Desulfovibrio vulgaris Miyazaki F hydrogenase using a cluster model that includes the truncated amino acids of the entire second coordination sphere of the enzyme. The optimized geometries, computed g tensors, hyperfine coupling constants, and IR stretching frequencies all agree well with experimental values. For the hydride in the bridging position, only a single minimum on the potential energy surface is found, indicating that the hydride bridges and binds to both nickel and iron. The influence of the second coordination sphere on the electronic structure is investigated by comparing results from the large cluster models with truncated models. The largest interactions of the second coordination sphere with the active site concern the hydrogen bonds with the cyanide ligands, which modulate the bond between iron and these ligands. Secondly, the electronic structure of the active site is found to be sensitive to the protonation state of His88. This residue forms a hydrogen bond with the spin-carrying sulfur atom of Cys549, which in turn tunes the spin density at the nickel and coordinating sulfur atoms. In addition, the unequal distribution of spin density over the equatorial cysteine residues results from different orientations of the cysteine side chains, which are kept in their particular orientation by the secondary structure of the protein.

Detailed Characteristics of Radiation Belt Electrons Revealed by CSSWE/REPTile Measurements

NASA Astrophysics Data System (ADS)

Zhang, K.; Li, X.; Schiller, Q.; Gerhardt, D. T.; Millan, R. M.

2016-12-01

The outer radiation belt electrons are highly dynamic. We study the detailed characteristics of the relativistic electrons in the outer belt using measurements from the Colorado Student Space Weather Experiment (CSSWE) mission, a low Earth orbit Cubesat, which transverses the radiation belt four times in one orbit ( 1.5 hr) and has the advantage of measuring the dynamic activities of the electrons including their rapid precipitations. Among the features of the relativistic electrons, we show the measured electron distribution as a function of geomagnetic activities and local magnetic field strength. Moreover, a specific precipitation band, which happened on 19 Jan 2013, is investigated based on the conjunctive measurement of CSSWE and the Balloon Array for Radiation belt Relativistic Electron Losses (BARREL). In this precipitation band event, the net loss of the 0.58 1.63 MeV electrons (L=3.5 6) is estimated to account for 6.84% of the total electron content.

Discovery of a Frank-Kasper [sigma] Phase in Sphere-Forming Block Copolymer Melts

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

Lee, Sangwoo; Bluemle, Michael J.; Bates, Frank S.

Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma ({sigma}) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the {sigma} phase in undiluted linear block copolymers (and certain branchedmore » dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.« less

Fabrication of malachite with a hierarchical sphere-like architecture.

PubMed

Xu, Jiasheng; Xue, Dongfeng

2005-09-15

Malachite (Cu2(OH)2CO3) with a hierarchical sphere-like architecture has been successfully synthesized via a simple and mild hydrothermal route in the absence of any external inorganic additives or organic structure-directing templates. Powder X-ray diffraction, scanning electron microscopy, and Fourier transmission infrared spectrometry are used to characterize various properties of the obtained malachite samples. The hierarchical malachite particles are uniform spheres with a diameter of 10-20 microm, which are comprised of numerous two-dimensional microplatelets paralleling the sphere surface. The initial concentration of reagents, the hydrothermal reaction time, and temperature are important factors which dominantly affect the evolution of crystal morphologies. The growth of the hierarchical architecture is believed to be a layer-by-layer growth process. Further, copper oxide with the similar morphology can be easily obtained from the as-prepared malachite.

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.

Phononic crystals of spherical particles: A tight binding approach

NASA Astrophysics Data System (ADS)

Mattarelli, M.; Secchi, M.; Montagna, M.

2013-11-01

The vibrational dynamics of a fcc phononic crystal of spheres is studied and compared with that of a single free sphere, modelled either by a continuous homogeneous medium or by a finite cluster of atoms. For weak interaction among the spheres, the vibrational dynamics of the phononic crystal is described by shallow bands, with low degree of dispersion, corresponding to the acoustic spheroidal and torsional modes of the single sphere. The phonon displacements are therefore related to the vibrations of a sphere, as the electron wave functions in a crystal are related to the atomic wave functions in a tight binding model. Important dispersion is found for the two lowest phonon bands, which correspond to zero frequency free translation and rotation of a free sphere. Brillouin scattering spectra are calculated at some values of the exchanged wavevectors of the light, and compared with those of a single sphere. With weak interaction between particles, given the high acoustic impedance mismatch in dry systems, the density of phonon states consist of sharp bands separated by large gaps, which can be well accounted for by a single particle model. Based on the width of the frequency gaps, tunable with the particle size, and on the small number of dispersive acoustic phonons, such systems may provide excellent materials for application as sound or heat filters.

Rapid Loss of Radiation Belt Relativistic Electrons by EMIC Waves

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

Su, Zhenpeng; Gao, Zhonglei; Zheng, Huinan

How relativistic electrons are lost is an important question surrounding the complex dynamics of the Earth's outer radiation belt. Radial loss to the magnetopause and local loss to the atmosphere are two main competing paradigms. Here on the basis of the analysis of a radiation belt storm event on 27 February 2014, we present new evidence for the electromagnetic ion cyclotron (EMIC) wave-driven local precipitation loss of relativistic electrons in the heart of the outer radiation belt. During the main phase of this storm, the radial profile of relativistic electron phase space density was quasi-monotonic, qualitatively inconsistent with the predictionmore » of radial loss theory. The local loss at low L shells was required to prevent the development of phase space density peak resulting from the radial loss process at high L shells. The rapid loss of relativistic electrons in the heart of outer radiation belt was observed as a dip structure of the electron flux temporal profile closely related to intense EMIC waves. Our simulations further confirm that the observed EMIC waves within a quite limited longitudinal region were able to reduce the off-equatorially mirroring relativistic electron fluxes by up to 2 orders of magnitude within about 1.5 h.« less

Rapid Loss of Radiation Belt Relativistic Electrons by EMIC Waves

DOE PAGES

Su, Zhenpeng; Gao, Zhonglei; Zheng, Huinan; ...

2017-08-31

How relativistic electrons are lost is an important question surrounding the complex dynamics of the Earth's outer radiation belt. Radial loss to the magnetopause and local loss to the atmosphere are two main competing paradigms. Here on the basis of the analysis of a radiation belt storm event on 27 February 2014, we present new evidence for the electromagnetic ion cyclotron (EMIC) wave-driven local precipitation loss of relativistic electrons in the heart of the outer radiation belt. During the main phase of this storm, the radial profile of relativistic electron phase space density was quasi-monotonic, qualitatively inconsistent with the predictionmore » of radial loss theory. The local loss at low L shells was required to prevent the development of phase space density peak resulting from the radial loss process at high L shells. The rapid loss of relativistic electrons in the heart of outer radiation belt was observed as a dip structure of the electron flux temporal profile closely related to intense EMIC waves. Our simulations further confirm that the observed EMIC waves within a quite limited longitudinal region were able to reduce the off-equatorially mirroring relativistic electron fluxes by up to 2 orders of magnitude within about 1.5 h.« less

Type III Solar Radio Burst Source Region Splitting due to a Quasi-separatrix Layer

NASA Astrophysics Data System (ADS)

McCauley, Patrick I.; Cairns, Iver H.; Morgan, John; Gibson, Sarah E.; Harding, James C.; Lonsdale, Colin; Oberoi, Divya

2017-12-01

We present low-frequency (80–240 MHz) radio imaging of type III solar radio bursts observed by the Murchison Widefield Array on 2015 September 21. The source region for each burst splits from one dominant component at higher frequencies into two increasingly separated components at lower frequencies. For channels below ∼132 MHz, the two components repetitively diverge at high speeds (0.1c–0.4c) along directions tangent to the limb, with each episode lasting just ∼2 s. We argue that both effects result from the strong magnetic field connectivity gradient that the burst-driving electron beams move into. Persistence mapping of extreme-ultraviolet jets observed by the Solar Dynamics Observatory reveals quasi-separatrix layers (QSLs) associated with coronal null points, including separatrix dome, spine, and curtain structures. Electrons are accelerated at the flare site toward an open QSL, where the beams follow diverging field lines to produce the source splitting, with larger separations at larger heights (lower frequencies). The splitting motion within individual frequency bands is interpreted as a projected time-of-flight effect, whereby electrons traveling along the outer field lines take slightly longer to excite emission at adjacent positions. Given this interpretation, we estimate an average beam speed of 0.2c. We also qualitatively describe the quiescent corona, noting in particular that a disk-center coronal hole transitions from being dark at higher frequencies to bright at lower frequencies, turning over around 120 MHz. These observations are compared to synthetic images based on the MHD algorithm outside a sphere (MAS) model, which we use to flux-calibrate the burst data.

Interactions between Silicon Oxide Nanoparticles (SONPs) and U(VI) Contaminations: Effects of pH, Temperature and Natural Organic Matters

PubMed Central

Wu, Hanyu; Li, Ping; Pan, Duoqiang; Yin, Zhuoxin; Fan, Qiaohui; Wu, Wangsuo

2016-01-01

The interactions between contaminations of U(VI) and silicon oxide nanoparticles (SONPs), both of which have been widely used in modern industry and induced serious environmental challenge due to their high mobility, bioavailability, and toxicity, were studied under different environmental conditions such as pH, temperature, and natural organic matters (NOMs) by using both batch and spectroscopic approaches. The results showed that the accumulation process, i.e., sorption, of U(VI) on SONPs was strongly dependent on pH and ionic strength, demonstrating that possible outer- and/or inner-sphere complexes were controlling the sorption process of U(VI) on SONPs in the observed pH range. Humic acid (HA), one dominated component of NOMs, bounded SONPs can enhance U(VI) sorption below pH~4.5, whereas restrain at high pH range. The reversible sorption of U(VI) on SONPs possibly indicated that the outer-sphere complexes were prevalent at pH 5. However, an irreversible interaction of U(VI) was observed in the presence of HA (Fig 1). It was mainly due to the ternary SONPs-HA-U(VI) complexes (Type A Complexes). After SONPs adsorbed U(VI), the particle size in suspension was apparently increased from ~240 nm to ~350 nm. These results showed that toxicity of both SONPs and U(VI) will decrease to some extent after the interaction in the environment. These findings are key for providing useful information on the possible mutual interactions among different contaminants in the environment. PMID:26930197

Eccentricity in planetary systems and the role of binarity. Sample definition, initial results, and the system of HD 211847

NASA Astrophysics Data System (ADS)

Moutou, C.; Vigan, A.; Mesa, D.; Desidera, S.; Thébault, P.; Zurlo, A.; Salter, G.

2017-06-01

We explore the multiplicity of exoplanet host stars with high-resolution images obtained with VLT/SPHERE. Two different samples of systems were observed: one containing low-eccentricity outer planets, and the other containing high-eccentricity outer planets. We find that 10 out of 34 stars in the high-eccentricity systems are members of a binary, while the proportion is 3 out of 27 for circular systems. Eccentric-exoplanet hosts are, therefore, significantly more likely to have a stellar companion than circular-exoplanet hosts. The median magnitude contrast over the 68 data sets is 11.26 and 9.25, in H and K, respectively, at 0.30 arcsec. The derived detection limits reveal that binaries with separations of less than 50 au are rarer for exoplanet hosts than for field stars. Our results also imply that the majority of high-eccentricity planets are not embedded in multiple stellar systems (24 out of 34), since our detection limits exclude the presence of a stellar companion. We detect the low-mass stellar companions of HD 7449 and HD 211847, both members of our high-eccentricity sample. HD 7449B was already detected and our independent observation is in agreement with this earlier work. HD 211847's substellar companion, previously detected by the radial velocity method, is actually a low-mass star seen face-on. The role of stellar multiplicity in shaping planetary systems is confirmed by this work, although it does not appear as the only source of dynamical excitation. Based on observations collected with SPHERE on the Very Large Telescope (ESO, Chile).

Influence of the shell thickness and charge distribution on the effective interaction between two like-charged hollow spheres.

PubMed

Angelescu, Daniel G; Caragheorgheopol, Dan

2015-10-14

The mean-force and the potential of the mean force between two like-charged spherical shells were investigated in the salt-free limit using the primitive model and Monte Carlo simulations. Apart from an angular homogeneous distribution, a discrete charge distribution where point charges localized on the shell outer surface followed an icosahedral arrangement was considered. The electrostatic coupling of the model system was altered by the presence of mono-, trivalent counterions or small dendrimers, each one bearing a net charge of 9 e. We analyzed in detail how the shell thickness and the radial and angular distribution of the shell charges influenced the effective interaction between the shells. We found a sequence of the potential of the mean force similar to the like-charged filled spheres, ranging from long-range purely repulsive to short-range purely attractive as the electrostatic coupling increased. Both types of potentials were attenuated and an attractive-to-repulsive transition occurred in the presence of trivalent counterions as a result of (i) thinning the shell or (ii) shifting the shell charge from the outer towards the inner surface. The potential of the mean force became more attractive with the icosahedrally symmetric charge model, and additionally, at least one shell tended to line up with 5-fold symmetry axis along the longest axis of the simulation box at the maximum attraction. The results provided a basic framework of understanding the non-specific electrostatic origin of the agglomeration and long-range assembly of the viral nanoparticles.

The Role of the Auroral Processes in the Formation of the Outer Electron Radiation Belt

NASA Astrophysics Data System (ADS)

Stepanova, M. V.; Antonova, E. E.; Pinto, V. A.; Moya, P. S.; Riazantseva, M.; Ovchinnikov, I.

2016-12-01

The role of the auroral processes in the formation of the outer electron radiation belt during storms is analyzed using the data of RBSP mission, low orbiting satellites and ground based observations. We analyze fluxes of the low energy precipitating ions using data of the Defense Meteorological Satellite Program (DMSP). The location of the auroral electrojet is obtained from the IMAGE magnetometer network, and of the electron distribution in the outer radiation belt from the RBSP mission. We take into account the latest results on the auroral oval mapping in accordance with which the most part of the auroral oval maps not to the plasma sheet. It maps into the surrounding the Earth plasma ring in which transverse currents are closed inside the magnetosphere. Such currents constitute the high latitude continuation of the ordinary ring current. The development of the ring current and its high latitude continuation generates strong distortion of the Earth's magnetic field and corresponding adiabatic variation of the relativistic electron fluxes. This adiabatic variation should be considered for the analysis of the processes of the acceleration of relativistic electrons and formation of the outer radiation belt. We also analyze the plasma pressure profiles during storms and demonstrate the formation of sharp plasma pressure peak at the equatorial boundary of the auroral oval. It is shown that the observed this peak is directly connected to the creation of the seed population of relativistic electrons. We discuss the possibility to predict the position of new radiation belt during recovery phase of the magnetic storm using data of low orbiting and ground based observations.

Appendage mountable electronic devices conformable to surfaces

DOEpatents

Rogers, John; Ying, Ming; Bonifas, Andrew; Lu, Nanshu

2017-01-24

Disclosed are appendage mountable electronic systems and related methods for covering and conforming to an appendage surface. A flexible or stretchable substrate has an inner surface for receiving an appendage, including an appendage having a curved surface, and an opposed outer surface that is accessible to external surfaces. A stretchable or flexible electronic device is supported by the substrate inner and/or outer surface, depending on the application of interest. The electronic device in combination with the substrate provides a net bending stiffness to facilitate conformal contact between the inner surface and a surface of the appendage provided within the enclosure. In an aspect, the system is capable of surface flipping without adversely impacting electronic device functionality, such as electronic devices comprising arrays of sensors, actuators, or both sensors and actuators.

Direct ultrasonic-assisted synthesis of sphere-like nanocrystals of spinel Co3O4 and Mn3O4.

PubMed

Askarinejad, Azadeh; Morsali, Ali

2009-01-01

A simple sonochemical method was developed to synthesize uniform sphere-like or cubic Co(3)O(4) and Mn(3)O(4) nanocrystals by using acetate salts and sodium hydroxide or tetramethylammonium hydroxide (TMAH) as precursors. Influence of some parameters such as time of reaction, alkali salts, and power of the ultrasound and the molar ratio of the starting materials on the size, morphology and degree of crystallinity of the products was studied. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), FTIR spectroscopy, Thermal gravimetry analysis and differential thermal analysis (TGA/DTA) were used to characterize the nanocrystals.

Preparation and magnetic properties of magnetic photonic crystal by using monodisperse polystyrene covered Fe3O4 nanoparticles onto glass substrate

NASA Astrophysics Data System (ADS)

Azizi, Zahra Sadat; Tehranchi, Mohammad Mehdi; Vakili, Seyed Hamed; Pourmahdian, Saeed

2018-05-01

Engineering approach towards combined photonic band gap properties and magnetic/polymer composite particles, attract considerable attention of researchers due to their unique properties. In this research, two different magnetic particles were prepared by nearly monodisperse polystyrene spheres as bead with two concentrations of Fe3O4 nanoparticles to prepare magnetic photonic crystals (MPCs). The crystal surfaces and particles morphology were investigated employing scanning electron microscopy and transmission electron microscopy. The volume fraction of magnetic material embedded into colloidal spheres and their morphology was found to be a key parameter in the optical and magneto-optical properties of transparent MPC.

Physical mechanism causing rapid changes in ultrarelativistic electron pitch angle distributions right after a shock arrival: Evaluation of an electron dropout event

NASA Astrophysics Data System (ADS)

Zhang, X.-J.; Li, W.; Thorne, R. M.; Angelopoulos, V.; Ma, Q.; Li, J.; Bortnik, J.; Nishimura, Y.; Chen, L.; Baker, D. N.; Reeves, G. D.; Spence, H. E.; Kletzing, C. A.; Kurth, W. S.; Hospodarsky, G. B.; Blake, J. B.; Fennell, J. F.

2016-09-01

Three mechanisms have been proposed to explain relativistic electron flux depletions (dropouts) in the Earth's outer radiation belt during storm times: adiabatic expansion of electron drift shells due to a decrease in magnetic field strength, magnetopause shadowing and subsequent outward radial diffusion, and precipitation into the atmosphere (driven by EMIC wave scattering). Which mechanism predominates in causing electron dropouts commonly observed in the outer radiation belt is still debatable. In the present study, we evaluate the physical mechanism that may be primarily responsible for causing the sudden change in relativistic electron pitch angle distributions during a dropout event observed by Van Allen Probes during the main phase of the 27 February 2014 storm. During this event, the phase space density of ultrarelativistic (>1 MeV) electrons was depleted by more than 1 order of magnitude over the entire radial extent of the outer radiation belt (3 < L* < 5) in less than 6 h after the passage of an interplanetary shock. We model the electron pitch angle distribution under a compressed magnetic field topology based on actual solar wind conditions. Although these ultrarelativistic electrons exhibit highly anisotropic (peaked in 90°), energy-dependent pitch angle distributions, which appear to be associated with the typical EMIC wave scattering, comparison of the modeled electron distribution to electron measurements indicates that drift shell splitting is responsible for this rapid change in electron pitch angle distributions. This further indicates that magnetopause loss is the predominant cause of the electron dropout right after the shock arrival.

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

USGS Publications Warehouse

Leenheer, J.A.; Brown, G.K.; MacCarthy, P.; Cabaniss, S.E.

1998-01-01

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The 'metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-1R spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short- chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The `metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.

Self-consistent average-atom scheme for electronic structure of hot and dense plasmas of mixture.

PubMed

Yuan, Jianmin

2002-10-01

An average-atom model is proposed to treat the electronic structures of hot and dense plasmas of mixture. It is assumed that the electron density consists of two parts. The first one is a uniform distribution with a constant value, which is equal to the electron density at the boundaries between the atoms. The second one is the total electron density minus the first constant distribution. The volume of each kind of atom is proportional to the sum of the charges of the second electron part and of the nucleus within each atomic sphere. By this way, one can make sure that electrical neutrality is satisfied within each atomic sphere. Because the integration of the electron charge within each atom needs the size of that atom in advance, the calculation is carried out in a usual self-consistent way. The occupation numbers of electron on the orbitals of each kind of atom are determined by the Fermi-Dirac distribution with the same chemical potential for all kinds of atoms. The wave functions and the orbital energies are calculated with the Dirac-Slater equations. As examples, the electronic structures of the mixture of Au and Cd, water (H2O), and CO2 at a few temperatures and densities are presented.

Adenosine/guanosine-3',5'-bis-phosphates as biocompatible and selective Zn2+-ion chelators. Characterization and comparison with adenosine/guanosine-5'-di-phosphate.

PubMed

Sayer, Alon Haim; Blum, Eliav; Major, Dan Thomas; Vardi-Kilshtain, Alexandra; Levi Hevroni, Bosmat; Fischer, Bilha

2015-04-28

Although involved in various physiological functions, nucleoside bis-phosphate analogues and their metal-ion complexes have been scarcely studied. Hence, here, we explored the solution conformation of 2′-deoxyadenosine- and 2′-deoxyguanosine-3′,5′-bisphosphates, 3 and 4, d(pNp), as well as their Zn(2+)/Mg(2+) binding sites and binding-modes (i.e. inner- vs. outer-sphere coordination), acidity constants, stability constants of their Zn(2+)/Mg(2+) complexes, and their species distribution. Analogues 3 and 4, in solution, adopted a predominant Southern ribose conformer (ca. 84%), gg conformation around C4'-C5' and C5'-O5' bonds, and glycosidic angle in the anti-region (213-270°). (1)H- and (31)P-NMR experiments indicated that Zn(2+)/Mg(2+) ions coordinated to P5' and P3' groups of 3 and 4 but not to N7 nitrogen atom. Analogues 3 and 4 formed ca. 100-fold more stable complexes with Zn(2+)vs. Mg(2+)-ions. Complexes of 3 and 4 with Mg(2+) at physiological pH were formed in minute amounts (11% and 8%, respectively) vs. Zn(2+) complexes (46% and 44%). Stability constants of Zn(2+)/Mg(2+) complexes of analogues 3 and 4 (log KML(M) = 4.65-4.75/2.63-2.79, respectively) were similar to those of the corresponding complexes of ADP and GDP (log KML(M) = 4.72-5.10/2.95-3.16, respectively). Based on the above findings, we hypothesized that the unexpectedly low log K values of Zn(2+)-d(pNp) as compared to Zn(2+)-NDP complexes, are possibly due to formation of outer-sphere coordination in the Zn(2+)-d(pNp) complex vs. inner-sphere in the NDP-Zn(2+) complex, in addition to loss of chelation to N7 nitrogen atom in Zn(2+)-d(pNp). Indeed, explicit solvent molecular dynamics simulations of 1 and 3 for 100 ns supported this hypothesis.

Surface-enhanced Raman spectroscopy substrate based on Ag-coated self-assembled polystyrene spheres

NASA Astrophysics Data System (ADS)

Mikac, Lara; Ivanda, Mile; Gotić, Marijan; Janicki, Vesna; Zorc, Hrvoje; Janči, Tibor; Vidaček, Sanja

2017-10-01

The silver (Ag) films were deposited on the monodispersed polystyrene spheres that were drop-coated on hydrophilic glass substrates in order to form a self-assembled 2D monolayer. Thus prepared Ag films over polystyrene nanospheres (AgFONs) were used to record the surface-enhanced Raman scattering (SERS) spectra of rhodamine 6G (R6G) and pyridine (λex = 514.5 nm). AgFONs were prepared by depositing 120, 180 and 240 nm thick Ag layer on the 1000 nm polystyrene spheres and 80, 120, 160 and 200 nm thick Ag layer on the 350 nm spheres as well as on their mixture (350 + 1000 nm). The silver was deposited by electron beam evaporation technique. The best enhancement of the Raman signal for both test molecules was obtained using 180 nm Ag film deposited on the 1000 nm spheres and using 80 nm Ag film deposited on the 350 nm polystyrene spheres. The lowest detectable concentrations of R6G and pyridine were 10-9 mol L-1 and 1.2 × 10-3 mol L-1, respectively. This study has shown that AgFONs could be regarded as good and reproducible SERS substrate for analytical detection of various organic molecules.

Plasmon tsunamis on metallic nanoclusters.

PubMed

Lucas, A A; Sunjic, M

2012-03-14

A model is constructed to describe inelastic scattering events accompanying electron capture by a highly charged ion flying by a metallic nanosphere. The electronic energy liberated by an electron leaving the Fermi level of the metal and dropping into a deep Rydberg state of the ion is used to increase the ion kinetic energy and, simultaneously, to excite multiple surface plasmons around the positively charged hole left behind on the metal sphere. This tsunami-like phenomenon manifests itself as periodic oscillations in the kinetic energy gain spectrum of the ion. The theory developed here extends our previous treatment (Lucas et al 2011 New J. Phys. 13 013034) of the Ar(q+)/C(60) charge exchange system. We provide an analysis of how the individual multipolar surface plasmons of the metallic sphere contribute to the formation of the oscillatory gain spectrum. Gain spectra showing characteristic, tsunami-like oscillations are simulated for Ar(15+) ions capturing one electron in distant collisions with Al and Na nanoclusters.

On the importance of local orbitals using second energy derivatives for d and f electrons

NASA Astrophysics Data System (ADS)

Karsai, Ferenc; Tran, Fabien; Blaha, Peter

2017-11-01

The all-electron linearized augmented plane wave (LAPW) methods are among the most accurate to solve the Kohn-Sham equations of density functional theory for periodic solids. In the LAPW methods, the unit cell is partitioned into spheres surrounding the atoms, inside which the wave functions are expanded into spherical harmonics, and the interstitial region, where the wave functions are expanded in Fourier series. Recently, Michalicek et al. (2013) reported an analysis of the so-called linearization error, which is inherent to the basis functions inside the spheres, and advocated the use of local orbital basis functions involving the second energy derivative of the radial part (HDLO). In the present work, we report the implementation of such basis functions into the WIEN2k code, and discuss in detail the improvement in terms of accuracy. From our tests, which involve atoms from the whole periodic table, it is concluded that for ground-state properties (e.g., equilibrium volume) the use of HDLO is necessary only for atoms with d or f electrons in the valence and large atomic spheres. For unoccupied states which are not too high above the Fermi energy, HDLO systematically improve the band structure, which may be of importance for the calculation of optical properties.

SCF-Xα-SW electron densities with the overlapping sphere approximation

NASA Astrophysics Data System (ADS)

McMaster, Blair N.; Smith, Vedene H., Jr.; Salahub, Dennis R.

Self consistent field-Xα-scattered wave (SCF-Xα-SW) calculations have been performed for a series of eight first and second row homonuclear diatomic molecules using both the touching (TS) and 25 per cent overlapping sphere (OS) versions. The OS deformation density maps exhibit much better quantitative agreement with those from other Xα methods, which do not employ the spherical muffin-tin (MT) potential approximation, than do the TS maps. The OS version thus compensates very effectively for the errors involved in the MT approximation in computing electron densities. A detailed comparison between the TS- and OS-Xα-SW orbitals reveals that the reasons for this improvement are surprisingly specific. The dominant effect of the OS approximation is to increase substantially the electron density near the midpoint of bonding σ orbitals, with a consequent reduction of the density behind the atoms. A similar effect occurs for the bonding π orbitals but is less pronounced. These effects are due to a change in hybridization of the orbitals, with the OS approximation increasing the proportion of the subdominant partial waves and hence changing the shapes of the orbitals. It is this increased orbital polarization which so effectively compensates for the lack of (non-spherically symmetric) polarization components in the MT potential, when overlapping spheres are used.

Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

PubMed Central

Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

2015-01-01

The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field. PMID:26670467

Self-assembly preparation of SiO2@Ni-Al layered double hydroxide composites and their enhanced electrorheological characteristics

NASA Astrophysics Data System (ADS)

Ji, Xuqiang; Zhang, Wenling; Shan, Lei; Tian, Yu; Liu, Jingquan

2015-12-01

The core-shell structured SiO2@Ni-Al layered double hydroxide (LDH) composites were prepared via self-assembly of Ni-Al LDH on the surface of SiO2 spheres. Only coating a layer of ultrathin Ni-Al LDH sheet, the resulting SiO2@Ni-Al LDH composites exhibit significantly enhanced electrorheological (ER) characteristics compared to conventional bare SiO2 spheres. The monodispersed SiO2 spheres with average diameters of 260 nm were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS), while the shell part, Ni-Al LDH sheet was prepared by the hydrothermal procedure. The morphology of the samples was investigated via scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure of the samples was characterized by X-ray diffraction (XRD). The species and distribution of elements in samples were confirmed by X-ray photoelectron spectroscopy (XPS), Energy dispersive analysis of X-ray (EDX) and elemental mapping in STEM. Subsequently, the ER characteristics of the composites dispersed in insulating oil were characterized by a rotational rheometer. The electric field-stimulated rheological performances (yield stress, viscosity, modulus, etc.) were observed under an external electric field, which is different from the Newtonian state in the free electric field.

ESR, spectroscopic, and quantum-chemical studies on the electronic structures of complexes formed by Cu(I) with radicals (in Russian)

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

Gritsan, N.P.; Usov, O.M.; Shokhirev, N.V.

1986-07-01

The optical and ESR spectra have been examined for complexes of Cu(I) with various radicals, which contain various numbers of Cl/sup -/ ions in the central-atom coordination sphere. The spin-Hamiltonian parameters have been determined for all these radical complexes, and the observed ESR spectra have been compared with those calculated with allowance for second-order effects. The observed values for the isotropic and anisotropic components of the HFI constant from the central ion have been used to estimate the contributions from the 4s and 3d/sup 2//sub z/ orbitals of the copper ion to the unpaired-electron MO. Quantum-chemical calculations have been performedmore » by the INDO method on the electronic structures and geometries of complexes formed by CH/sub 2/OH with Cu(I) for various Cl/sup -/ contents in the coordination sphere. The radical is coordinated by the ..pi.. orbital on the carbon atom, and the stabilities of the radical complexes decrease as the number of Cl/sup -/ ions in the coordination sphere increases. A geometry close to planar for the CuCl/sub 4//sup 3 -/ fragment in a complex containing four Cl/sup -/ ions.« less

Hierarchical hollow spheres of Fe2O3 @polyaniline for lithium ion battery anodes.

PubMed

Jeong, Jae-Min; Choi, Bong Gill; Lee, Soon Chang; Lee, Kyoung G; Chang, Sung-Jin; Han, Young-Kyu; Lee, Young Boo; Lee, Hyun Uk; Kwon, Soonjo; Lee, Gaehang; Lee, Chang-Soo; Huh, Yun Suk

2013-11-20

Hierarchical hollow spheres of Fe2 O3 @polyaniline are fabricated by template-free synthesis of iron oxides followed by a post in- and exterior construction. A combination of large surface area with porous structure, fast ion/electron transport, and mechanical integrity renders this material attractive as a lithium-ion anode, showing superior rate capability and cycling performance. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AIE-doped poly(ionic liquid) photonic spheres: a single sphere-based customizable sensing platform for the discrimination of multi-analytes† †Electronic supplementary information (ESI) available: Synthesis and characterization of the AIE luminogen, experimental details, response profiles and results of the multivariate analysis. See DOI: 10.1039/c7sc02409f Click here for additional data file.

PubMed Central

Zhang, Wanlin; Gao, Ning; Cui, Jiecheng; Wang, Chen; Wang, Shiqiang; Zhang, Guanxin; Dong, Xiaobiao

2017-01-01

By simultaneously exploiting the unique properties of ionic liquids and aggregation-induced emission (AIE) luminogens, as well as photonic structures, a novel customizable sensing system for multi-analytes was developed based on a single AIE-doped poly(ionic liquid) photonic sphere. It was found that due to the extraordinary multiple intermolecular interactions involved in the ionic liquid units, one single sphere could differentially interact with broader classes of analytes, thus generating response patterns with remarkable diversity. Moreover, the optical properties of both the AIE luminogen and photonic structure integrated in the poly(ionic liquid) sphere provide multidimensional signal channels for transducing the involved recognition process in a complementary manner and the acquisition of abundant and sufficient sensing information could be easily achieved on only one sphere sensor element. More importantly, the sensing performance of our poly(ionic liquid) photonic sphere is designable and customizable through a simple ion-exchange reaction and target-oriented multi-analyte sensing can be conveniently realized using a selective receptor species, such as counterions, showing great flexibility and extendibility. The power of our single sphere-based customizable sensing system was exemplified by the successful on-demand detection and discrimination of four multi-analyte challenge systems: all 20 natural amino acids, nine important phosphate derivatives, ten metal ions and three pairs of enantiomers. To further demonstrate the potential of our spheres for real-life application, 20 amino acids in human urine and their 26 unprecedented complex mixtures were also discriminated between by the single sphere-based array. PMID:28989662

Preparation of SiO2-Protecting Metallic Fe Nanoparticle/SiO2 Composite Spheres for Biomedical Application

PubMed Central

Hsieh, Pin-Wei; Tseng, Ching-Li; Kuo, Dong-Hau

2015-01-01

Functionalized Fe nanoparticles (NPs) have played an important role in biomedical applications. In this study, metallic Fe NPs were deposited on SiO2 spheres to form a Fe/SiO2 composite. To protect the Fe from oxidation, a thin SiO2 layer was coated on the Fe/SiO2 spheres thereafter. The size and morphology of the SiO2@Fe/SiO2 composite spheres were examined by transmission electron microscopy (TEM). The iron form and its content and magnetic properties were examined by X-ray diffraction (XRD), inductively-coupled plasma mass spectrometry (ICP-MS) and a superconducting quantum interference device (SQUID). The biocompatibility of the SiO2@Fe/SiO2 composite spheres was examined by Cell Counting Kit-8 (CCK-8) and lactate dehydrogenase (LDH) tests. The intracellular distribution of the SiO2@Fe/SiO2 composite spheres was observed using TEM. XRD analysis revealed the formation of metallic iron on the surface of the SiO2 spheres. According to the ICP-MS and SQUID results, using 0.375 M FeCl3·6H2O for Fe NPs synthesis resulted in the highest iron content and magnetization of the SiO2@Fe/SiO2 spheres. Using a dye loading experiment, a slow release of a fluorescence dye from SiO2@Fe/SiO2 composite spheres was confirmed. The SiO2@Fe/SiO2 composite spheres co-cultured with L929 cells exhibit biocompatibility at concentrations <16.25 µg/mL. The TEM images show that the SiO2@Fe/SiO2 composite spheres were uptaken into the cytoplasm and retained in the endosome. The above results demonstrate that the SiO2@Fe/SiO2 composite spheres could be used as a multi-functional agent, such as a magnetic resonance imaging (MRI) contrast agent or drug carriers in biomedical applications.

Effect of pressure on viscosity of liquid Fe-alloys up to 16 GPa

NASA Astrophysics Data System (ADS)

Terasaki, H.; Ohtani, E.; Suzuki, A.; Nishida, K.; Sakamaki, T.; Shindo, S.; Funakoshi, K.

2005-12-01

Viscosity of liquid Fe-alloy is closely related to a convection behavior of the Earth's liquid outer core and also time scale of planetary core formation. In previous studies, viscosity of liquid Fe-S has been measured up to 7 GPa using X-ray radiography falling sphere method [Terasaki et al. 2001]. However, some technical problems, such as chemical reaction between the metal marker sphere and the Fe-alloy sample and insufficient image recording time for less viscous material, have been suggested. In this study, we have measured the viscosity of Fe-S and Fe-C liquids without those problems by using novel techniques combined with in situ X-ray radiography falling sphere method and extended the pressure range to 16 GPa. Falling sphere viscometry was carried out under high pressure and temperature using high speed CCD camera with 1500 ton Kawai-type multi-anvil device at BL04B1, SPring-8 in Japan. Starting compositions of Fe-alloy were Fe78S22 and Fe86C14 which correspond to near eutectic compositions at the experimental pressures. Viscosity marker sphere, which was made of Re or Pt, was coated by alumina in order to prevent the reaction between the sphere and the Fe-alloy sample. Falling sphere images were obtained with recording rate of 50 - 125 frame/second. Viscosity of liquid Fe-S was measured up to 16.1 GPa and 1763 K. Measured viscosity coefficients were in the range of 8.8 - 9.2 mPa-s which indicates that the activation volume of viscous flow is approximately a half of the previous estimations (1.5 cm3/mol). Viscosity of liquid Fe-C was measured up to 5 GPa and 1843 K. Viscosity coefficients are 4.7 - 4.9 mPa-s. Activation volume of Fe-C liquid is estimated to be 0.8 cm3/mol. This pressure dependence is consistent with the result of Lucas (1964) measured at ambient pressure. Consequently, viscosity of Fe-alloy liquids are likely to stay small in the Earth's interior and there is no large difference in viscosity coefficient and activation volume between Fe-S and Fe-C eutectic liquids in the range of measurements.

Radiation belt electron observations following the January 1997 magnetic cloud event

NASA Astrophysics Data System (ADS)

Selesnick, R. S.; Blake, J. B.

Relativistic electrons in the outer radiation belt associated with the January 1997 magnetic cloud event were observed by the HIST instrument on POLAR at kinetic energies from 0.7 to 7 MeV and L shells from 3 to 9. The electron enhancement occurred on a time scale of hours or less throughout the outer radiation belt, except for a more gradual rise in the higher energy electrons at the lower L values indicative of local acceleration and inward radial diffusion. At the higher L values, variations on a time scale of several days following the initial injection on January 10 are consistent with data from geosynchronous orbit and may be an adiabatic response.

Charging of a conducting sphere in a weakly ionized collisional plasma: Temporal dynamics and stationary state

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

Grach, V. S., E-mail: vsgrach@app.sci-nnov.ru; Garasev, M. A.

2015-07-15

We consider the interaction of a isolated conducting sphere with a collisional weakly ionized plasma in an external field. We assume that the plasma consists of two species of ions neglecting of electrons. We take into account charging of the sphere due to sedimentation of plasma ions on it, the field of the sphere charge and the space charge, as well as recombination and molecular diffusion. The nonstationary problem of interaction of the sphere with the surrounding plasma is solved numerically. The temporal dynamics of the sphere charge and plasma perturbations is analyzed, as well as the properties of themore » stationary state. It is shown that the duration of transient period is determined by the recombination time and by the reverse conductivity of ions. The temporal dynamics of the sphere charge and plasma perturbations is determined by the intensity of recombination processes relative to the influence of the space charge field and diffusion. The stationary absolute value of the sphere charge increases linearly with the external electric field, decreases with the relative intensity of recombination processes and increases in the presence of substantial diffusion. The scales of the perturbed region in the plasma are determined by the radius of the sphere, the external field, the effect of diffusion, and the relative intensity of recombination processes. In the limiting case of the absence of molecular diffusion and a strong external field, the properties of the stationary state coincide with those obtained earlier as a result of approximate solution.« less

Identification and onset of inertial modes in the wide-gap spherical Couette system

NASA Astrophysics Data System (ADS)

Barik, A.; Wicht, J.; Triana, S. A.; Hoff, M.

2016-12-01

The spherical Couette system consists of two concentric rotating spheres with a fluid filling the shell in between. The system has been studied for a long time by fluid dynamicists and is ideal for studying flow instabilities due to differential rotation and the interaction of the same with magnetic fields - important for understanding dynamics of planetary and stellar interiors. The system is also a basis for a new generation of dynamo experiments because of its closer geometrical resemblance to real astrophysical objects as compared to past experiments. We simulate this system using the two different pseudo-spectral codes MagIC and XSHELLS. We focus here on a very interesting and general instability in this system - inertial modes. A rotating body of fluid is known to sustain oscillatory waves due to the restoring action of the Coriolis force. In a bounded container, these form a discrete spectrum called inertial modes. These modes have been analytically known for a rotating full sphere for over a century now. In a spherical shell, they cannot be formulated analytically. However, many of these inertial modes are observed in spherical Couette experiments as well as in simulations. Past studies have tried to explain the onset of these modes invoking wave over-reflection or critical layer instabilities on the cylinder tangent to the inner sphere. In this study, we present the inertial modes found in our simulations and try to explain their onset as secondary instabilities due to the destabilization of the fundamental non-axisymmetric instability, forming a triadic resonance with the fundamental instability. We run various simulations varying the rotation rate of the inner sphere, while keeping the rotation rate of the outer sphere constant. We track velocities and induced magnetic field and produce spectrograms similar to those of the experiments. Our results match very well the experimental data from spherical Couette set-ups at BTU Cottbus and the University of Maryland.

Cu-modified carbon spheres/reduced graphene oxide as a high sensitivity of gas sensor for NO2 detection at room temperature

NASA Astrophysics Data System (ADS)

Su, Zhibin; Tan, Li; Yang, Ruiqiang; Zhang, Yu; Tao, Jin; Zhang, Nan; Wen, Fusheng

2018-03-01

Nitrogen dioxide (NO2) as one of the most serious air pollution is harmful to people's health, therefore high-performance gas sensors is critically needed. Here, Cu-modified carbon spheres/reduced graphene oxide (Cu@CS/RGO) composite have been prepared as NO2 gas sensor material. Carbon sphere in the interlayer of RGO can increase the specific surface area of RGO. Copper nanoparticles decorated on the surface of CS can effectively enhance the adsorption activity of RGO as supplier of free electrons. The experimental results showed that its particular structure improved the gas sensitivity of RGO at different NO2 concentrations at room temperature.

Light-scattering efficiency of starch acetate pigments as a function of size and packing density.

PubMed

Penttilä, Antti; Lumme, Kari; Kuutti, Lauri

2006-05-20

We study theoretically the light-scattering efficiency of paper coatings made of starch acetate pigments. For the light-scattering code we use a discrete dipole approximation method. The coating layer is assumed to consists of roughly equal-sized spherical pigments packed either at a packing density of 50% (large cylindrical slabs) or at 37% or 57% (large spheres). Because the scanning electron microscope images of starch acetate samples show either a particulate or a porous structure, we model the coatings in two complementary ways. The material can be either inside the constituent spheres (particulate case) or outside of those (cheeselike, porous medium). For the packing of our spheres we use either a simulated annealing or a dropping code. We can estimate, among other things, that the ideal sphere diameter is in the range 0.25-0.4 microm.

Light-scattering efficiency of starch acetate pigments as a function of size and packing density

NASA Astrophysics Data System (ADS)

Penttilä, Antti; Lumme, Kari; Kuutti, Lauri

2006-05-01

We study theoretically the light-scattering efficiency of paper coatings made of starch acetate pigments. For the light-scattering code we use a discrete dipole approximation method. The coating layer is assumed to consists of roughly equal-sized spherical pigments packed either at a packing density of 50% (large cylindrical slabs) or at 37% or 57% (large spheres). Because the scanning electron microscope images of starch acetate samples show either a particulate or a porous structure, we model the coatings in two complementary ways. The material can be either inside the constituent spheres (particulate case) or outside of those (cheeselike, porous medium). For the packing of our spheres we use either a simulated annealing or a dropping code. We can estimate, among other things, that the ideal sphere diameter is in the range 0.25-0.4 μm.

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

Electron content of the ionosphere and the plasma sphere on the basis of ATS-6-Data, NNSS-data, and ionograms. [Navy Navigation Satellite System

NASA Technical Reports Server (NTRS)

Leitinger, R.; Hartmann, G. K.; Davies, K.

1976-01-01

The reported investigation takes into account data obtained with the aid of the geostationary satellite ATS-6, the satellites of the U.S. navy navigation system (NNSS) at an altitude between 900 and 1200 km, and the satellites ISIS 1 and ISIS 2. The altitude range between ground and ATS-6 is divided into two regions, including the 'ionosphere', involving the region with an upper limit of 2000 km, and the 'plasma sphere', involving the region above an altitude of 2000 km. Data concerning the electron content obtained from different sources are compared, taking into account discrepancies between ionogram-derived values and values computed on the basis of satellite measurements. Attention is also given to the vertical electron content of the ionosphere on the basis of a combination of data obtained with the aid of the ATS-6 and the NNSS.

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

Energetic electrons observed in higher latitude regions of the plasma sheet near the outer radiation belt

NASA Astrophysics Data System (ADS)

Yoshizumi, M.; Shinohara, I.; Nagai, T.; Kanazawa, K.; Mitani, T.; Kasahara, S.; Kazama, Y.; Wang, B. J.; Wang, S. Y.; Tam, S. W. Y.; Higashio, N.; Matsuoka, A.; Asamura, K.; Yokota, S.; Takashima, T.

2017-12-01

The Arase satellite was successfully launched on Dec. 20, 2016, and it has started the regular mission observation since the end of March, 2017. The orbital inclination of Arase is about 31 degree, so that Arase is possible to observe higher L-value plasma sheet close to the plasma sheet boundary. During this summer, the local time of the apogee is located at near the midnight, and Arase observed the plasma sheet just outside of the outer radiation belt as expected. In these observations, we found that energetic electron bursts up to 500 keV frequently appear in the plasma sheet. Possible sources of these energetic electron bursts of a few hundreds keV near thein higher L-value region are (1) directly accelerated from magnetotail reconnection sites and (2) dispersion-less injections. It is interesting to distinguish the acceleration source of them and address each contribution of the energy input to the outer radiation belt for understanding the relation between magnetotail reconnection and the acceleration of MeV electrons in the radiation belts. We will present the initial results on the characteristics of the observed energetic electron bursts by using the wide-range electron distribution measurements from 10 eV to 20 MeV.

Beyond Pluto: The Search for the Edge of the Solar System

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

Funsten, Herb

In July, we finally visited the last major body of our solar system, Pluto. But what lies beyond? The stellar wind from our Sun forms an enormous bubble in interstellar space. This “sphere of our Sun,” or heliosphere, extends far beyond Pluto and forms a protective cocoon that shields us from cosmic radiation. In this talk, we will travel to the edge of the solar system, peer into the structure and dynamics of the outer heliosphere as it interacts with the interstellar medium and anticipate the future of the solar system as it moves through our galactic neighborhood.

Magnetic field variation caused by rotational speed change in a magnetohydrodynamic dynamo.

PubMed

Miyagoshi, Takehiro; Hamano, Yozo

2013-09-20

We have performed numerical magnetohydrodynamic dynamo simulations in a spherical shell with rotational speed or length-of-day (LOD) variation, which is motivated by correlations between geomagnetic field and climatic variations with ice and non-ice ages. The results show that LOD variation leads to magnetic field variation whose amplitude is considerably larger than that of LOD variation. The heat flux at the outer sphere and the zonal flow also change. The mechanism of the magnetic field variation due to LOD variation is also found. The keys are changes of dynamo activity and Joule heating.

Neutron field characterization at the independent spent fuel storage installation of the Trillo nuclear power plant.

PubMed

Campo, Xandra; Méndez, Roberto; Embid, Miguel; Ortego, Alberto; Novo, Manuel; Sanz, Javier

2018-05-01

Neutron fields inside and outside the independent spent fuel storage installation of Trillo Nuclear Power Plant are characterized exhaustively in terms of neutron spectra and ambient dose equivalent, measured by Bonner sphere system and LB6411 monitor. Measurements are consistent with storage casks and building shield characteristics, and also with casks distribution inside the building. Outer values at least five times lower than dose limit for free access area are found. Measurements with LB6411 and spectrometer are consistent with each other. Copyright © 2018 Elsevier Ltd. All rights reserved.

Natural variations in the geomagnetically trapped electron population

NASA Technical Reports Server (NTRS)

Vampola, A. L.

1972-01-01

Temporal variations in the trapped natural electron flux intensities and energy spectra are discussed and demonstrated using recent satellite data. These data are intended to acquaint the space systems engineer with the types of natural variations that may be encountered during a mission and to augment the models of the electron environment currently being used in space system design and orbit selection. An understanding of the temporal variations which may be encountered should prove helpful. Some of the variations demonstrated here which are not widely known include: (1) addition of very energetic electrons to the outer zone during moderate magnetic storms: (2) addition of energetic electrons to the inner zone during major magnetic storms; (3) inversions in the outer zone electron energy spectrum during the decay phase of a storm injection event and (4) occasional formation of multiple maxima in the flux vs altitude profile of moderately energetic electrons.

Estimation of absorbed fraction to the anterior nose from inhaled beta emitters

NASA Astrophysics Data System (ADS)

Moussa, Hanna Moussa

2000-08-01

The main purpose of this research is to introduce a new and more realistic geometry for the anterior nose region (ET1) as an alternative to the one provided in ICRP Publication 66. For a more accurate estimation of electron absorbed fraction (AF) to the nuclei of basal cells in the ET 1 region, the proposed new geometry (frustum of a cone) replaces the cylinder geometry, which was used in ICRP 66. Since the electron absorbed fraction (AF) data in ICRP 66 are calculated based on the nose size for an adult Caucasian male, a second purpose of this research is to investigate how the nose size (different ethnic groups) and nose tissue composition (male, female and adolescent), affects the electron absorbed fraction values. The third aim of this research is to develop a Monte Carlo program to estimate the electron energies that emerge from the surface of spherical dust particles. Given that electrons can be located anywhere between the center and the surface of the sphere, we vary the sphere radius from 0.5 to 50 μm and investigate the effects of self-absorption on the emitted electron energies and absorbed fraction.

Ethanol Gas Detection Using a Yolk-Shell (Core-Shell) α-Fe2O3 Nanospheres as Sensing Material.

PubMed

Wang, LiLi; Lou, Zheng; Deng, Jianan; Zhang, Rui; Zhang, Tong

2015-06-17

Three-dimensional (3D) nanostructures of α-Fe2O3 materials, including both hollow sphere-shaped and yolk-shell (core-shell)-shaped, have been successfully synthesized via an environmentally friendly hydrothermal approach. By expertly adjusting the reaction time, the solid, hollow, and yolk-shell shaped α-Fe2O3 can be selectively synthesized. Yolk-shell α-Fe2O3 nanospheres display outer diameters of 350 nm, and the interstitial hollow spaces layer is intimately sandwiched between the inner and outer shell of α-Fe2O3 nanostructures. The possible growth mechanism of the yolk-shell nanostructure is proposed. The results showed that the well-defined bilayer interface effectively enhanced the sensing performance of the α-Fe2O3 nanostructures (i.e., yolk-shell α-Fe2O3@α-Fe2O3), owing predominantly to the unique nanostructure, thus facilitated the transport rate and augmented the adsorption quantity of the target gas molecule under gas detection.

Inviscid dynamics of a wet foam drop with monodisperse bubble size distribution

NASA Astrophysics Data System (ADS)

McDaniel, J. Gregory; Akhatov, Iskander; Holt, R. Glynn

2002-06-01

Motivated by recent experiments involving the acoustic levitation of foam drops, we develop a model for nonlinear oscillations of a spherical drop composed of monodisperse aqueous foam with void fraction below 0.1. The model conceptually divides a foam drop into many cells, each cell consisting of a spherical volume of liquid with a bubble at its center. By treating the liquid as incompressible and inviscid, a nonlinear equation is obtained for bubble motion due to a pressure applied at the outer radius of the liquid sphere. Upon linearizing this equation and connecting the cells at their outer radii, a wave equation is obtained with a dispersion relation for the sound waves in a bubbly liquid. For the spherical drop, this equation is solved by a normal mode expansion that yields the natural frequencies as functions of standard foam parameters. Numerical examples illustrate how the analysis may be used to extract foam parameters, such as void fraction and bubble radius, from the experimentally measured natural frequencies of a foam drop.

The Hollow Spheres of the Orgueil Meteorite: A Re-Examination

NASA Technical Reports Server (NTRS)

Hoover, Richard B.; Jerman, Gregory; Rossignold-Strick, Maritine

2005-01-01

In 1971, Rossignol-Strick and Barghoorn provided images and a description of a number of spherical hollow microstructures showing well-defined walls in acid macerated extract of the Orgueil CI carbonaceous meteorite. Other forms such as membranes and spiral shaped structures were also reported. The carbon-rich (kerogen) hollow spheres were found to be in a narrowly constrained distribution of sizes (mainly 7 to 10 microns in diameter). Electron microprobe analysis revealed that these spheres contained Carbon, possibly P, N, and K. It was established that these forms could not be attributed to pollen or other recent terrestrial contaminants. It was concluded that they most probably represented organic coatings on globules of glass, olivine or magnetite in the meteorite. However, recent studies of the Orgueil meteorite have been carried out at the NASA/Marshall Space Flight Center with the S-4000 Hitachi Field Emission Scanning Electron Microscope (FESEM). These investigations have revealed the presence of numerous carbon encrusted spherical magnetite platelets and spherical and ovoidal bodies of elemental iron in-situ in freshly fractured interior surfaces of the meteorite. Their size range is also very narrowly constrained (typically approximately 6 to 12 microns) in diameter. High resolution images reveal that these bodies are also encrusted with a thin carbonaceous sheath and are surrounded by short nanofibrils that are shown to be composed of high purity iron by EDAX elemental analysis. We present Secondary and Backscatter Electron FESEM images and associated EDAX elemental analyses and 2D X-ray maps of these forms as we re-examine the hollow spheres of Orgueil and attempt to determine if they are representatives of the same population of indigenous microstructures.

Shewanella oneidensis MR-1 nanowires are outer membrane and periplasmic extensions of the extracellular electron transport components

PubMed Central

Pirbadian, Sahand; Barchinger, Sarah E.; Leung, Kar Man; Byun, Hye Suk; Jangir, Yamini; Bouhenni, Rachida A.; Reed, Samantha B.; Romine, Margaret F.; Saffarini, Daad A.; Shi, Liang; Gorby, Yuri A.; Golbeck, John H.; El-Naggar, Mohamed Y.

2014-01-01

Bacterial nanowires offer an extracellular electron transport (EET) pathway for linking the respiratory chain of bacteria to external surfaces, including oxidized metals in the environment and engineered electrodes in renewable energy devices. Despite the global, environmental, and technological consequences of this biotic–abiotic interaction, the composition, physiological relevance, and electron transport mechanisms of bacterial nanowires remain unclear. We report, to our knowledge, the first in vivo observations of the formation and respiratory impact of nanowires in the model metal-reducing microbe Shewanella oneidensis MR-1. Live fluorescence measurements, immunolabeling, and quantitative gene expression analysis point to S. oneidensis MR-1 nanowires as extensions of the outer membrane and periplasm that include the multiheme cytochromes responsible for EET, rather than pilin-based structures as previously thought. These membrane extensions are associated with outer membrane vesicles, structures ubiquitous in Gram-negative bacteria, and are consistent with bacterial nanowires that mediate long-range EET by the previously proposed multistep redox hopping mechanism. Redox-functionalized membrane and vesicular extensions may represent a general microbial strategy for electron transport and energy distribution. PMID:25143589

Shewanella oneidensis MR-1 nanowires are outer membrane and periplasmic extensions of the extracellular electron transport components.

PubMed

Pirbadian, Sahand; Barchinger, Sarah E; Leung, Kar Man; Byun, Hye Suk; Jangir, Yamini; Bouhenni, Rachida A; Reed, Samantha B; Romine, Margaret F; Saffarini, Daad A; Shi, Liang; Gorby, Yuri A; Golbeck, John H; El-Naggar, Mohamed Y

2014-09-02

Bacterial nanowires offer an extracellular electron transport (EET) pathway for linking the respiratory chain of bacteria to external surfaces, including oxidized metals in the environment and engineered electrodes in renewable energy devices. Despite the global, environmental, and technological consequences of this biotic-abiotic interaction, the composition, physiological relevance, and electron transport mechanisms of bacterial nanowires remain unclear. We report, to our knowledge, the first in vivo observations of the formation and respiratory impact of nanowires in the model metal-reducing microbe Shewanella oneidensis MR-1. Live fluorescence measurements, immunolabeling, and quantitative gene expression analysis point to S. oneidensis MR-1 nanowires as extensions of the outer membrane and periplasm that include the multiheme cytochromes responsible for EET, rather than pilin-based structures as previously thought. These membrane extensions are associated with outer membrane vesicles, structures ubiquitous in Gram-negative bacteria, and are consistent with bacterial nanowires that mediate long-range EET by the previously proposed multistep redox hopping mechanism. Redox-functionalized membrane and vesicular extensions may represent a general microbial strategy for electron transport and energy distribution.

Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine

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

Kim, W.D.; Sherry, A.D.; Kiefer, G.E.

Four Gd{sup 3+} complexes [Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}] with polyazamacrocyclic ligands that contain a pyridine moiety were prepared and examined for possible use as MRI contrast enhancement agents. The authors estimated the number of inner sphere water molecules (q{sub Gd}) for the Gd{sup 3+} complexes from the values of q found for the Tb{sup 3+} and/or Eu{sup 3+} complexes by luminescence lifetime measurements. It was estimated that q{sub Gd} = 3.5, 3.3, 2.4, and 0.2 for Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}, respectively. The inner sphere relaxivities (r{sub 1,inner}) of these tetraazamore » macrocyclic complexes were higher than that of Gd(DOTA){sup {minus}} [i.e. 6.79 for Gd(BP2A){sup +}, 6.21 for Gd(PC2A){sup +}, and 4.60 for Gd(PCTA){sup 0} mM{sup {minus}1}s{sup {minus}1} at 40 MHz and 25{degrees}C], but the normalized relaxivities per q{sub Gd} (1.94, 1.88, and 1.92 mM{sup {minus}1}s{sup {minus}1}, respectively) were comparable to that of Gd(DOTA){sup {minus}}. A quantitative treatment of the NMRD profiles based on Solomon-Bloembergen-Morgan theory, using the NMRD profile of Gd(BPO4A){sup {minus}} to correct for an outer sphere contribution, showed that the complexes exhibit characteristics similar to that of Gd(DOTA){sup {minus}} but with shorter electronic relaxation times. Tissue biodistribution results using radioactive {sup 153}Sm and {sup 159}Gd complexes in rats indicate that the cationic [{sup 153}Sm-(BP2A){sup +} and {sup 153}Sm(PC2A){sup +}] complexes accumulate preferably in the bone tissue while the neutral [{sup 153}Sm-(PCTA){sup 0}] and anionic [{sup 153}Sm(BPO4A){sup {minus}}] complexes appear to have renal clearances similar to those of other low molecular weight contrast agents [i.e. Gd(DTPA){sup 2{minus}} and Gd(DOTA){sup {minus}}].« less

Coupling of Outward Radial Diffusion and Losses at the Magnetopause in the Outer Radiation Belt

NASA Astrophysics Data System (ADS)

Castillo Tibocha, A. M.; Shprits, Y.; Drozdov, A.; Kellerman, A. C.; Aseev, N.

2017-12-01

Sudden dropouts observed in relativistic electron fluxes within the radiation belts are one the most studied and yet poorly understood features of the dynamics of radiation belts. A number of physical processes contributing to these dropout events are triggered by solar wind drivers. Magnetopause losses are one of the most effective mechanisms involved here and usually occur when drifting particles reach the boundary or when inward motion of the magnetopause crosses closed particle drift shells. In both cases, particles are rapidly transported into interplanetary space generating sharp gradients in electron PSD that will promote further outward radial diffusion of particles due to adiabatic transport and the influence of outward ULF waves. Studies suggest that the coupling of these two mechanisms explains nearly all the depletion of MeV electrons observed in the outer region of the radiation belts (L*>5). In this study, we present a simple approach to model electron losses at the magnetopause and outward radial diffusion in the outer radiation belt during geomagnetic storm time. Measured upstream solar wind parameters were used to calculate the radial distance of the subsolar point as proposed by Shue et al. (1997), which was defined as the radial extent of our assumed dipole field configuration. Radial diffusion was modelled using the empirical Kp-dependent DLL [Brautigam and Albert, JGR 2000] diffusion coefficient, which is included in the 3D Versatile Electron Radiation Belt (VERB) code. Simulations of geomagnetic storms were performed in order to evaluate the effects of the integrated mechanisms and the results were compared with Van Allen probe satellite data. Our simulation results reproduce well the observed loss at the magnetopause and electron depletion in the outer radiation belt.

Morphology conserving aminopropyl functionalization of hollow silica nanospheres in toluene

NASA Astrophysics Data System (ADS)

Dobó, Dorina G.; Berkesi, Dániel; Kukovecz, Ákos

2017-07-01

Inorganic nanostructures containing cavities of monodisperse diameter distribution find applications in e.g. catalysis, adsorption and drug delivery. One of their possible synthesis routes is the template assisted core-shell synthesis. We synthesized hollow silica spheres around polystyrene cores by the sol-gel method. The polystyrene template was removed by heat treatment leaving behind a hollow spherical shell structure. The surface of the spheres was then modified by adding aminopropyl groups. Here we present the first experimental evidence that toluene is a suitable alternative functionalization medium for the resulting thin shells, and report the comprehensive characterization of the amino-functionalized hollow silica spheres based on scanning electron microscopy, transmission electron microscopy, N2 adsorption, FT-IR spectroscopy, Raman spectroscopy and electrokinetic potential measurement. Both the presence of the amino groups and the preservation of the hollow spherical morphology were unambiguously proven. The introduction of the amine functionality adds amphoteric character to the shell as shown by the zeta potential vs. pH function. Unlike pristine silica particles, amino-functionalized nanosphere aqueous sols can be stable at both acidic and basic conditions.

Synthesis, self-assembly, and properties of Mn doped ZnO nanoparticles.

PubMed

Barick, K C; Bahadur, D

2007-06-01

We report here a novel process to prepare Mn doped ZnO nanoparticles by a soft chemical route at low temperature. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and manganese acetate tetrahydrate heated under reflux to 160-175 degrees C using diethylene glycol as a solvent. X-ray diffraction analysis reveals that the Mn doped ZnO crystallizes in a wurtzite structure with crystal size of 15-25 nm. These nano size crystallites of Mn doped ZnO self-organize into polydisperse spheres in size ranging from 100-400 nm. Transmission Electron Microscopy image also shows that each sphere is made up of numerous nanocrystals of average diameter 15-25 nm. By means of X-ray photoelectron spectroscopy and electron spin resonance spectroscopy, we determined the valence state of Mn ions as 2+. These nanoparticles were found to be ferromagnetic at room temperature. Monodisperse porous spheres (approximately 250 nm) were obtained by size selective separation technique and then self-assembled in a closed pack periodic array through sedimentation with slow solvent evaporation, which gives strong opalescence in visible region.

Infiltrating sulfur into a highly porous carbon sphere as cathode material for lithium–sulfur batteries

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

Zhao, Xiaohui; Kim, Dul-Sun; Ahn, Hyo-Jun

2014-10-15

Highlights: • A highly porous carbon (HPC) with regular spherical morphology was synthesized. • Sulfur/HPC composites were prepared by melt–diffusion method. • Sulfur/HPC composites showed improved cyclablity and long-term cycle life. - Abstract: Sulfur composite material with a highly porous carbon sphere as the conducting container was prepared. The highly porous carbon sphere was easily synthesized with resorcinol–formaldehyde precursor as the carbon source. The morphology of the carbon was observed with field emission scanning electron microscope and transmission electron microscope, which showed a well-defined spherical shape. Brunauer–Emmett–Teller analysis indicated that it possesses a high specific surface area of 1563 m{supmore » 2} g{sup −1} and a total pore volume of 2.66 cm{sup 3} g{sup −1} with a bimodal pore size distribution, which allow high sulfur loading and easy transportation of lithium ions. Sulfur carbon composites with varied sulfur contents were prepared by melt–diffusion method and lithium sulfur cells with the sulfur composites showed improved cyclablity and long-term cycle life.« less

Rapid acceleration of outer radiation belt electrons associated with solar wind pressure pulse: Simulation study with Arase and Van Allen Probe observations

NASA Astrophysics Data System (ADS)

Hayashi, M.; Yoshizumi, M.; Saito, S.; Matsumoto, Y.; Kurita, S.; Teramoto, M.; Hori, T.; Matsuda, S.; Shoji, M.; Machida, S.; Amano, T.; Seki, K.; Higashio, N.; Mitani, T.; Takashima, T.; Kasahara, Y.; Kasaba, Y.; Yagitani, S.; Ishisaka, K.; Tsuchiya, F.; Kumamoto, A.; Matsuoka, A.; Shinohara, I.; Blake, J. B.; Fennell, J. F.; Claudepierre, S. G.

2017-12-01

Relativistic electron fluxes of the outer radiation belt rapidly change in response to solar wind variations. One of the shortest acceleration processes of electrons in the outer radiation belt is wave-particle interactions between drifting electrons and fast-mode waves induced by compression of the dayside magnetopause caused by interplanetary shocks. In order to investigate this process by a solar wind pressure pulse, we perform a code-coupling simulation using the GEMSIS-RB test particle simulation (Saito et al., 2010) and the GEMSIS-GM global MHD magnetosphere simulation (Matsumoto et al., 2010). As a case study, an interplanetary pressure pulse with the enhancement of 5 nPa is used as the up-stream condition. In the magnetosphere, the fast mode waves with the azimuthal electric field ( negative 𝐸𝜙 : |𝐸&;#120601;| 10 mV/m, azimuthal mode number : m ≤ 2) propagates from the dayside to nightside, interacting with electrons. From the simulation results, we derived effective acceleration model and condition : The electrons whose drift velocities vd ≥ (π/2)Vfast are accelerated efficiently. On December 20, 2016, the Arase (ERG) satellite was launched , allowing more accurate multi-point simultaneous observation with other satellites. We will compare our simulation results with observations from Arase and Van Allen Probes, and investigate the acceleration condition of relativistic electrons associated with storm sudden commencement (SSC).

Donor states in inverse opals

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

Mahan, G. D.

We calculate the binding energy of an electron bound to a donor in a semiconductor inverse opal. Inverse opals have two kinds of cavities, which we call octahedral and tetrahedral, according to their group symmetry. We put the donor in the center of each of these two cavities and obtain the binding energy. The binding energies become very large when the inverse opal is made from templates with small spheres. For spheres less than 50 nm in diameter, the donor binding can increase to several times its unconfined value. Then electrons become tightly bound to the donor and are unlikelymore » to be thermally activated to the semiconductor conduction band. This conclusion suggests that inverse opals will be poor conductors.« less

The structure of K3C60 and the mechanism of superconductivity.

PubMed Central

Pauling, L

1991-01-01

Analysis of the interatomic distances in the superconducting substance K3C60 indicates that each of the K atoms in tetrahedral interstices between C60 spheres accepts three electrons from C60, thus becoming quadricovalent; its four bonds resonate among the 24 adjacent carbon atoms to give a strong framework in which the negative charges are localized on these K atoms. The electric current is carried by the motion of positive charges (holes) through the network of C60 spheres and the K atoms in octahedral holes. Superconductivity is favored by the localization of the negative charges on the tetrahedral K atoms and their noninvolvement in valence-bond resonance, decreasing the rate of mutual extinction of electrons and holes. PMID:11607222

Structure factor and radial distribution function of some liquid lanthanides using charged hard sphere

NASA Astrophysics Data System (ADS)

Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

2017-05-01

The structure factor S(q) and radial distribution function g(r) play vital role to study the various structural properties like electronic, dynamic, magnetic etc. The present paper deals with the structural studies of foresaid properties using our newly constructed parameter free model potential with the Charged Hard Sphere (CHS) approximation. The local field correction due to Sarkar et al. is used to incorporate exchange and correlation among the conduction electrons in dielectric screening. Here we report the S(q) and g(r) for some liquid lanthanides viz: La, Ce, Pr, Nd and Eu. Present computed results are compared with the available experimental data. Lastly we found that our parameter free model potential successfully explains the structural propertiesof4fliquidlanthanides.

Physical mechanism causing rapid changes in ultrarelativistic electron pitch angle distributions right after a shock arrival: Evaluation of an electron dropout event: Drift Shell Splitting on the Dayside

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

Zhang, X. -J.; Li, W.; Thorne, R. M.

Three mechanisms have been proposed to explain relativistic electron flux depletions (dropouts) in the Earth's outer radiation belt during storm times: adiabatic expansion of electron drift shells due to a decrease in magnetic field strength, magnetopause shadowing and subsequent outward radial diffusion, and precipitation into the atmosphere (driven by EMIC wave scattering). Which mechanism predominates in causing electron dropouts commonly observed in the outer radiation belt is still debatable. In the present study, we evaluate the physical mechanism that may be primarily responsible for causing the sudden change in relativistic electron pitch angle distributions during a dropout event observed bymore » Van Allen Probes during the main phase of the 27 February 2014 storm. During this event, the phase space density of ultrarelativistic (>1MeV) electrons was depleted by more than 1 order of magnitude over the entire radial extent of the outer radiation belt (3 < L* < 5) in less than 6 h after the passage of an interplanetary shock. We model the electron pitch angle distribution under a compressed magnetic field topology based on actual solar wind conditions. Although these ultrarelativistic electrons exhibit highly anisotropic (peaked in 90°), energy-dependent pitch angle distributions, which appear to be associated with the typical EMIC wave scattering, comparison of the modeled electron distribution to electron measurements indicates that drift shell splitting is responsible for this rapid change in electron pitch angle distributions. This further indicates that magnetopause loss is the predominant cause of the electron dropout right after the shock arrival.« less

Physical mechanism causing rapid changes in ultrarelativistic electron pitch angle distributions right after a shock arrival: Evaluation of an electron dropout event: Drift Shell Splitting on the Dayside

DOE PAGES

Zhang, X. -J.; Li, W.; Thorne, R. M.; ...

2016-08-13

Three mechanisms have been proposed to explain relativistic electron flux depletions (dropouts) in the Earth's outer radiation belt during storm times: adiabatic expansion of electron drift shells due to a decrease in magnetic field strength, magnetopause shadowing and subsequent outward radial diffusion, and precipitation into the atmosphere (driven by EMIC wave scattering). Which mechanism predominates in causing electron dropouts commonly observed in the outer radiation belt is still debatable. In the present study, we evaluate the physical mechanism that may be primarily responsible for causing the sudden change in relativistic electron pitch angle distributions during a dropout event observed bymore » Van Allen Probes during the main phase of the 27 February 2014 storm. During this event, the phase space density of ultrarelativistic (>1MeV) electrons was depleted by more than 1 order of magnitude over the entire radial extent of the outer radiation belt (3 < L* < 5) in less than 6 h after the passage of an interplanetary shock. We model the electron pitch angle distribution under a compressed magnetic field topology based on actual solar wind conditions. Although these ultrarelativistic electrons exhibit highly anisotropic (peaked in 90°), energy-dependent pitch angle distributions, which appear to be associated with the typical EMIC wave scattering, comparison of the modeled electron distribution to electron measurements indicates that drift shell splitting is responsible for this rapid change in electron pitch angle distributions. This further indicates that magnetopause loss is the predominant cause of the electron dropout right after the shock arrival.« less

Observational constraints on relativistic electron dynamics: temporal evolution of electron spectra and flux isotropization

NASA Astrophysics Data System (ADS)

Kanekal, S. G.; Selesnick, R. S.; Baker, D. N.; Blake, J. B.

2007-05-01

Models of energization of electrons in the Earth's outer radiation belts invoke two classes of processes, radial transport and in-situ wave-particle interactions. Temporal evolution of electron spectra and flux isotropization during energization events provide useful observational constraints on models of electron energization. Events dominated by radial diffusion result in pancake type pitch angle distributions whereas some in-situ wave-particle energization mechanisms include pitch angle scattering leading to rapid flux isotropization. We present a survey of flux isotrpization time scales and electron spectra during relativstic electron enhancement events. We will use data collected by detectors onboard SAMPEX in low earth orbit and Polar which measures electron fluxes at higher altitude to measure flux isotropization. Electron spectra are obtained by pulse height analyzed data from the PET detector onboard SAMPEX.SAMPEX measurements cover the entire outer zone for more than a decade from mid 1992 to mid 2004 and Polar covers the time period from mid 1996 to the present.

Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

PubMed

Zhang, Pan; Ni, Shao-Fei; Dang, Li

2016-09-20

The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ATR-FTIR Spectroscopic Evidence for Biomolecular Phosphorus and Carboxyl Groups Facilitating Bacterial Adhesion to Iron Oxides

PubMed Central

Parikh, Sanjai J.; Mukome, Fungai N.D.; Zhang, Xiaoming

2014-01-01

Attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to probe the binding of bacteria to hematite (α-Fe2O3) and goethite (α-FeOOH). In situ ATR-FTIR experiments with bacteria (Pseudomonas putida, P. aeruginosa, Escherichia coli), mixed amino acids, polypeptide extracts, deoxyribonucleic acid (DNA), and a suite of model compounds were conducted. These compounds represent carboxyl, catecholate, amide, and phosphate groups present in siderophores, amino acids, polysaccharides, phospholipids, and DNA. Due in part to the ubiquitous presence of carboxyl groups in biomolecules, numerous IR peaks corresponding to outer-sphere or unbound (1400 cm−1) and inner-sphere (1310-1320 cm−1) coordinated carboxyl groups are noted following reaction of bacteria and biomolecules with α-Fe2O3 and α-FeOOH. However, the data also reveal that the presence of low-level amounts (i.e., 0.45-0.79%) of biomolecular phosphorous groups result in strong IR bands at ~1043 cm−1, corresponding to inner-sphere Fe-O-P bonds, underscoring the importance of bacteria associated P-containing groups in biomolecule and cell adhesion. Spectral comparisons also reveal slightly greater P-O-Fe contributions for bacteria (Pseudomonad, E. coli) deposited on α-FeOOH, as compared to α-Fe2O3. This data demonstrates that slight differences in bacterial adhesion to Fe oxides can be attributed to bacterial species and Fe-oxide minerals. However, more importantly, the strong binding affinity of phosphate in all bacteria samples to both Fe-oxides results in the formation of inner-sphere Fe-O-P bonds, signifying the critical role of biomolecular P in the initiation of bacterial adhesion. PMID:24859052

Prediction of high-energy radiation belt electron fluxes using a combined VERB-NARMAX model

NASA Astrophysics Data System (ADS)

Pakhotin, I. P.; Balikhin, M. A.; Shprits, Y.; Subbotin, D.; Boynton, R.

2013-12-01

This study is concerned with the modelling and forecasting of energetic electron fluxes that endanger satellites in space. By combining data-driven predictions from the NARMAX methodology with the physics-based VERB code, it becomes possible to predict electron fluxes with a high level of accuracy and across a radial distance from inside the local acceleration region to out beyond geosynchronous orbit. The model coupling also makes is possible to avoid accounting for seed electron variations at the outer boundary. Conversely, combining a convection code with the VERB and NARMAX models has the potential to provide even greater accuracy in forecasting that is not limited to geostationary orbit but makes predictions across the entire outer radiation belt region.

Radiation belt seed population and its association with the relativistic electron dynamics: A statistical study: Radiation Belt Seed Population

DOE PAGES

Tang, C. L.; Wang, Y. X.; Ni, B.; ...

2017-05-19

Using the Van Allen Probes data, we study the radiation belt seed population and it associated with the relativistic electron dynamics during 74 geomagnetic storm events. Based on the flux changes of 1 MeV electrons before and after the storm peak, these storm events are divided into two groups of “non-preconditioned” and “preconditioned”. The statistical study shows that the storm intensity is of significant importance for the distribution of the seed population (336 keV electrons) in the outer radiation belt. However, substorm intensity can also be important to the evolution of the seed population for some geomagnetic storm events. Formore » non-preconditioned storm events, the correlation between the peak fluxes and their L-shell locations of the seed population and relativistic electrons (592 keV, 1.0 MeV, 1.8 MeV, and 2.1 MeV) is consistent with the energy-dependent dynamic processes in the outer radiation belt. For preconditioned storm events, the correlation between the features of the seed population and relativistic electrons is not fully consistent with the energy-dependent processes. It is suggested that the good correlation between the radiation belt seed population and ≤1.0 MeV electrons contributes to the prediction of the evolution of ≤1.0 MeV electrons in the Earth’s outer radiation belt during periods of geomagnetic storms.« less

Radiation belt seed population and its association with the relativistic electron dynamics: A statistical study: Radiation Belt Seed Population

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

Tang, C. L.; Wang, Y. X.; Ni, B.

Using the Van Allen Probes data, we study the radiation belt seed population and it associated with the relativistic electron dynamics during 74 geomagnetic storm events. Based on the flux changes of 1 MeV electrons before and after the storm peak, these storm events are divided into two groups of “non-preconditioned” and “preconditioned”. The statistical study shows that the storm intensity is of significant importance for the distribution of the seed population (336 keV electrons) in the outer radiation belt. However, substorm intensity can also be important to the evolution of the seed population for some geomagnetic storm events. Formore » non-preconditioned storm events, the correlation between the peak fluxes and their L-shell locations of the seed population and relativistic electrons (592 keV, 1.0 MeV, 1.8 MeV, and 2.1 MeV) is consistent with the energy-dependent dynamic processes in the outer radiation belt. For preconditioned storm events, the correlation between the features of the seed population and relativistic electrons is not fully consistent with the energy-dependent processes. It is suggested that the good correlation between the radiation belt seed population and ≤1.0 MeV electrons contributes to the prediction of the evolution of ≤1.0 MeV electrons in the Earth’s outer radiation belt during periods of geomagnetic storms.« less

Inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

NASA Astrophysics Data System (ADS)

Ridley, Moira K.; Hiemstra, Tjisse; van Riemsdijk, Willem H.; Machesky, Michael L.

2009-04-01

Acid-base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multi-component mineral-aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488-508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca 2+ and Sr 2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 1 1 0 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Předota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Bénézeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties. Langmuir20, 4954-4969]. Our CD modeling results are consistent with these adsorbed configurations provided adsorbed cation charge is allowed to be distributed between the surface (0-plane) and Stern plane (1-plane). Additionally, a complete description of our titration data required inclusion of outer-sphere binding, principally for Cl - which was common to all solutions, but also for Rb + and K +. These outer-sphere species were treated as point charges positioned at the Stern layer, and hence determined the Stern layer capacitance value. The modeling results demonstrate that a multi-component suite of experimental data can be successfully rationalized within a CD and MUSIC model using a Stern-based description of the EDL. Furthermore, the fitted CD values of the various inner-sphere complexes of the mono- and divalent ions can be linked to the microscopic structure of the surface complexes and other data found by spectroscopy as well as molecular dynamics (MD). For the Na + ion, the fitted CD value points to the presence of bidenate inner-sphere complexation as suggested by a recent MD study. Moreover, its MD dominance quantitatively agrees with the CD model prediction. For Rb +, the presence of a tetradentate complex, as found by spectroscopy, agreed well with the fitted CD and its predicted presence was quantitatively in very good agreement with the amount found by spectroscopy.

inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

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

Ridley, Mora K.; Hiemstra, T; Van Riemsdijk, Willem H.

Acid base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multicomponent mineral aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise,more » molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488 508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 110 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Pr edota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Be ne zeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile water interface: linking molecular and macroscopic properties. Langmuir 20, 4954 4969]. Our CD modeling results are consistent with these adsorbed configurations provided adsorbed cation charge is allowed to be distributed between the surface (0-plane) and Stern plane (1-plane). Additionally, a complete description of our titration data required inclusion of outer-sphere binding, principally for Cl which was common to all solutions, but also for Rb+ and K+. These outer-sphere species were treated as point charges positioned at the Stern layer, and hence determined the Stern layer capacitance value. The modeling results demonstrate that a multi-component suite of experimental data can be successfully rationalized within a CD and MUSIC model using a Stern-based description of the EDL. Furthermore, the fitted CD values of the various inner-sphere complexes of the mono- and divalent ions can be linked to the microscopic structure of the surface complexes and other data found by spectroscopy as well as molecular dynamics (MD). For the Na+ ion, the fitted CD value points to the presence of bidenate inner-sphere complexation as suggested by a recent MD study. Moreover, its MD dominance quantitatively agrees with the CD model prediction. For Rb+, the presence of a tetradentate complex, as found by spectroscopy, agreed well with the fitted CD and its predicted presence was quantitatively in very good agreement with the amount found by spectroscopy.« less

Nano-micro carbon spheres anchored on porous carbon derived from dual-biomass as high rate performance supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Liu, Shaobo; Zhao, Yang; Zhang, Baihui; Xia, Hui; Zhou, Jianfei; Xie, Wenke; Li, Hongjian

2018-03-01

Hierarchical nano-micro carbon spheres@rice straw-derived porous carbon composites are successfully synthesized by the in situ decoration of the porous carbon with carbon spheres from glucose under the assistance of cetyltrimethyl ammonium bromide micelles and further activated by KOH. The scanning electron microscope images clearly show the carbon spheres disperse homogeneously and orderly onto the surface and in the inner macropores of the porous carbon. The diameter of the carbon spheres varies from 475 nm to 1.6 μm, which can be easily controlled by introducing extra inducing agent. The optimal composites exhibit a large specific surface area (1122 m2 g-1), rich content of oxygen (14.2 wt %), and tunable hierarchical porous structure. When used as supercapacitor electrodes, the novel composites with abundant fruits present a high specific capacitance of 337 F g-1 at 1 A g-1, excellent rate retention of 83% from 1 to 20 A g-1 and a good cycling stability with 96% capacitance retention after 10000 cycles. In this strategy, the thought of shared ion-buffering reservoirs is proposed and the mutual promotion effects between the carbon spheres and porous carbon in the composites are also practically demonstrated to contribute the enhanced electrochemical performances.

Sugar apple-shaped TiO2 hierarchical spheres for highly efficient dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Lei, Bing-Xin; Zeng, Li-Li; Zhang, Ping; Qiao, He-Kang; Sun, Zhen-Fan

2014-05-01

The sugar apple-shaped TiO2 hierarchical spheres are prepared by a facile hydrothermal method using polyethylene glycol 600 as stabilized reagent, (NH4)2TiF6 and urea as starting materials at 180 °C. The characterizations show that the TiO2 hierarchical sphere has well-defined pyramid-shaped crystal facets. The as-prepared TiO2 hierarchical spheres are crystalline of the anatase phase, with a diameter of about 2-4 μm and a surface area of 36.846 m2 g-1. The optical investigation evidences that the sugar apple-shaped TiO2 hierarchical sphere film exhibits a prominent light scattering effect at a wavelength range of 600-800 nm due to the unique hierarchical morphology. Furthermore, the sugar apple-shaped TiO2 hierarchical spheres are deposited as the scattering layer to balance the dye adsorption and light scattering effect in DSSCs and a 7.20% solar energy conversion efficiency is demonstrated, indicating an improvement compared with the P25 cell (6.68%). Based on the optical and electrochemical investigations, the high conversion efficiency is mainly due to the effective suppression of the back reaction of the injected electron with the I3- in the electrolyte and excellent light scattering ability.

Recombinant Reflectin-Based Optical Materials

DTIC Science & Technology

2012-01-01

sili- con substrates were placed in a sealed plastic box. The RH was controlled using a Dydra electronic cigar humidifier and monitored using a Fisher...diffraction gratings to generate diffraction patterns. Nano-spheres and la- mellar microstructures of refCBA samples were observed by scanning electron ...samples were observed by scanning electron microscopy and atomic force microscopy. Despite the reduced complexity of the refCBA protein compared to natural

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.

Electron beam device

DOEpatents

Beckner, E.H.; Clauser, M.J.

1975-08-12

This patent pertains to an electron beam device in which a hollow target is symmetrically irradiated by a high energy, pulsed electron beam about its periphery and wherein the outer portion of the target has a thickness slightly greater than required to absorb the electron beam pulse energy. (auth)

The link between a negative high resolution resist contrast/developer performance and the Flory-Huggins parameter estimated from the Hansen solubility sphere

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

StCaire, Lorri; Olynick, Deirdre L.; Chao, Weilun L.

We have implemented a technique to identify candidate polymer solvents for spinning, developing, and rinsing for a high resolution, negative electron beam resist hexa-methyl acetoxy calix(6)arene to elicit the optimum pattern development performance. Using the three dimensional Hansen solubility parameters for over 40 solvents, we have constructed a Hansen solubility sphere. From this sphere, we have estimated the Flory Huggins interaction parameter for solvents with hexa-methyl acetoxy calix(6)arene and found a correlation between resist development contrast and the Flory-Huggins parameter. This provides new insights into the development behavior of resist materials which are necessary for obtaining the ultimate lithographic resolution.

Temperature-dependent charge transport mechanisms in carbon sphere/polyaniline composite

NASA Astrophysics Data System (ADS)

Nieves, Cesar A.; Martinez, Luis M.; Meléndez, Anamaris; Ortiz, Margarita; Ramos, Idalia; Pinto, Nicholas J.; Zimbovskaya, Natalya

2017-12-01

Charge transport in the temperature range 80 K < T < 300 K was studied in a composite of carbon spheres (CS), prepared via hydrothermal carbonization of sucrose, and the conducting polymer polyaniline (PANi). PANi was synthesized via the oxidative polymerization of aniline with ammonium peroxydisulfate (APS) in acidic media. The CS/PANi composite was prepared by coating the spheres with a thin polyaniline (PANi) film doped with hydrochloric acid (HCl) in situ during the polymerization process. Temperature dependent conductivity measurements show that three dimensional variable range hopping of electrons between polymeric chains in PANi-filled gaps between CS is the predominant transport mechanism through CS/PANi composites. The high conductivity of the CS/PANi composite makes the material attractive for the fabrication of devices and sensors.

A New 3D Multi-fluid Dust Model: A Study of the Effects of Activity and Nucleus Rotation on Dust Grain Behavior at Comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Shou, Y.; Combi, M.; Toth, G.; Tenishev, V.; Fougere, N.; Jia, X.; Rubin, M.; Huang, Z.; Hansen, K.; Gombosi, T.

2017-11-01

Improving our capability to interpret observations of cometary dust is necessary to deepen our understanding of the role of dust in the formation of comets and in altering the cometary environments. Models including dust grains are in demand to interpret observations and test hypotheses. Several existing models have taken into account the gas-dust interaction, varying sizes of dust grains and the cometary gravitational force. In this work, we develop a multi-fluid dust model based on the BATS-R-US code. This model not only incorporates key features of previous dust models, but also has the capability of simulating time-dependent phenomena. Since the model is run in the rotating comet reference frame, the centrifugal and Coriolis forces are included. The boundary conditions on the nucleus surface can be set according to the distribution of activity and the solar illumination. The Sun revolves around the comet in this frame. A newly developed numerical mesh is also used to resolve the real-shaped nucleus in the center and to facilitate prescription of the outer boundary conditions that accommodate the rotating frame. The inner part of the mesh is a box composed of Cartesian cells and the outer surface is a smooth sphere, with stretched cells filled in between the box and the sphere. Our model achieved comparable results to the Direct Simulation Monte Carlo method and the Rosetta/OSIRIS observations. It is also applied to study the effects of the rotating nucleus and the cometary activity and offers interpretations of some dust observations of comet 67P/Churyumov-Gerasimenko.

A new 3D multi-fluid dust model: a study of the effects of activity and nucleus rotation on the dust grains' behavior in the cometary environment

NASA Astrophysics Data System (ADS)

Shou, Y.; Combi, M. R.; Toth, G.; Fougere, N.; Tenishev, V.; Huang, Z.; Jia, X.; Hansen, K. C.; Gombosi, T. I.; Bieler, A. M.; Rubin, M.

2016-12-01

Cometary dust observations may deepen our understanding of the role of dust in the formation of comets and in altering the cometary environment. Models including dust grains are in demand to interpret observations and test hypotheses. Several existing models have taken into account the gas-dust interaction, varying sizes of dust grains and the cometary gravitational force. In this work, we develop a multi-fluid dust model based on BATS-R-US in the University of Michigan's Space Weather Modeling Framework (SWMF). This model not only incorporates key features of previous dust models, but also has the capability of simulating time-dependent phenomena. Since the model is running in the rotating comet reference frame with a real shaped nucleus in the computational domain, the fictitious centrifugal and Coriolis forces are included. The boundary condition on the nucleus surface can be set according to the distribution of activity and the solar illumination. The Sun, which drives sublimation and the radiation pressure force, revolves around the comet in this frame. A newly developed numerical mesh is also used to resolve the real shaped nucleus in the center and to facilitate prescription of the outer boundary conditions that accommodate the rotating frame. The inner part of the grid is a box composed of Cartesian cells and the outer surface is a smooth sphere, with stretched cells filled in between the box and the sphere. The effects of the rotating nucleus and the activity region on the surface are discussed and preliminary results are presented. This work has been partially supported by grant NNX14AG84G from the NASA Planetary Atmospheres Program, and US Rosetta contracts JPL #1266313, JPL #1266314 and JPL #1286489.

Scanning electron microscopy of echinoid podia.

PubMed

Florey, E; Cahill, M A

1982-01-01

Tube feet of the sea urchin Strongylocentrotus franciscanus were studied with the scanning electron microscope (SEM). By use of fractured preparations it was possible to obtain views of all components of the layered tube-foot wall. The outer epithelium was found to bear tufts of cilia possibly belonging to sensory cells. The nerve plexus was clearly revealed as being composed of bundles of varicose axons. The basal lamina, which covers the outer and inner surfaces of the connective tissue layer, was found to be a mechanically resistant and elastic membrane. The connective tissue appears as dense bundles of (collagen) fibers. The luminal epithelium (coelothelium) is a single layer of flagellated collar cells. There is no indication that the muscle fibers, which insert on the inner basal lamina of the connective tissue layer are innervated by axons from the basi-epithelial nerve plexus. The results agree with previous conclusions concerning tube-foot structure based on transmission electron microscopy, and provide additional information, particularly with regard to the outer and inner epithelia.

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

Tunable porosities and shapes of fullerene-like spheres.

PubMed

Dielmann, Fabian; Fleischmann, Matthias; Heindl, Claudia; Peresypkina, Eugenia V; Virovets, Alexander V; Gschwind, Ruth M; Scheer, Manfred

2015-04-13

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 Cu(I) 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. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Sorption properties of Th(IV) on the raw diatomite--effects of contact time, pH, ionic strength and temperature.

PubMed

Sheng, Guodong; Hu, Jun; Wang, Xiangke

2008-10-01

Diatomite has a number of unique physicochemical properties and has diversified industrial uses. Natural diatomite has been tested as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that sorption of Th(IV) is strongly dependent on ionic strength at pH<3, and is independent of ionic strength at pH>3. Outer-sphere complexation or ion exchange may be the main sorption mechanism of Th(IV) to diatomite at low pH values, whereas the sorption of Th(IV) at pH>3 is mainly dominated by inner-sphere complexation or precipitation. The competition for Th(IV) between aqueous or surface adsorbed anions (e.g., herein ClO(4)(-), NO(3)(-) and Cl(-)) and surface functional groups of diatomite is important for Th(IV) sorption. The thermodynamic data (DeltaH(0), DeltaS(0), DeltaG(0)) are calculated from the temperature-dependent sorption isotherms. The results suggest that sorption process of Th(IV) on diatomite is spontaneous and endothermic.

Carbonaceous structures in the Tissint Martian Meteorite: evidence of a biogenetic origin

NASA Astrophysics Data System (ADS)

Wallis, Jamie; Wickramasinghe, N. C.; Wallis, Daryl H.; Miyake, Nori; Wallis, M. K.; Hoover, Richard B.

2015-09-01

We report for the first time in situ observations of 5-50μm spherical carbonaceous structures in the Tissint Martian meteorite comprising of pyrite (FeS2) cores and carbonaceous outer coatings. The structures are characterized as smooth immiscible spheres with curved boundaries occasionally following the contours of the pyrite inclusion. The structures bear striking resemblance to similar-sized immiscible carbonaceous spheres found in hydrothermal calcite vein deposits in the Mullaghwornia Quarry in central Ireland. Similar structures have been reported in Proterozoic and Ordovician sandstones from Canada as well as in a variety of astronomical sources including carbonaceous chondrites, chondritic IDPs and primitive chondritic meteorites. SEM and X-Ray elemental mapping confirmed the presence of organic carbon filling the crack and cleavage space in the pyroxene substrate, with further evidence of pyrite acting as an attractive substrate for the collection of organic matter. The detection of precipitated carbon collecting around pyrite grains is at variance with an igneous origin as proposed for the reduced organic component in Tissint, and is more consistent with a biogenetic origin.

Investigation of mechanism and critical parameters for removal of arsenic from water using Zr-TiO2 composite.

PubMed

Anđelković, I; Amaizah, N R R; Marković, S B; Stanković, D; Marković, M; Kuzmanović, D; Roglić, G

2017-09-01

Using the microwave-hydrothermal method for the synthesis of composite, high surface density of hydroxyl groups, as an active adsorption sites for arsenic, was obtained. Adsorption mechanisms of As(III) and As(V) onto zirconium-doped titanium dioxide (Zr-TiO 2 ) were investigated and proposed using macroscopic and microscopic methods. Obtained results are suggesting inner-sphere and outer-sphere adsorption mechanisms for As(III) and As(V), respectively. This allowed us to identify parameters that are critical for the successful removal of arsenic from water, which is essential information for further optimization of the removal process. The composite was further applied for the removal of As(III) and As(V) from water in a dynamic flow through the reactor. Column study proved that the removal of both arsenic species below the value recommended by WHO can be achieved. Elution of As(III) and As(V) from the composite can be done by using small amounts of 0.01 M NaOH solution resulting in preconcentration of arsenic species and possible multiple usage of composite.

Characterization of radiation belt electron energy spectra from CRRES observations

NASA Astrophysics Data System (ADS)

Johnston, W. R.; Lindstrom, C. D.; Ginet, G. P.

2010-12-01

Energetic electrons in the outer radiation belt and the slot region exhibit a wide variety of energy spectral forms, more so than radiation belt protons. We characterize the spatial and temporal dependence of these forms using observations from the CRRES satellite Medium Electron Sensor A (MEA) and High-Energy Electron Fluxmeter (HEEF) instruments, together covering an energy range 0.15-8 MeV. Spectra were classified with two independent methods, data clustering and curve-fitting analyses, in each case defining categories represented by power law, exponential, and bump-on-tail (BOT) or other complex shapes. Both methods yielded similar results, with BOT, exponential, and power law spectra respectively dominating in the slot region, outer belt, and regions just beyond the outer belt. The transition from exponential to power law spectra occurs at higher L for lower magnetic latitude. The location of the transition from exponential to BOT spectra is highly correlated with the location of the plasmapause. In the slot region during the days following storm events, electron spectra were observed to evolve from exponential to BOT yielding differential flux minima at 350-650 keV and maxima at 1.5-2 MeV; such evolution has been attributed to energy-dependent losses from scattering by whistler hiss.

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.

Pyrometer mount for a closed-circuit thermal medium cooled gas turbine

DOEpatents

Jones, Raymond Joseph; Kirkpatrick, Francis Lawrence; Burns, James Lee; Fulton, John Robert

2002-01-01

A steam-cooled second-stage nozzle segment has an outer band and an outer cover defining a plenum therebetween for receiving cooling steam for flow through the nozzles to the inner band and cover therefor and return flow through the nozzles. To measure the temperature of the buckets of the stage forwardly of the nozzle stage, a pyrometer boss is electron beam-welded in an opening through the outer band and TIG-welded to the outer cover plate. By machining a hole through the boss and seating a linearly extending tube in the boss, a line of sight between a pyrometer mounted on the turbine frame and the buckets is provided whereby the temperature of the buckets can be ascertained. The welding of the boss to the outer band and outer cover enables steam flow through the plenum without leakage, while providing a line of sight through the outer cover and outer band to measure bucket temperature.

Comparison of Geant4-DNA simulation of S-values with other Monte Carlo codes

NASA Astrophysics Data System (ADS)

André, T.; Morini, F.; Karamitros, M.; Delorme, R.; Le Loirec, C.; Campos, L.; Champion, C.; Groetz, J.-E.; Fromm, M.; Bordage, M.-C.; Perrot, Y.; Barberet, Ph.; Bernal, M. A.; Brown, J. M. C.; Deleuze, M. S.; Francis, Z.; Ivanchenko, V.; Mascialino, B.; Zacharatou, C.; Bardiès, M.; Incerti, S.

2014-01-01

Monte Carlo simulations of S-values have been carried out with the Geant4-DNA extension of the Geant4 toolkit. The S-values have been simulated for monoenergetic electrons with energies ranging from 0.1 keV up to 20 keV, in liquid water spheres (for four radii, chosen between 10 nm and 1 μm), and for electrons emitted by five isotopes of iodine (131, 132, 133, 134 and 135), in liquid water spheres of varying radius (from 15 μm up to 250 μm). The results have been compared to those obtained from other Monte Carlo codes and from other published data. The use of the Kolmogorov-Smirnov test has allowed confirming the statistical compatibility of all simulation results.

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.

A non-storm time enhancement of outer radiation belt electrons

NASA Astrophysics Data System (ADS)

Schiller, Q.; Li, X.; Blum, L. W.; Jaynes, A. N.; Malaspina, D.; Tu, W.; Turner, D. L.; Blake, J. B.

2013-12-01

On January 13th, 2013, a high-speed solar wind stream impacted Earth's magnetosphere, resulting in low geomagnetic activity (Real-Time Dst minimum of -30 nT). However, the relativistic electron population was enhanced by over two orders of magnitude in the outer radiation belt. Fortunately, during the event, the outer belt was well sampled by a variety of missions, including the Van Allen Probes, THEMIS, GOES, and the Colorado Student Space Weather Experiment (CSSWE). The energetic electrons are measured in-situ using flux and phase space density observations from the Magnetic Electron Ion Spectrometer (MagEIS) onboard the Van Allen Probes, the Relativistic Electron and Proton Telescope integrated little experiment (REPTile) onboard CSSWE, and SST onboard THEMIS. These measured electron populations are the net result of the balance between concurrent loss and acceleration processes. Precipitation loss is quantified using REPTile measurements at low altitudes, while the energization mechanisms, namely interactions with whistler-mode chorus and Pc5 ULF waves, are investigated using Van Allen Probes' MagEIS and Electric Fields and Waves Suite (EFW), THEMIS' EFI and SCM instrument suites, and GOES magnetometers. The quantity and quality of measurements during this event provide a rare opportunity to address outstanding science questions; such as, whether the energetic electrons originate from inward injections associated with substorms or are accelerated via local heating, as well as what the energy dependence of the enhancement is during a period of such low geomagnetic activity.

Analysis of a non-storm time enhancement in outer belt electrons

NASA Astrophysics Data System (ADS)

Schiller, Q.; Li, X.; Godinez, H. C.; Sarris, T. E.; Tu, W.; Malaspina, D.; Turner, D. L.; Blake, J. B.; Koller, J.

2014-12-01

A high-speed solar wind stream impacted Earth's magnetosphere on January 13th, 2013, and is associated with a large enhancement (>2.5 orders) of outer radiation belt electron fluxes despite a small Dst signature (-30 nT). Fortunately, the outer belt was well sampled by a variety of missions during the event, including the Van Allen Probes, THEMIS, and the Colorado Student Space Weather Experiment (CSSWE). In-situ flux and phase space density observations are used from MagEIS (Magnetic Electron Ion Spectrometer) onboard the Van Allen Probes, REPTile (Relativistic Electron and Proton Telescope integrated little experiment) onboard CSSWE, and SST onboard THEMIS. The observations show a rapid increase in 100's keV electron fluxes, followed by a more gradual enhancement of the MeV energies. The 100's keV enhancement is associated with a substorm injection, and the futher energization to MeV energies is associated with wave activity as measured by the Van Allen Probes and THEMIS. Furthermore, the phase space density radial profiles show an acceleration region occurring between 5

Evolution of relativistic outer belt electrons during extended quiescent period

NASA Astrophysics Data System (ADS)

Jaynes, A. N.; Li, X.; Schiller, Q.; Blum, L. W.; Tu, W.; Malaspina, D.; Turner, D.; Baker, D. N.; Kanekal, S. G.; Blake, J. B.; Wygant, J. R.

2013-12-01

To effectively study loss due to precipitation of relativistic electron fluxes in the radiation belt, it is necessary to isolate this loss from the Dst effect and magnetopause shadowing by studying loss during a time of relatively quiet geomagnetic activity. We present a study of the slow decay of 200 keV - 2 MeV electron populations in the outer radiation belt during an extended quiescent period from ~15 Dec 2012 - 10 Jan 2013, wherein Dst never extended below -25 nT. We incorporate particle measurements from the Relativistic Electron and Proton Telescope integrated little experiment (REPTile) onboard the Colorado Student Space Weather Experiment (CSSWE) CubeSat with measurements from the Relativistic Electron Proton Telescope (REPT) and the Magnetic Electron Ion Spectrometer (MagEIS) on the Van Allen Probes twin spacecraft to understand the evolution of the electron populations across pitch angle and energy. First, we present REPTile measurements of the precipitating populations (along with trapped & quasi-trapped) at a low-earth orbit, offering a view into the loss cone that is not as easily resolved using only the Van Allen Probes. Electron loss to the atmosphere during this event is quantified through use of a precipitation loss model, using the REPTile measurements. Additionally, phase space densities are derived using pitch-angle-resolved flux data from the REPT and MagEIS instruments, as well as from THEMIS SST data. Finally, we present the net loss effect on the outer radiation belt content during this time, by incorporating the modeled precipitation loss (from REPTile measurements) with Van Allen Probes electron flux data. Hiss and chorus wave data, along with approximate plasmapause location, from Van Allen Probes' Electric Field and Waves Suite (EFW) completes the picture by suggesting mechanisms for the precipitation loss of relativistic electrons during quiet time.

Prediction of MeV electron fluxes throughout the outer radiation belt using multivariate autoregressive models

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

Sakaguchi, Kaori; Nagatsuma, Tsutomu; Reeves, Geoffrey D.

The Van Allen radiation belts surrounding the Earth are filled with MeV-energy electrons. This region poses ionizing radiation risks for spacecraft that operate within it, including those in geostationary orbit (GEO) and medium Earth orbit. In order to provide alerts of electron flux enhancements, 16 prediction models of the electron log-flux variation throughout the equatorial outer radiation belt as a function of the McIlwain L parameter were developed using the multivariate autoregressive model and Kalman filter. Measurements of omnidirectional 2.3 MeV electron flux from the Van Allen Probes mission as well as >2 MeV electrons from the GOES 15 spacecraftmore » were used as the predictors. Furthermore, we selected model explanatory parameters from solar wind parameters, the electron log-flux at GEO, and geomagnetic indices. For the innermost region of the outer radiation belt, the electron flux is best predicted by using the Dst index as the sole input parameter. For the central to outermost regions, at L≥4.8 and L ≥5.6, the electron flux is predicted most accurately by including also the solar wind velocity and then the dynamic pressure, respectively. The Dst index is the best overall single parameter for predicting at 3 ≤ L ≤ 6, while for the GEO flux prediction, the K P index is better than Dst. Finally, a test calculation demonstrates that the model successfully predicts the timing and location of the flux maximum as much as 2 days in advance and that the electron flux decreases faster with time at higher L values, both model features consistent with the actually observed behavior.« less

Prediction of MeV electron fluxes throughout the outer radiation belt using multivariate autoregressive models

DOE PAGES

Sakaguchi, Kaori; Nagatsuma, Tsutomu; Reeves, Geoffrey D.; ...

2015-12-22

The Van Allen radiation belts surrounding the Earth are filled with MeV-energy electrons. This region poses ionizing radiation risks for spacecraft that operate within it, including those in geostationary orbit (GEO) and medium Earth orbit. In order to provide alerts of electron flux enhancements, 16 prediction models of the electron log-flux variation throughout the equatorial outer radiation belt as a function of the McIlwain L parameter were developed using the multivariate autoregressive model and Kalman filter. Measurements of omnidirectional 2.3 MeV electron flux from the Van Allen Probes mission as well as >2 MeV electrons from the GOES 15 spacecraftmore » were used as the predictors. Furthermore, we selected model explanatory parameters from solar wind parameters, the electron log-flux at GEO, and geomagnetic indices. For the innermost region of the outer radiation belt, the electron flux is best predicted by using the Dst index as the sole input parameter. For the central to outermost regions, at L≥4.8 and L ≥5.6, the electron flux is predicted most accurately by including also the solar wind velocity and then the dynamic pressure, respectively. The Dst index is the best overall single parameter for predicting at 3 ≤ L ≤ 6, while for the GEO flux prediction, the K P index is better than Dst. Finally, a test calculation demonstrates that the model successfully predicts the timing and location of the flux maximum as much as 2 days in advance and that the electron flux decreases faster with time at higher L values, both model features consistent with the actually observed behavior.« less

Prediction of MeV electron fluxes throughout the outer radiation belt using multivariate autoregressive models

NASA Astrophysics Data System (ADS)

Sakaguchi, Kaori; Nagatsuma, Tsutomu; Reeves, Geoffrey D.; Spence, Harlan E.

2015-12-01

The Van Allen radiation belts surrounding the Earth are filled with MeV-energy electrons. This region poses ionizing radiation risks for spacecraft that operate within it, including those in geostationary orbit (GEO) and medium Earth orbit. To provide alerts of electron flux enhancements, 16 prediction models of the electron log-flux variation throughout the equatorial outer radiation belt as a function of the McIlwain L parameter were developed using the multivariate autoregressive model and Kalman filter. Measurements of omnidirectional 2.3 MeV electron flux from the Van Allen Probes mission as well as >2 MeV electrons from the GOES 15 spacecraft were used as the predictors. Model explanatory parameters were selected from solar wind parameters, the electron log-flux at GEO, and geomagnetic indices. For the innermost region of the outer radiation belt, the electron flux is best predicted by using the Dst index as the sole input parameter. For the central to outermost regions, at L ≧ 4.8 and L ≧ 5.6, the electron flux is predicted most accurately by including also the solar wind velocity and then the dynamic pressure, respectively. The Dst index is the best overall single parameter for predicting at 3 ≦ L ≦ 6, while for the GEO flux prediction, the KP index is better than Dst. A test calculation demonstrates that the model successfully predicts the timing and location of the flux maximum as much as 2 days in advance and that the electron flux decreases faster with time at higher L values, both model features consistent with the actually observed behavior.

Co(II) Coordination in Prokaryotic Zinc Finger Domains as Revealed by UV-Vis Spectroscopy

PubMed Central

Sivo, Valeria; D'Abrosca, Gianluca; Russo, Luigi; Iacovino, Rosa; Pedone, Paolo Vincenzo; Fattorusso, Roberto

2017-01-01

Co(II) electronic configuration allows its use as a spectroscopic probe in UV-Vis experiments to characterize the metal coordination sphere that is an essential component of the functional structure of zinc-binding proteins and to evaluate the metal ion affinities of these proteins. Here, exploiting the capability of the prokaryotic zinc finger to use different combinations of residues to properly coordinate the structural metal ion, we provide the UV-Vis characterization of Co(II) addition to Ros87 and its mutant Ros87_C27D which bears an unusual CysAspHis2 coordination sphere. Zinc finger sites containing only one cysteine have been infrequently characterized. We show for the CysAspHis2 coordination an intense d-d transition band, blue-shifted with respect to the Cys2His2 sphere. These data complemented by NMR and CD data demonstrate that the tetrahedral geometry of the metal site is retained also in the case of a single-cysteine coordination sphere. PMID:29386985

Apparatus and methods for controlling electron microscope stages

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

Duden, Thomas

Methods and apparatus for generating an image of a specimen with a microscope (e.g., TEM) are disclosed. In one aspect, the microscope may generally include a beam generator, a stage, a detector, and an image generator. A plurality of crystal parameters, which describe a plurality of properties of a crystal sample, are received. In a display associated with the microscope, an interactive control sphere based at least in part on the received crystal parameters and that is rotatable by a user to different sphere orientations is presented. The sphere includes a plurality of stage coordinates that correspond to a pluralitymore » of positions of the stage and a plurality of crystallographic pole coordinates that correspond to a plurality of polar orientations of the crystal sample. Movement of the sphere causes movement of the stage, wherein the stage coordinates move in conjunction with the crystallographic coordinates represented by pole positions so as to show a relationship between stage positions and the pole positions.« less

Co(II) Coordination in Prokaryotic Zinc Finger Domains as Revealed by UV-Vis Spectroscopy.

PubMed

Sivo, Valeria; D'Abrosca, Gianluca; Russo, Luigi; Iacovino, Rosa; Pedone, Paolo Vincenzo; Fattorusso, Roberto; Isernia, Carla; Malgieri, Gaetano

2017-01-01

Co(II) electronic configuration allows its use as a spectroscopic probe in UV-Vis experiments to characterize the metal coordination sphere that is an essential component of the functional structure of zinc-binding proteins and to evaluate the metal ion affinities of these proteins. Here, exploiting the capability of the prokaryotic zinc finger to use different combinations of residues to properly coordinate the structural metal ion, we provide the UV-Vis characterization of Co(II) addition to Ros87 and its mutant Ros87_C27D which bears an unusual CysAspHis 2 coordination sphere. Zinc finger sites containing only one cysteine have been infrequently characterized. We show for the CysAspHis 2 coordination an intense d - d transition band, blue-shifted with respect to the Cys 2 His 2 sphere. These data complemented by NMR and CD data demonstrate that the tetrahedral geometry of the metal site is retained also in the case of a single-cysteine coordination sphere.

Hierarchical TiO{sub 2} submicron-sized spheres for enhanced power conversion efficiency in dye-sensitized solar cells

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

Wang, Hao; State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000; Guo, Zhiguang, E-mail: zguo@licp.cas.cn

Hierarchical TiO{sub 2} submicron-sized sphere scattering layer, with relatively large surface area and effective light scattering, shows enhanced power conversion efficiency in dye-sensitized solar cells. - Highlights: • Hierarchical TiO{sub 2} submicron-sized spheres (TiO{sub 2} HSSs) with diameters of 400–600 nm were synthesized. • The HSSs composed of nanoparticles of ∼14 nm have a relatively large surface area of ∼35 m{sup 2}/g. • DSC exhibited the highest cell efficiency (6.23%) compared with ones with pure P25 (5.50%) or HSS (2.00%) photoanodes. - Abstract: Hierarchical TiO{sub 2} submicron-sized spheres (TiO{sub 2} HSSs) with diameters of 400–600 nm were synthesized by amore » facile one-step solvothermal method in ethanol solvent. The HSSs composed of nanoparticles of ∼14 nm have a relatively large surface area of ∼35 m{sup 2}/g. When applied as the scattering overlayer in dye-sensitized solar cells (DSCs), such TiO{sub 2} HSSs effectively improved light harvesting and led to the increase of photocurrent in DSCs. Furthermore, bilayer-structured photoanode also provided fast electron transportation and long electron lifetime as confirmed by electrochemical impedance spectra. As a result, DSC based on P25 nanoparticle underlayer and HSS-2 overlayer exhibited the highest cell efficiency (6.23%) compared with ones with pure P25 (5.50%) or HSS-2 (2.00%) photoanodes.« less

Source and seed populations for relativistic electrons: Their roles in radiation belt changes

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

Jaynes, A. N.; Baker, D. N.; Singer, H. J.

Strong enhancements of outer Van Allen belt electrons have been shown to have a clear dependence on solar wind speed and on the duration of southward interplanetary magnetic field. However, individual case study analyses also have demonstrated that many geomagnetic storms produce little in the way of outer belt enhancements and, in fact, may produce substantial losses of relativistic electrons. In this study, focused upon a key period in August–September 2014, we use GOES geostationary orbit electron flux data and Van Allen Probes particle and fields data to study the process of radiation belt electron acceleration. One particular interval, 13–22more » September, initiated by a short-lived geomagnetic storm and characterized by a long period of primarily northward interplanetary magnetic field (IMF), showed strong depletion of relativistic electrons (including an unprecedented observation of long-lasting depletion at geostationary orbit) while an immediately preceding, and another immediately subsequent, storm showed strong radiation belt enhancement. We demonstrate with these data that two distinct electron populations resulting from magnetospheric substorm activity are crucial elements in the ultimate acceleration of highly relativistic electrons in the outer belt: the source population (tens of keV) that give rise to VLF wave growth and the seed population (hundreds of keV) that are, in turn, accelerated through VLF wave interactions to much higher energies. ULF waves may also play a role by either inhibiting or enhancing this process through radial diffusion effects. Furthermore, if any components of the inner magnetospheric accelerator happen to be absent, the relativistic radiation belt enhancement fails to materialize.« less

Source and seed populations for relativistic electrons: Their roles in radiation belt changes

DOE PAGES

Jaynes, A. N.; Baker, D. N.; Singer, H. J.; ...

2015-09-09

Strong enhancements of outer Van Allen belt electrons have been shown to have a clear dependence on solar wind speed and on the duration of southward interplanetary magnetic field. However, individual case study analyses also have demonstrated that many geomagnetic storms produce little in the way of outer belt enhancements and, in fact, may produce substantial losses of relativistic electrons. In this study, focused upon a key period in August–September 2014, we use GOES geostationary orbit electron flux data and Van Allen Probes particle and fields data to study the process of radiation belt electron acceleration. One particular interval, 13–22more » September, initiated by a short-lived geomagnetic storm and characterized by a long period of primarily northward interplanetary magnetic field (IMF), showed strong depletion of relativistic electrons (including an unprecedented observation of long-lasting depletion at geostationary orbit) while an immediately preceding, and another immediately subsequent, storm showed strong radiation belt enhancement. We demonstrate with these data that two distinct electron populations resulting from magnetospheric substorm activity are crucial elements in the ultimate acceleration of highly relativistic electrons in the outer belt: the source population (tens of keV) that give rise to VLF wave growth and the seed population (hundreds of keV) that are, in turn, accelerated through VLF wave interactions to much higher energies. ULF waves may also play a role by either inhibiting or enhancing this process through radial diffusion effects. Furthermore, if any components of the inner magnetospheric accelerator happen to be absent, the relativistic radiation belt enhancement fails to materialize.« less

Double ionization in R -matrix theory using a two-electron outer region

NASA Astrophysics Data System (ADS)

Wragg, Jack; Parker, J. S.; van der Hart, H. W.

2015-08-01

We have developed a two-electron outer region for use within R -matrix theory to describe double ionization processes. The capability of this method is demonstrated for single-photon double ionization of He in the photon energy region between 80 and 180 eV. The cross sections are in agreement with established data. The extended R -matrix with time dependence method also provides information on higher-order processes, as demonstrated by the identification of signatures for sequential double ionization processes involving an intermediate He+ state with n =2 .

COMPOSITION, STRUCTURE, ET MODE DE FORMATION DES CONCRÉTIONS MINÉRALES DANS L'INTESTIN MOYEN DES HOMOPTERES CERCOPIDES

PubMed Central

Gouranton, Jean

1968-01-01

The granules which occur in the cells of a part of the midgut wall in Cercopid larvae and adults (Homoptera) have been studied by biochemical and cytochemical methods and by electron microscopy. The granules have a diameter up to about 2µ and contain calcium, magnesium, iron, carbonates, and phosphates. Protein and acid mucopolysaccharide have also been detected. A chromatographic study shows that uric acid and guanine are not present. The young concretions occur primarily in ergastoplasmic cisternae. They are first wholly electron-opaque, but their center becomes more and more clear. In very old spheres, only a thin shell of electron-opaque material remains. The spheres which have reached about 1µ in diameter are all associated with myelin figures. The granule-containing cells, which nearly occlude the lumen of the midgut in larvae, are eliminated in the very young adults, but the storage excretion still continue in adults. PMID:4231917

Beyond Pluto: The Search for the Edge of the Solar System

ScienceCinema

Funsten, Herb

2018-01-16

In July, we finally visited the last major body of our solar system, Pluto. But what lies beyond? The stellar wind from our Sun forms an enormous bubble in interstellar space. This “sphere of our Sun,” or heliosphere, extends far beyond Pluto and forms a protective cocoon that shields us from cosmic radiation. In this talk, we will travel to the edge of the solar system, peer into the structure and dynamics of the outer heliosphere as it interacts with the interstellar medium and anticipate the future of the solar system as it moves through our galactic neighborhood.

PICsar: Particle in cell pulsar magnetosphere simulator

NASA Astrophysics Data System (ADS)

Belyaev, Mikhail A.

2016-07-01

PICsar simulates the magnetosphere of an aligned axisymmetric pulsar and can be used to simulate other arbitrary electromagnetics problems in axisymmetry. Written in Fortran, this special relativistic, electromagnetic, charge conservative particle in cell code features stretchable body-fitted coordinates that follow the surface of a sphere, simplifying the application of boundary conditions in the case of the aligned pulsar; a radiation absorbing outer boundary, which allows a steady state to be set up dynamically and maintained indefinitely from transient initial conditions; and algorithms for injection of charged particles into the simulation domain. PICsar is parallelized using MPI and has been used on research problems with 1000 CPUs.

Near-earth injection of MeV electrons associated with intense dipolarization electric fields: Van Allen Probes observations

DOE PAGES

Dai, Lei; Wang, Chi; Duan, Suping; ...

2015-08-10

Substorms generally inject tens to hundreds of keV electrons, but intense substorm electric fields have been shown to inject MeV electrons as well. An intriguing question is whether such MeVelectron injections can populate the outer radiation belt. Here we present observations of a substorm injection of MeV electrons into the inner magnetosphere. In the premidnight sector at L ~ 5.5, Van Allen Probes (Radiation Belt Storm Probes)-A observed a large dipolarization electric field (50 mV/m) over ~40 s and a dispersionless injection of electrons up to ~3 MeV. Pitch angle observations indicated betatron acceleration of MeV electrons at the dipolarizationmore » front. Corresponding signals of MeV electron injection were observed at LANL-GEO, THEMIS-D, and GOES at geosynchronous altitude. Through a series of dipolarizations, the injections increased the MeV electron phase space density by 1 order of magnitude in less than 3 h in the outer radiation belt (L > 4.8). Our observations provide evidence that deep injections can supply significant MeV electrons.« less

Development of a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA), and its application to Auger photoelectron coincidence spectroscopy (APECS)

NASA Astrophysics Data System (ADS)

Kobayashi, Eiichi; Seo, Junya; Nambu, Akira; Mase, Kazuhiko

2007-09-01

We have developed a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA) with an outer diameter of 26 mm. The DPCMA consists of a shield for the electric field, inner and outer cylinders, two pinholes with a diameter of 2.0 mm, and an electron multiplier. By assembling the DPCMA in a coaxially symmetric mirror electron energy analyzer (ASMA) coaxially and confocally we developed an analyzer for Auger photoelectron coincidence spectroscopy (APECS). The performance was estimated by measuring the Si-LVV-Auger Si-1s-photoelectron coincidence spectra of clean Si(1 1 1). The electron-energy resolution of the DPCMA was estimated to be E/Δ E = 20. This value is better than that of the miniature single-pass CMA ( E/Δ E = 12) that was used in the previous APECS analyzer.

L-cysteine-assisted synthesis of hierarchical NiS2 hollow spheres supported carbon nitride as photocatalysts with enhanced lifetime

NASA Astrophysics Data System (ADS)

Zhu, Chengzhang; Jiang, Zhifeng; Chen, Linlin; Qian, Kun; Xie, Jimin

2017-03-01

Novel hierarchical NiS2 hollow spheres modified by graphite-like carbon nitride were prepared using a facile L-cysteine-assisted solvothermal route. The NiS2/g-C3N4 composites exhibited excellent photocatalytic efficiency in rhodamine B, methyl orange and ciprofloxacin degradation as compared to single g-C3N4 and NiS2, which could be due to the synergistic effects of the unique hollow sphere-like structure, strong visible-light absorption and increased separation rate of the photoinduced electron-hole pairs at the intimate interface of heterojunctions. A suitable combination of g-C3N4 with NiS2 showed the best photocatalytic performance. In addition, an electron spin resonance and trapping experiment demonstrated that the photogenerated hydroxyl radicals and superoxide radicals were the two main photoactive species in photocatalysis. A possible photocatalytic mechanism of NiS2/g-C3N4 composites under visible light irradiation is also proposed. The strategy presented here can be extended to a general strategy for constructing 3D/2D heterostructured photocatalysts for broad applications in photocatalysis.

Incidence of the muffin-tin approximation on the electronic structure of large clusters calculated by the MS-LSD method: The typical case of C{sub 60}

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

Razafinjanahary, H.; Rogemond, F.; Chermette, H.

The MS-LSD method remains a method of interest when rapidity and small computer resources are required; its main drawback is some lack of accuracy, mainly due to the muffin-tin distribution of the potential. In the case of large clusters or molecules, the use of an empty sphere to fill, in part, the large intersphere region can improve greatly the results. Calculations bearing on C{sub 60} has been undertaken to underline this trend, because, on the one hand, the fullerenes exhibit a remarkable possibility to fit a large empty sphere in the center of the cluster and, on the other hand,more » numerous accurate calculations have already been published, allowing quantitative comparison with results. The author`s calculations suggest that in case of added empty sphere the results compare well with the results of more accurate calculations. The calculated electron affinity for C{sub 60} and C{sub 60}{sup {minus}} are in reasonable agreement with experimental values, but the stability of C{sub 60}{sup 2-} in gas phase is not found. 35 refs., 3 figs., 5 tabs.« less

Synthesis of hydroxyapatite nanoparticles by a novel ultrasonic assisted with mixed hollow sphere template method

NASA Astrophysics Data System (ADS)

Gopi, D.; Indira, J.; Kavitha, L.; Sekar, M.; Mudali, U. Kamachi

Hydroxyapatite (HAP) is the main inorganic component of bone material and is widely used in various biomedical applications due to its excellent bioactivity and biocompatibility. In this paper, we have reported the synthesis of hydroxyapatite nanoparticles by a novel ultrasonic assisted mixed template directed method. In this method glycine-acrylic acid (GLY-AA) hollow spheres were used as an organic template which could be prepared by mixing of glycine with acrylic acid. The as-synthesized HAP nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) and tunnelling electron microscope (TEM) to investigate the nature of bonding, crystallinity, size and shape. The thermal stability of as-synthesized nanoparticles was also investigated by the thermo gravimetric analysis (TGA). The effect of ultrasonic irradiation time on the crystallinity and size of the HAP nanoparticles in presence of glycine-acrylic acid hollow spheres template were investigated. From the inspection of the above results it is confirmed that the crystallinity and size of the HAP nanoparticles decrease with increasing ultrasonic irradiation time. Hence the proposed synthesis strategy provides a facile pathway to obtain nano sized HAP with high quality, suitable size and morphology.

Novel morphology of calcium carbonate controlled by poly(L-lysine).

PubMed

Yao, Yuan; Dong, Wenyong; Zhu, Shenmin; Yu, Xinhai; Yan, Deyue

2009-11-17

The novel calcium carbonate (CaCO(3)) morphology, twin-sphere with an equatorial girdle, has been obtained under the control of poly(L-lysine) (PLys) through gas-diffusion method. The effect of the concentration of calcium cation and PLys, the reaction time, and the initial pH value are investigated, and various interesting morphologies, including twin-sphere, discus-like, hexagonal plate, and hallow structure are observed by using scanning electronic microscopy. Laser microscopic Raman spectroscopy studies indicated that all these CaCO(3) are vaterite. A possible mechanism is suggested to explain the formation of the twin-sphere based morphologies according to the results. It is proven that alkaline polypeptides can control the mineralization of CaCO(3) precisely as the reported acidic polypeptides and double hydrophilic block copolymers.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

PubMed

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

2017-09-28

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

Capacitively-coupled inductive sensor

DOEpatents

Ekdahl, Carl A.

1984-01-01

A capacitively coupled inductive shunt current sensor which utilizes capacitive coupling between flanges having an annular inductive channel formed therein. A voltage dividing capacitor is connected between the coupling capacitor and ground to provide immediate capacitive division of the output signal so as to provide a high frequency response of the current pulse to be detected. The present invention can be used in any desired outer conductor such as the outer conductor of a coaxial transmission line, the outer conductor of an electron beam transmission line, etc.

Tribochemical Studies of Hard Carbon Films as a Function of Load and Environment

DTIC Science & Technology

2010-08-13

the wear tracks on the flat as well as the wear scar on the sphere. The BNL imaging apparatus uses a magnetic field to guide the photoemitted...from the sample surface, and the electron optics, which can filter electrons with the wrong path or energy. The BNL imaging chamber is not able to

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…

Research on a 170 GHz, 2 MW coaxial cavity gyrotron with inner-outer corrugation

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

Hou, Shenyong, E-mail: houshenyong@sohu.com; Yu, Sheng; Li, Hongfu

2015-03-15

In this paper, a coaxial cavity gyrotron with inner-outer corrugation is researched. The electron kineto-equations and the first order transmission line equations of the gyrotron are derived from Lorentz force equation and the transmission line theory, respectively. And then, a 2 MW, 170 GHz coaxial cavity gyrotron with inner-outer corrugation is designed. By means of numerical calculation, the beam-wave interaction of the coaxial cavity gyrotron with inner-outer corrugation is investigated. Results show that the efficient and the outpower of the gyrotron are 42.3% and 2.38 MW, respectively.

Changes in divertor conditions in response to changing core density with RMPs

DOE PAGES

Briesemeister, Alexis R.; Ahn, Joon -Wook; Canik, John M.; ...

2017-06-07

The effects of changes in core density on divertor electron temperature, density and heat flux when resonant magnetic perturbations (RMPs) are applied are presented, notably a reduction in RMP induced secondary radial peaks in the electron temperature profile at the target plate is observed when the core density is increased, which is consistent with modeling. RMPs is used here to indicated non-axisymmetric magnetic field perturbations, created using in-vessel control coils, which have components which has at least one but typically many resonances with the rotational transform of the plasma. RMPs are found to alter inter-ELM heat flux to the divertormore » by modifying the core plasma density. It is shown that applying RMPs reduces the core density and increases the inter-ELM heat flux to both the inner and outer targets. Using gas puffing to return the core density to the pre-RMP levels more than eliminates the increase in inter-ELM heat flux, but a broadening of the heat flux to the outer target remains. These measurements were made at a single toroidal location, but the peak in the heat flux profile was found near the outer strike point where simulations indicate little toroidal variation should exist and tangentially viewing diagnostics showed no evidence of strong asymmetries. In experiments where divertor Thomson scattering measurements were available it is shown that, local secondary peaks in the divertor electron temperature profile near the target plate are reduced as the core density is increased, while peaks in the divertor electron density profile near the target are increased. Furthermore, these trends observed in the divertor electron temperature and density are qualitatively reproduced by scanning the upstream density in EMC3-Eirene modeling. Measurements are presented showing that higher densities are needed to induce detachment of the outer strike point in a case where an increase in electron temperature, likely due to a change in MHD activity, is seen after RMPs are applied.« less

Changes in divertor conditions in response to changing core density with RMPs

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

Briesemeister, Alexis R.; Ahn, Joon -Wook; Canik, John M.

The effects of changes in core density on divertor electron temperature, density and heat flux when resonant magnetic perturbations (RMPs) are applied are presented, notably a reduction in RMP induced secondary radial peaks in the electron temperature profile at the target plate is observed when the core density is increased, which is consistent with modeling. RMPs is used here to indicated non-axisymmetric magnetic field perturbations, created using in-vessel control coils, which have components which has at least one but typically many resonances with the rotational transform of the plasma. RMPs are found to alter inter-ELM heat flux to the divertormore » by modifying the core plasma density. It is shown that applying RMPs reduces the core density and increases the inter-ELM heat flux to both the inner and outer targets. Using gas puffing to return the core density to the pre-RMP levels more than eliminates the increase in inter-ELM heat flux, but a broadening of the heat flux to the outer target remains. These measurements were made at a single toroidal location, but the peak in the heat flux profile was found near the outer strike point where simulations indicate little toroidal variation should exist and tangentially viewing diagnostics showed no evidence of strong asymmetries. In experiments where divertor Thomson scattering measurements were available it is shown that, local secondary peaks in the divertor electron temperature profile near the target plate are reduced as the core density is increased, while peaks in the divertor electron density profile near the target are increased. Furthermore, these trends observed in the divertor electron temperature and density are qualitatively reproduced by scanning the upstream density in EMC3-Eirene modeling. Measurements are presented showing that higher densities are needed to induce detachment of the outer strike point in a case where an increase in electron temperature, likely due to a change in MHD activity, is seen after RMPs are applied.« less

Extension of Nikiforov-Uvarov method for the solution of Heun equation

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

Karayer, H., E-mail: hale.karayer@gmail.com; Demirhan, D.; Büyükkılıç, F.

2015-06-15

We report an alternative method to solve second order differential equations which have at most four singular points. This method is developed by changing the degrees of the polynomials in the basic equation of Nikiforov-Uvarov (NU) method. This is called extended NU method for this paper. The eigenvalue solutions of Heun equation and confluent Heun equation are obtained via extended NU method. Some quantum mechanical problems such as Coulomb problem on a 3-sphere, two Coulombically repelling electrons on a sphere, and hyperbolic double-well potential are investigated by this method.

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...

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.

Jupiter's magnetosphere and radiation belts

NASA Technical Reports Server (NTRS)

Kennel, C. F.; Coroniti, F. V.

1979-01-01

Radioastronomy and Pioneer data reveal the Jovian magnetosphere as a rotating magnetized source of relativistic particles and radio emission, comparable to astrophysical cosmic ray and radio sources, such as pulsars. According to Pioneer data, the magnetic field in the outer magnetosphere is radially extended into a highly time variable disk-shaped configuration which differs fundamentally from the earth's magnetosphere. The outer disk region, and the energetic particles confined in it, are modulated by Jupiter's 10 hr rotation period. The entire outer magnetosphere appears to change drastically on time scales of a few days to a week. In addition to its known modulation of the Jovian decametric radio bursts, Io was found to absorb some radiation belt particles and to accelerate others, and most importantly, to be a source of neutral atoms, and by inference, a heavy ion plasma which may significantly affect the hydrodynamic flow in the magnetosphere. Another important Pioneer finding is that the Jovian outer magnetosphere generates, or permits to escape, fluxes of relativistic electrons of such intensities that Jupiter may be regarded as the dominant source of 1 to 30 MeV cosmic ray electrons in the heliosphere.

Heat capacity of a self-gravitating spherical shell of radiations

NASA Astrophysics Data System (ADS)

Kim, Hyeong-Chan

2017-10-01

We study the heat capacity of a static system of self-gravitating radiations analytically in the context of general relativity. To avoid the complexity due to a conical singularity at the center, we excise the central part and replace it with a regular spherically symmetric distribution of matters of which specifications we are not interested in. We assume that the mass inside the inner boundary and the locations of the inner and the outer boundaries are given. Then, we derive a formula relating the variations of physical parameters at the outer boundary with those at the inner boundary. Because there is only one free variation at the inner boundary, the variations at the outer boundary are related, which determines the heat capacity. To get an analytic form for the heat capacity, we use the thermodynamic identity δ Srad=β δ Mrad additionally, which is derived from the variational relation of the entropy formula with the restriction that the mass inside the inner boundary does not change. Even if the radius of the inner boundary of the shell goes to zero, in the presence of a central conical singularity, the heat capacity does not go to the form of the regular sphere. An interesting discovery is that another legitimate temperature can be defined at the inner boundary which is different from the asymptotic one β-1.

CNTs in situ attached to α-Fe2O3 submicron spheres for enhancing lithium storage capacity.

PubMed

Gao, Guo; Zhang, Qiang; Cheng, Xin-Bing; Qiu, Peiyu; Sun, Rongjin; Yin, Ting; Cui, Daxiang

2015-01-14

In this work, we developed a facile hydrothermal method for synthesis of hybrid α-Fe2O3-carbon nanotubes (CNTs) architectures (α-Fe2O3-CNTs-1 and α-Fe2O3-CNTs-2). The CNTs are in situ attached to the α-Fe2O3 submicron spheres and form three-dimensional network robust architectures. The increase in the amount of CNTs in the network α-Fe2O3-CNTs architectures will significantly enhance the cycling and rate performance, as the flexible and robust CNTs could ensure the fast electron transport pathways, enhance the electronic conductivity, and improve the structural stability of the electrode. As for pure α-Fe2O3 submicron spheres, the capacity decreased significantly and retained at 377.4 mAh g(-1) after 11 cycles, and the capacity has a slightly increasing trend at the following cycling. In contrast, the network α-Fe2O3-CNTs-2 electrode shows the most remarkable performance. At the 60th cycle, the capacity of network α-Fe2O3-CNTs-2 (764.5 mAh g(-1)) is 1.78 times than that of α-Fe2O3 submicron spheres (428.3 mAh g(-1)). The long-term cycling performance (1000 cycles) of samples at a high current density of 5 C showed that the capacity of α-Fe2O3 submicron spheres fade to ∼37.3 mAh g(-1) at the 400th cycle and gradually increased to ∼116.7 mAh g(-1) at the 1000th cycle. The capacity of network α-Fe2O3-CNTs-2 maintained at ∼220.2 mAh g(-1) before the 400th cycle, arrived at ∼326.5 mAh g(-1) in the 615th, cycle and retained this value until 1000th cycle. The network α-Fe2O3-CNTs-2 composite could significantly enhance the cycling and rate performance than pure α-Fe2O3 submicron spheres composite.

Metal-filled carbon nanotube based optical nanoantennas: bubbling, reshaping, and in situ characterization.

PubMed

Fan, Zheng; Tao, Xinyong; Cui, Xudong; Fan, Xudong; Zhang, Xiaobin; Dong, Lixin

2012-09-21

Controlled fabrication of metal nanospheres on nanotube tips for optical antennas is investigated experimentally. Resembling soap bubble blowing using a straw, the fabrication process is based on nanofluidic mass delivery at the attogram scale using metal-filled carbon nanotubes (m@CNTs). Two methods have been investigated including electron-beam-induced bubbling (EBIB) and electromigration-based bubbling (EMBB). EBIB involves the bombardment of an m@CNT with a high energy electron beam of a transmission electron microscope (TEM), with which the encapsulated metal is melted and flowed out from the nanotube, generating a metallic particle on a nanotube tip. In the case where the encapsulated materials inside the CNT have a higher melting point than what the beam energy can reach, EMBB is an optional process to apply. Experiments show that, under a low bias (2.0-2.5 V), nanoparticles can be formed on the nanotube tips. The final shape and crystallinity of the nanoparticles are determined by the cooling rate. Instant cooling occurs with a relatively large heat sink and causes the instant shaping of the solid deposit, which is typically similar to the shape of the molten state. With a smaller heat sink as a probe, it is possible to keep the deposit in a molten state. Instant cooling by separating the deposit from the probe can result in a perfect sphere. Surface and volume plasmons characterized with electron energy loss spectroscopy (EELS) prove that resonance occurs between a pair of as-fabricated spheres on the tip structures. Such spheres on pillars can serve as nano-optical antennas and will enable devices such as scanning near-field optical microscope (SNOM) probes, scanning anodes for field emitters, and single molecule detectors, which can find applications in bio-sensing, molecular detection, and high-resolution optical microscopy.

Monodisperse mesoporous silica nanoparticles of distinct topology.

PubMed

Luo, Leilei; Liang, Yucang; Erichsen, Egil Sev; Anwander, Reiner

2017-06-01

Monodisperse and uniform high-quality MCM(Mobil Composition of Matter)-48-type CMSNs (Cubic Mesoporous Silica Nanoparticles) are readily prepared by simply optimizing the molar ratio of ethanol and surfactant in the system TEOS-CTAB-NaOH-H 2 O-EtOH (TEOS=tetraethyl orthosilicate, CTAB=cetyltrimethylammonium bromide, EtOH=ethanol). In the absence of ethanol only hexagonal mesoporous silica with ellipsoidal and spherical morphology are obtained. The presence of ethanol drives a mesophase transformation from hexagonal to mixed hexagonal/cubic, further to purely cubic, and finally to a mixed cubic/lamellar. This is accompanied by a morphology evolution involving a mixture of ellipses/spheres, regular rods, uniform spheres, and finally a mixture of spheres/flakes. Preserving the three-dimensional (3D) cubic MCM-48 structure, use of a small amount of ethanol is beneficial to the improvement of the monodispersity of the CMSNs. Moreover, the quality of the CMSNs can also be controlled by changing the surfactant concentration or adjusting the stirring rate. All MSNs were characterized using powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and N 2 physisorption, indicating highly long-range ordered pore arrays, high specific surface areas (max. 1173 m 2 g -1 ) as well as high pore volumes (max. 1.14 cm 3 g -1 ). The monodispersity of the CMSNs was verified by statistical particle size distribution from SEM (scanning electron microscopy)/TEM (transmission electron microscopy) images and DLS (dynamic light scattering). The mesophase transformation can be rationalized on the basis of an ethanol-driven change of the surfactant packing structure and charge matching at the surfactant/silicate interface. The corresponding morphology evolution can be elucidated by an ethanol-controlled hydrolysis rate of TEOS and degree of condensation of oligomeric silicate species via a nucleation and growth process. Copyright © 2017 Elsevier Inc. All rights reserved.

Organozinc Precursor-Derived Crystalline ZnO Nanoparticles: Synthesis, Characterization and Their Spectroscopic Properties.

PubMed

Liang, Yucang; Wicker, Susanne; Wang, Xiao; Erichsen, Egil Severin; Fu, Feng

2018-01-04

Crystalline ZnO -ROH and ZnO -OR (R = Me, Et, i Pr, n Bu) nanoparticles (NPs) have been successfully synthesized by the thermal decomposition of in-situ-formed organozinc complexes Zn(OR)₂ deriving from the reaction of Zn[N(SiMe₃)₂]₂ with ROH and of the freshly prepared Zn(OR)₂ under an identical condition, respectively. With increasing carbon chain length of alkyl alcohol, the thermal decomposition temperature and dispersibility of in-situ-formed intermediate zinc alkoxides in oleylamine markedly influenced the particle sizes of ZnO -ROH and its shape (sphere, plate-like aggregations), while a strong diffraction peak-broadening effect is observed with decreasing particle size. For ZnO -OR NPs, different particle sizes and various morphologies (hollow sphere or cuboid-like rod, solid sphere) are also observed. As a comparison, the calcination of the fresh-prepared Zn(OR)₂ generated ZnO -R NPs possessing the particle sizes of 5.4~34.1 nm. All crystalline ZnO nanoparticles are characterized using X-ray diffraction analysis, electron microscopy and solid-state ¹H and 13 C nuclear magnetic resonance (NMR) spectroscopy. The size effect caused by confinement of electrons' movement and the defect centres caused by unpaired electrons on oxygen vacancies or ionized impurity heteroatoms in the crystal lattices are monitored by UV-visible spectroscopy, electron paramagnetic resonance (EPR) and photoluminescent (PL) spectroscopy, respectively. Based on the types of defects determined by EPR signals and correspondingly defect-induced probably appeared PL peak position compared to actual obtained PL spectra, we find that it is difficult to establish a direct relationship between defect types and PL peak position, revealing the complication of the formation of defect types and photoluminescence properties.

Combining Sequential Extractions and X-ray Absorption Spectroscopy for Quantitative and Qualitative Zinc Speciation in Soil

NASA Astrophysics Data System (ADS)

Bauer, Tatiana; Minkina, Tatiana; Batukaev, Abdulmalik; Nevidomskaya, Dina; Burachevskaya, Marina; Tsitsuashvili, Viktoriya; Urazgildieva, Kamilya

2017-04-01

The combined use of X-ray absorption spectrometry and extractive fractionation is an effective approach for studying the interaction of metal ions with soil compounds and identifying the phases-carriers of metals in soil and their stable fixation. These studies were carried out using the technique of X-ray absorption spectroscopy and chemical extractive fractionation. In a model experiment the samples taken in Calcic Chernozem were artificially contaminated with higher portion of Zn(NO3)2 (2000 mg/kg). The metal were incubated in soil samples for 2 year. The samples of soil mineral and organic phases (calcite, kaolinite, bentonite, humic acids) were saturated with Zn2+ from a solution of nitrate salts of metal. The total content of Zn in soil and soil various phases was determined using the X-ray fluorescence method. Extended X-ray absorption fine structure (EXAFS) Zn was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation. Sequential fractionation of Zn in soil conducted by Tessier method (Tessier et al., 1979) which determining 5 fractions of metals in soil: exchangeable, bound to Fe-Mn oxide, bound to carbonate, bound to the organic matter, and bound to silicate (residual). This methodology has so far more than 4000 citations (Web of Science), which demonstrates the popularity of this approach. Much Zn compounds are contained in uncontaminated soils in stable primary and secondary silicates inherited from the parental rocks (67% of the total concentrations in all fractions), which is a regional trait of soils in the fore-Caucasian plain. Extracted fractionation of metal compounds in soil samples, artificially contaminated with Zn salts, indicates the priority holding of Zn2+ ions by silicates, carbonates and Fe-Mn oxides. The Zn content significantly increases in the exchangeable fraction. Atomic structure study of the soil various phases saturated with Zn2+ ion by using (XANES) X-ray absorption spectroscopy allowed the determination of mechanism of metal ions interaction with soil phases and the resulting types of chemical bonds. Interaction with soil components modifies the electron structure of the metal ions themselves. The soil contamination with Zn is accompanied by decreasing the stable connection between metal and soil components. Interacting with humic acids in chernozem, the Zn2+ ion is coordinated by functional groups and ligands and forms unstable outer-sphere complexes. Zinc included into octahedral structures of layered minerals and hydro(oxides) can be inner-and outer-sphere adsorbed. The Zn2+ ions enable to replace Ca2+ ions in octahedral positions being coordinated with carbonate ions as ligands, thus forming absorbed complexes at the surface of mineral calcite. This work was supported by grant of the Russian Scientific Foundation № 16-14-10217.

INTRACELLULAR FORMS OF POX VIRUSES AS SHOWN BY THE ELECTRON MICROSCOPE (VACCINIA, ECTROMELIA, MOLLUSCUM CONTAGIOSUM)

PubMed Central

Gaylord, William H.; Melnick, Joseph L.

1953-01-01

The intracellular development of three pox viruses has been studied with the electron microscope using thin sections of infected tissue. Cells infected with vaccinia, ectromelia, and molluscum contagiosum viruses all form developmental bodies preliminary to the production of mature virus. Developmental bodies, believed to be virus precursors, are round to oval, slightly larger than mature virus particles, less dense to electrons, and have a more varied morphology. It is suggested as a working hypothesis that the process of maturation of a virus particle takes place as follows. In the earliest form the developmental bodies appear as hollow spheres, imbedded in a very dense cytoplasmic mass constituting an inclusion body, or in a less dense matrix near the nucleus in cells without typical inclusion bodies. The spheres become filled with a homogeneous material of low electron density. A small, dense granule appears in each developmental body and grows in size at the expense of the low density material. Following growth of the granule, particles are found with the dimensions of mature virus and having complex internal structure resembling bars or dumbells. Mature virus is ovoid and very dense to electrons. An "empty" interior may be found within its thick walls. PMID:13069658

Electronic Informational and Educational Environment as a Factor of Competence-Oriented Higher Pedagogical Education in the Sphere of Health, Safety and Environment

ERIC Educational Resources Information Center

Kamerilova, Galina S.; Kartavykh, Marina A.; Ageeva, Elena L.; Veryaskina, Marina A.; Ruban, Elena M.

2016-01-01

The authors consider the question of computerisation in health, safety and environment teachers' training in the context of the general approaches and requirements of the Federal National Standard of Higher Education, which is realised through designing of electronic informational and educational environment. The researchers argue indispensability…

Measurements of the asymmetric dynamic sheath around a pulse biased sphere immersed in flowing metal plasma

NASA Astrophysics Data System (ADS)

Wu, Hongchen; Anders, André

2008-08-01

A long-probe technique was utilized to record the expansion and retreat of the dynamic sheath around a spherical substrate immersed in pulsed cathode arc metal plasma. Positively biased, long cylindrical probes were placed on the side and downstream of a negatively pulsed biased stainless steel sphere of 1 in. (25.4 mm) diameter. The amplitude and width of the negative high voltage pulses (HVPs) were 2 kV, 5 kV, 10 kV, and 2 µs, 4 µs, 10 µs, respectively. The variation of the probe (electron) current during the HVP is a direct measure for the sheath expansion and retreat. Maximum sheath sizes were determined for the different parameters of the HVP. The expected rarefaction zone behind the biased sphere (wake) due to the fast plasma flow was clearly established and quantified.

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.

Direct Visualization of the Outer Membrane of Mycobacteria and Corynebacteria in Their Native State▿ †

PubMed Central

Zuber, Benoît; Chami, Mohamed; Houssin, Christine; Dubochet, Jacques; Griffiths, Gareth; Daffé, Mamadou

2008-01-01

The cell envelope of mycobacteria, which include the causative agents of tuberculosis and leprosy, is crucial for their success as pathogens. Despite a continued strong emphasis on identifying the multiple chemical components of this envelope, it has proven difficult to combine its components into a comprehensive structural model, primarily because the available ultrastructural data rely on conventional electron microscopy embedding and sectioning, which are known to induce artifacts. The existence of an outer membrane bilayer has long been postulated but has never been directly observed by electron microscopy of ultrathin sections. Here we have used cryo-electron microscopy of vitreous sections (CEMOVIS) to perform a detailed ultrastructural analysis of three species belonging to the Corynebacterineae suborder, namely, Mycobacterium bovis BCG, Mycobacterium smegmatis, and Corynebacterium glutamicum, in their native state. We provide new information that accurately describes the different layers of the mycobacterial cell envelope and challenges current models of the organization of its components. We show a direct visualization of an outer membrane, analogous to that found in gram-negative bacteria, in the three bacterial species examined. Furthermore, we demonstrate that mycolic acids, the hallmark of mycobacteria and related genera, are essential for the formation of this outer membrane. In addition, a granular layer and a low-density zone typifying the periplasmic space of gram-positive bacteria are apparent in CEMOVIS images of mycobacteria and corynebacteria. Based on our observations, a model of the organization of the lipids in the outer membrane is proposed. The architecture we describe should serve as a reference for future studies to relate the structure of the mycobacterial cell envelope to its function. PMID:18567661

Direct visualization of the outer membrane of mycobacteria and corynebacteria in their native state.

PubMed

Zuber, Benoît; Chami, Mohamed; Houssin, Christine; Dubochet, Jacques; Griffiths, Gareth; Daffé, Mamadou

2008-08-01

The cell envelope of mycobacteria, which include the causative agents of tuberculosis and leprosy, is crucial for their success as pathogens. Despite a continued strong emphasis on identifying the multiple chemical components of this envelope, it has proven difficult to combine its components into a comprehensive structural model, primarily because the available ultrastructural data rely on conventional electron microscopy embedding and sectioning, which are known to induce artifacts. The existence of an outer membrane bilayer has long been postulated but has never been directly observed by electron microscopy of ultrathin sections. Here we have used cryo-electron microscopy of vitreous sections (CEMOVIS) to perform a detailed ultrastructural analysis of three species belonging to the Corynebacterineae suborder, namely, Mycobacterium bovis BCG, Mycobacterium smegmatis, and Corynebacterium glutamicum, in their native state. We provide new information that accurately describes the different layers of the mycobacterial cell envelope and challenges current models of the organization of its components. We show a direct visualization of an outer membrane, analogous to that found in gram-negative bacteria, in the three bacterial species examined. Furthermore, we demonstrate that mycolic acids, the hallmark of mycobacteria and related genera, are essential for the formation of this outer membrane. In addition, a granular layer and a low-density zone typifying the periplasmic space of gram-positive bacteria are apparent in CEMOVIS images of mycobacteria and corynebacteria. Based on our observations, a model of the organization of the lipids in the outer membrane is proposed. The architecture we describe should serve as a reference for future studies to relate the structure of the mycobacterial cell envelope to its function.

Multianode cylindrical proportional counter for high count rates

DOEpatents

Hanson, J.A.; Kopp, M.K.

1980-05-23

A cylindrical, multiple-anode proportional counter is provided for counting of low-energy photons (< 60 keV) at count rates of greater than 10/sup 5/ counts/sec. A gas-filled proportional counter cylinder forming an outer cathode is provided with a central coaxially disposed inner cathode and a plurality of anode wires disposed in a cylindrical array in coaxial alignment with and between the inner and outer cathodes to form a virtual cylindrical anode coaxial with the inner and outer cathodes. The virtual cylindrical anode configuration improves the electron drift velocity by providing a more uniform field strength throughout the counter gas volume, thus decreasing the electron collection time following the detection of an ionizing event. This avoids pulse pile-up and coincidence losses at these high count rates. Conventional RC position encoding detection circuitry may be employed to extract the spatial information from the counter anodes.

Multianode cylindrical proportional counter for high count rates

DOEpatents

Hanson, James A.; Kopp, Manfred K.

1981-01-01

A cylindrical, multiple-anode proportional counter is provided for counting of low-energy photons (<60 keV) at count rates of greater than 10.sup.5 counts/sec. A gas-filled proportional counter cylinder forming an outer cathode is provided with a central coaxially disposed inner cathode and a plurality of anode wires disposed in a cylindrical array in coaxial alignment with and between the inner and outer cathodes to form a virtual cylindrical anode coaxial with the inner and outer cathodes. The virtual cylindrical anode configuration improves the electron drift velocity by providing a more uniform field strength throughout the counter gas volume, thus decreasing the electron collection time following the detection of an ionizing event. This avoids pulse pile-up and coincidence losses at these high count rates. Conventional RC position encoding detection circuitry may be employed to extract the spatial information from the counter anodes.

Characterizing Relativistic Electrons Flux Enhancement Events using sensors onboard SAMPEX and POLAR

NASA Astrophysics Data System (ADS)

Kanekal, S. G.; Selesnick, R. S.; Baker, D. N.; Blake, J. B.

2004-12-01

Relativistic electron fluxes in the Earth's outer Van Allen belt are highly variable with flux enhancements of several orders of magnitude occurring on time scales of a few days. Radiation belt electrons often are energized to relativistic energies when the magnetosphere is subjected to high solar wind speed and the southward turning of the interplanetary magnetic field. Characterization of electron acceleration properties such as electron spectra and flux isotropization are important in understanding acceleration models. We use sensors onboard SAMPEX and POLAR to measure and survey systematically these properties. SAMPEX measurements cover the entire outer zone for more than a decade from mid 1992 to mid 2004 and POLAR covers the time period from mid 1996 to the present. We use the pulse height analyzed data from the PET detector onboard SAMPEX to measure electron spectra. Fluxes measured by the HIST detector onboard POLAR together with the PET measurements are used to characterize isotropization times. This paper presents electron spectra and isotropization time scales for a few representative events. We will eventually extend these measurements and survey the entire solar cycle 23.

Self-sterilization of bodies during outer planet entry

NASA Technical Reports Server (NTRS)

Hoffman, A. R.; Jaworski, W.; Taylor, D. M.

1974-01-01

A body encountering the atmosphere of an outer planet is subjected to heat loads which could result in high temperature conditions that render terrestrial organisms on or within the body nonviable. To determine whether an irregularly shaped entering body, consisting of several different materials, would be sterilized during inadvertent entry at high velocity, the thermal response of a typical outer planet spacecraft instrument was studied. The results indicate that the Teflon insulated cable and electronic circuit boards may not experience sterilizing temperatures during a Jupiter, Saturn, or Titan entry. Another conclusion of the study is that small plastic particles entering Saturn from outer space have wider survival corridors than do those at Jupiter.

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).

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).

Confined Assembly of Hollow Carbon Spheres in Carbonaceous Nanotube: A Spheres-in-Tube Carbon Nanostructure with Hierarchical Porosity for High-Performance Supercapacitor.

PubMed

Chen, Ze; Ye, Sunjie; Evans, Stephen D; Ge, Yuanhang; Zhu, Zhifeng; Tu, Yingfeng; Yang, Xiaoming

2018-05-01

Carbonaceous nanotubes (CTs) represent one of the most popular and effective carbon electrode materials for supercapacitors, but the electrochemistry performance of CTs is largely limited by their relatively low specific surface area, insufficient usage of intratube cavity, low content of heteroatom, and poor porosity. An emerging strategy for circumventing these issues is to design novel porous CT-based nanostructures. Herein, a spheres-in-tube nanostructure with hierarchical porosity is successfully engineered, by encapsulating heteroatom-doping hollow carbon spheres into one carbonaceous nanotube (HCSs@CT). This intriguing nanoarchitecture integrates the merits of large specific surface area, good porosity, and high content of heteroatoms, which synergistically facilitates the transportation and exchange of ions and electrons. Accordingly, the as-prepared HCSs@CTs possess outstanding performances as electrode materials of supercapacitors, including superior capacitance to that of CTs, HCSs, and their mixtures, coupled with excellent cycling life, demonstrating great potential for applications in energy storage. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inner and Outer Coordination Shells of Mg(2+) in CorA Selectivity Filter from Molecular Dynamics Simulations.

PubMed

Kitjaruwankul, Sunan; Wapeesittipan, Pattama; Boonamnaj, Panisak; Sompornpisut, Pornthep

2016-01-28

Structural data of CorA Mg(2+) channels show that the five Gly-Met-Asn (GMN) motifs at the periplasmic loop of the pentamer structure form a molecular scaffold serving as a selectivity filter. Unfortunately, knowledge about the cation selectivity of Mg(2+) channels remains limited. Since Mg(2+) in aqueous solution has a strong first hydration shell and apparent second hydration sphere, the coordination structure of Mg(2+) in a CorA selectivity filter is expected to be different from that in bulk water. Hence, this study investigated the hydration structure and ligand coordination of Mg(2+) in a selectivity filter of CorA using molecular dynamics (MD) simulations. The simulations reveal that the inner-shell structure of Mg(2+) in the filter is not significantly different from that in aqueous solution. The major difference is the characteristic structural features of the outer shell. The GMN residues engage indirectly in the interactions with the metal ion as ligands in the second shell of Mg(2+). Loss of hydrogen bonds between inner- and outer-shell waters observed from Mg(2+) in bulk water is mostly compensated by interactions between waters in the first solvation shell and the GMN motif. Some water molecules in the second shell remain in the selectivity filter and become less mobile to support the metal binding. Removal of Mg(2+) from the divalent cation sensor sites of the protein had an impact on the structure and metal binding of the filter. From the results, it can be concluded that the GMN motif enhances the affinity of the metal binding site in the CorA selectivity filter by acting as an outer coordination ligand.

Development of a low energy electron spectrometer for SCOPE

NASA Astrophysics Data System (ADS)

Tominaga, Yuu; Saito, Yoshifumi; Yokota, Shoichiro

We are newly developing a low-energy charged particle analyzer for the future satellite mission SCOPE (cross Scale COupling in the Plasma universE). The main purpose of the mission is to understand the cross scale coupling between macroscopic MHD scale phenomena and microscopic ion and electron-scale phenomena. In order to under-stand the dynamics of plasma in small scales, we need to observe the plasma with an analyzer which has high time resolution. For ion-scale phenomena, the time resolution must be as high as ion cyclotron frequency (-10 sec) in Earth's magnetosphere. However, for electron-scale phe-nomena, the time resolution must be as high as electron cyclotron frequency (-1 msec). The GEOTAIL satellite that observes Earth's magnetosphere has the analyzer whose time resolution is 12 sec, so the satellite can observe ion-scale phenomena. However in the SCOPE mission, we will go further to observe electron-scale phenomena. Then we need analyzers that have at least several msec time resolution. Besides, we need to make the analyzer as small as possible for the volume and weight restrictions of the satellite. The diameter of the top-hat analyzer must be smaller than 20 cm. In this study, we are developing an electrostatic analyzer that meets such requirements using numerical simulations. The electrostatic analyzer is a spherical/toroidal top-hat electrostatic analyzer with three nested spherical/toroidal deflectors. Using these deflectors, the analyzer measures charged particles simultaneously in two different energy ranges. Therefore time res-olution of the analyzer can be doubled. With the analyzer, we will measure energies from 10 eV to 22.5 keV. In order to obtain three-dimensional distribution functions of low energy parti-cles, the analyzer must have 4-pi str field of view. Conventional electrostatic analyzers use the spacecraft spin to have 4-pi field of view. So the time resolution of the analyzer depends on the spin frequency of the spacecraft. However, we cannot secure the several msec time resolution by using the spacecraft spin. In the SCOPE mission, we set 8 pairs of two nested electrostatic analyzers on each side of the spacecraft, which enable us to secure 4-pi field of view altogether. Then the time resolution of the analyzer does not depend on the spacecraft spin. Given that the sampling time of the analyzer is 0.5 msec, the time resolution of the analyzer can be 8 msec. In order to secure the time resolution as high as 10 msec, the geometric factor of the analyzer has to be as high as 8*10-3 (cm2 str eV/eV/22.5deg). Higher geometric factor requires bigger instrument. However, we have to reduce the volume and weight of the instrument to set it on the satellite. Under these restrictions, we have realized the analyzer which has the geometric factors of 7.5*10-3 (cm2 str eV/eV/22.5deg) (inner sphere) and 10.0*10-3 (cm2 str eV/eV/22.5deg) (outer sphere) with diameter of 17.4 cm.

Vanadium(V) Reduction by Shewanella oneidensis MR-1 Requires Menaquinone and Cytochromes from the Cytoplasmic and Outer Membranes

PubMed Central

Myers, Judith M.; Antholine, William E.; Myers, Charles R.

2004-01-01

The metal-reducing bacterium Shewanella oneidensis MR-1 displays remarkable anaerobic respiratory plasticity, which is reflected in the extensive number of electron transport components encoded in its genome. In these studies, several cell components required for the reduction of vanadium(V) were determined. V(V) reduction is mediated by an electron transport chain which includes cytoplasmic membrane components (menaquinone and the tetraheme cytochrome CymA) and the outer membrane (OM) cytochrome OmcB. A partial role for the OM cytochrome OmcA was evident. Electron spin resonance spectroscopy demonstrated that V(V) was reduced to V(IV). V(V) reduction did not support anaerobic growth. This is the first report delineating specific electron transport components that are required for V(V) reduction and of a role for OM cytochromes in the reduction of a soluble metal species. PMID:15006760

Ca2+ and Mg2+-enhanced reduction of arsenazo III to its anion free radical metabolite and generation of superoxide anion by an outer mitochondrial membrane azoreductase.

PubMed

Moreno, S N; Mason, R P; Docampo, R

1984-12-10

At the concentrations usually employed as a Ca2+ indicator, arsenazo III underwent a one-electron reduction by rat liver mitochondria to produce an azo anion radical as demonstrated by electron-spin resonance spectroscopy. Either NADH or NADPH could serve as a source of reducing equivalents for the production of this free radical by intact rat liver mitochondria. Under aerobic conditions, addition of arsenazo III to rat liver mitochondria produced an increase in electron flow from NAD(P)H to molecular oxygen, generating superoxide anion. NAD(P)H generated from endogenous mitochondrial NAD(P)+ by intramitochondrial reactions could not be used for the NAD(P)H azoreductase reaction unless the mitochondria were solubilized by detergent or anaerobiosis. In addition, NAD(P)H azoreductase activity was higher in the crude outer mitochondrial membrane fraction than in mitoplasts and intact mitochondria. The steady-state concentration of the azo anion radical and the arsenazo III-stimulated cyanide-insensitive oxygen consumption were enhanced by calcium and magnesium, suggesting that, in addition to an enhanced azo anion radical-stabilization by complexation with the metal ions, enhanced reduction of arsenazo III also occurred. Accordingly, addition of cations to crude outer mitochondrial membrane preparations increased arsenazo III-stimulated cyanide-insensitive O2 consumption, H2O2 formation, and NAD(P)H oxidation. Antipyrylazo III was much less effective than arsenazo III in increasing superoxide anion formation by rat liver mitochondria and gave a much weaker electron spin resonance spectrum of an azo anion radical. These results provide direct evidence of an azoreductase activity associated with the outer mitochondrial membrane and of a stimulation of arsenazo III reduction by cations.

Outer Radiation Belt Dropout Dynamics Following the Arrival of Two Interplanetary Coronal Mass Ejections

NASA Technical Reports Server (NTRS)

Alves, L. R.; Da Silva, L. A.; Souza, V. M.; Sibeck, D. G.; Jauer, P. R.; Vieira, L. E. A.; Walsh, B. M.; Silveira, M. V. D.; Marchezi, J. P.; Rockenbach, M.;

A long-lived relativistic electron storage ring embedded in Earth's Outer Van Allen belt

DOE PAGES

Baker, D. N.; Kanekal, S. G.; Hoxie, V. C.; ...

2013-02-28

Since their discovery over 50 years ago, the Earth’s Van Allen radiation belts are thought to consist of two distinct zones of trapped, highly energetic charged particles. The outer zone is comprised predominantly of mega-electron volt (MeV) electrons that wax and wane in intensity on time scales ranging from hours to days depending primarily on external forcing by the solar wind. Thus, the spatially separated inner zone is comprised of commingled high-energy electrons and very energetic positive ions (mostly protons), the latter being stable in intensity levels over years to decades. In situ energy-specific and temporally resolved spacecraft observations revealmore » an isolated third ring, or torus, of high-energy (E > 2 MeV) electrons that formed on 2 September 2012 and persisted largely unchanged in the geocentric radial range of 3.0 to ~3.5 Earth radii for over four weeks before being disrupted (and virtually annihilated) by a powerful interplanetary shock wave passage.« less

Gradual Diffusion and Punctuated Phase Space Density Enhancements of Highly Relativistic Electrons: Van Allen Probes Observations

NASA Technical Reports Server (NTRS)

Baker, D. N.; Jaynes, A. N.; Li, X.; Henderson, M. G.; Kanekal, S. G.; Reeves, G. D.; Spence, H. E.; Claudepierre, S. G.; Fennell, J. F.; Hudson, M. K.

2014-01-01

The dual-spacecraft Van Allen Probes mission has provided a new window into mega electron volt (MeV) particle dynamics in the Earth's radiation belts. Observations (up to E (is) approximately 10MeV) show clearly the behavior of the outer electron radiation belt at different timescales: months-long periods of gradual inward radial diffusive transport and weak loss being punctuated by dramatic flux changes driven by strong solar wind transient events. We present analysis of multi-MeV electron flux and phase space density (PSD) changes during March 2013 in the context of the first year of Van Allen Probes operation. This March period demonstrates the classic signatures both of inward radial diffusive energization and abrupt localized acceleration deep within the outer Van Allen zone (L (is) approximately 4.0 +/- 0.5). This reveals graphically that both 'competing' mechanisms of multi-MeV electron energization are at play in the radiation belts, often acting almost concurrently or at least in rapid succession.

Molecular-Scale Study of Aspartate Adsorption on Goethite and Competition with Phosphate.

PubMed

Yang, Yanli; Wang, Shengrui; Xu, Yisheng; Zheng, Binghui; Liu, Jingyang

2016-03-15

Knowledge of the interfacial interactions between aspartate and minerals, especially its competition with phosphate, is critical to understanding the fate and transport of amino acids in the environment. Adsorption reactions play important roles in the mobility, bioavailability, and degradation of aspartate and phosphate. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements and density functional theory (DFT) calculations were used to investigate the interfacial structures and their relative contributions in single-adsorbate and competition systems. Our results suggest three dominant mechanisms for aspartate: bidentate inner-sphere coordination involving both α- and γ-COO(-), outer-sphere complexation via electrostatic attraction and H-bonding between aspartate NH2 and goethite surface hydroxyls. The interfacial aspartate is mainly governed by pH and is less sensitive to changes of ionic strength and aspartate concentration. The phosphate competition significantly reduces the adsorption capacity of aspartate on goethite. Whereas phosphate adsorption is less affected by the presence of aspartate, including the relative contributions of diprotonated monodentate, monoprotonated bidentate, and nonprotonated bidentate structures. The adsorption process facilitates the removal of bioavailable aspartate and phosphate from the soil solution as well as from the sediment pore water and the overlying water.

The implementation of aerial object recognition algorithm based on contour descriptor in FPGA-based on-board vision system

NASA Astrophysics Data System (ADS)

Babayan, Pavel; Smirnov, Sergey; Strotov, Valery

2017-10-01

This paper describes the aerial object recognition algorithm for on-board and stationary vision system. Suggested algorithm is intended to recognize the objects of a specific kind using the set of the reference objects defined by 3D models. The proposed algorithm based on the outer contour descriptor building. The algorithm consists of two stages: learning and recognition. Learning stage is devoted to the exploring of reference objects. Using 3D models we can build the database containing training images by rendering the 3D model from viewpoints evenly distributed on a sphere. Sphere points distribution is made by the geosphere principle. Gathered training image set is used for calculating descriptors, which will be used in the recognition stage of the algorithm. The recognition stage is focusing on estimating the similarity of the captured object and the reference objects by matching an observed image descriptor and the reference object descriptors. The experimental research was performed using a set of the models of the aircraft of the different types (airplanes, helicopters, UAVs). The proposed orientation estimation algorithm showed good accuracy in all case studies. The real-time performance of the algorithm in FPGA-based vision system was demonstrated.

Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

PubMed

Yan, Wei; Hu, Shan; Jing, Chuanyong

2012-04-15

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs

Reaction of Hydroquinone with Hematite I. Study of Adsorption by Electrochemical-Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy

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

Stack, Andrew G; Eggleston, Carrick M; Engelhard, Mark H

2004-06-15

The reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate ofreductive dissolution, especially by iron-reducing bacteria. Here, the electrochemical and physical properties of hydroquinone adsorbed on hematite surfaces at pH 2.5–3 were investigated with cyclic voltammetry (CV), electrochemical-scanning tunneling microscopy (EC-STM), and X-ray photoelectron spectroscopy (XPS). An oxidation peak for hydroquinone was observed in the CV experiments, as well as (photo)reduction of iron and decomposition of the solvent. The EC-STM results indicate that hydroquinone sometimes forms an ordered monolayer with ~1.1 H₂/nm², but can be fairly disordered (especiallymore » when viewed at larger scales). XPS results indicate that hydroquinone and benzoquinone are retained at the interface in increasing amounts as the reaction proceeds, but reduced iron is not observed. These results suggest that quinones do not adsorb by an inner-sphere complex where adsorbate–surface interactions determine the adsorbate surface structure, but rather in an outer-sphere complex where interactions among the adsorbate molecules dominate.« less

Reaction of hydroquinone with hematite I. Study of asdsorption by electrochemical-scanning tunneling microscopy and X-ray photoelectron spectroscopy.

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

Stack, Andrew G; Eggleston, Carrick M; Engelhard, Mark H

2003-12-01

The reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate of reductive dissolution, especially by iron-reducing bacteria. Here, the electrochemical and physical properties of hydroquinone adsorbed on hematite surfaces at pH 2.5-3 were investigated with cyclic voltammetry (CV), electrochemical-scanning tunneling microscopy (EC-STM), and X-ray photoelectron spectroscopy (XPS). An oxidation peak for hydroquinone was observed in the CV experiments, as well as (photo)reduction of iron and decomposition of the solvent. The EC-STM results indicate that hydroquinone sometimes forms an ordered monolayer with {approx}1.1 QH{sub 2}/nm{sup 2}, but can bemore » fairly disordered (especially when viewed at larger scales). XPS results indicate that hydroquinone and benzoquinone are retained at the interface in increasing amounts as the reaction proceeds, but reduced iron is not observed. These results suggest that quinones do not adsorb by an inner-sphere complex where adsorbate-surface interactions determine the adsorbate surface structure, but rather in an outer-sphere complex where interactions among the adsorbate molecules dominate.« less

Heterobimetallic Catalysis: Platinum-Gold-Catalyzed Tandem Cyclization/C-X Coupling Reaction of (Hetero)Arylallenes with Nucleophiles.

PubMed

Alonso, José Miguel; Muñoz, María Paz

2018-04-16

Heterobimetallic catalysis offers new opportunities for reactivity and selectivity but still presents challenges, and only a few metal combinations have been explored so far. Reported here is a Pt-Au heterobimetallic catalyst system for the synthesis of a family of multi-heteroaromatic structures through tandem cyclization/C-X coupling reaction. Au-catalyzed 6-endo-cyclization takes place as the first fast step. Pt-Au clusters are proposed to be responsible for the increased reactivity in the second step, that is, the intermolecular nucleophilic addition which occurs through an outer-sphere mechanism by hybrid homogeneous-heterogeneous catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

1H NMR study of inclusion compounds of phenylurea derivatives in β-cyclodextrin

NASA Astrophysics Data System (ADS)

Dupuy, N.; Barbry, D.; Bria, M.; Marquis, S.; Vrielynck, L.; Kister, J.

2005-04-01

Proton nuclear magnetic resonance spectroscopy ( 1H NMR), which has become an important tool for the study "in situ" of β-cyclodextrin (β-CD) complexes, was used to study and structurally characterize the inclusion complexes formed between β-CD and isoproturon, fenuron, monuron and diuron. The high variation of the chemical shifts from the proton located inside the cavity (H-3, H-5 and H-6) coupled with the non variation of the one located outer sphere of the β-CD (H-1, H-2 and H-4) provided clear evidence of the inclusion phenomena. Two-dimensional rotating frame Overhauser effect spectroscopy (ROESY) experiments were carried out to further support the proposed inclusion mode.

Strong efficiency improvement in dye-sensitized solar cells by novel multi-dimensional TiO2 photoelectrode

NASA Astrophysics Data System (ADS)

Zhao, Fengyang; Ma, Rong; Jiang, Yongjian

2018-03-01

Titanium dioxide (TiO2) based dye-sensitized solar cells (DSSCs) often exhibit superior power conversion performance. Here we report a DSSC with novel hierarchical TiO2 composite structure (TCS) composed of anatase TiO2 micro-spheres and rutile TiO2 nanobelt framework by hydrothermal approach for high-performance. As photoanode, the TCS based DSSC shows a strong efficiency enhancement by 58% compared with Degussa TiO2 (P25)-DSSC (4.33%). The excellent performance is mainly attribute to its special multi-dimensional structures of TiO2: much active sites of 0D nanoparticle with exposed excellent {001} facet, special electronic transmission channel of 1D nanobelt, good dye adsorption capacity of 2D nanosheet and high light scattering ability of 3D micro-spheres. The novel multi-dimensional TCS materials will open up a new avenue to the electronic devices fields.

Tribological properties of graphene oxide and carbon spheres as lubricating additives

NASA Astrophysics Data System (ADS)

Song, Haojie; Wang, Zhiqiang; Yang, Jin

2016-10-01

The purpose of this paper was to investigate the tribological properties of carbon materials with various morphologies [i.e., graphene oxide (GO) and carbon spheres (CSs)] utilized as lubricating additives on a ball-plate tribotester. The morphology and spectroscopy characterization of GO and CSs were investigated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. Friction and wear properties of the sunflower seed oil filled with GO and CSs were investigated by using a MS-T3000 ball-on-disk apparatus. Results show that the sunflower seed oil containing 0.3 wt% GO nanosheets exhibited a substantial diminution in friction and wear compared with the 3.0 wt% CSs as sunflower seed oil additives. Formation of low-shear strength tribofilms containing GO and its self-lubricating behavior was the key factor in reduction of the friction and prevention from wear and deformation. In addition, friction mechanism of CSs was also discussed.

Solvothermal synthesis of monodisperse LiFePO4 micro hollow spheres as high performance cathode material for lithium ion batteries.

PubMed

Yang, Shiliu; Hu, Mingjun; Xi, Liujiang; Ma, Ruguang; Dong, Yucheng; Chung, C Y

2013-09-25

A microspherical, hollow LiFePO4 (LFP) cathode material with polycrystal structure was simply synthesized by a solvothermal method using spherical Li3PO4 as the self-sacrificed template and FeCl2·4H2O as the Fe(2+) source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the LFP micro hollow spheres have a quite uniform size of ~1 μm consisting of aggregated nanoparticles. The influences of solvent and Fe(2+) source on the phase and morphology of the final product were chiefly investigated, and a direct ion exchange reaction between spherical Li3PO4 templates and Fe(2+) ions was firstly proposed on the basis of the X-ray powder diffraction (XRD) transformation of the products. The LFP nanoparticles in the micro hollow spheres could finely coat a uniform carbon layer ~3.5 nm by a glucose solution impregnating-drying-sintering process. The electrochemical measurements show that the carbon coated LFP materials could exhibit high charge-discharge capacities of 158, 144, 125, 101, and even 72 mAh g(-1) at 0.1, 1, 5, 20, and 50 C, respectively. It could also maintain 80% of the initial discharge capacity after cycling for 2000 times at 20 C.

Synthesis of hydroxyapatite nanoparticles by a novel ultrasonic assisted with mixed hollow sphere template method.

PubMed

Gopi, D; Indira, J; Kavitha, L; Sekar, M; Mudali, U Kamachi

2012-07-01

Hydroxyapatite (HAP) is the main inorganic component of bone material and is widely used in various biomedical applications due to its excellent bioactivity and biocompatibility. In this paper, we have reported the synthesis of hydroxyapatite nanoparticles by a novel ultrasonic assisted mixed template directed method. In this method glycine-acrylic acid (GLY-AA) hollow spheres were used as an organic template which could be prepared by mixing of glycine with acrylic acid. The as-synthesized HAP nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) and tunnelling electron microscope (TEM) to investigate the nature of bonding, crystallinity, size and shape. The thermal stability of as-synthesized nanoparticles was also investigated by the thermo gravimetric analysis (TGA). The effect of ultrasonic irradiation time on the crystallinity and size of the HAP nanoparticles in presence of glycine-acrylic acid hollow spheres template were investigated. From the inspection of the above results it is confirmed that the crystallinity and size of the HAP nanoparticles decrease with increasing ultrasonic irradiation time. Hence the proposed synthesis strategy provides a facile pathway to obtain nano sized HAP with high quality, suitable size and morphology. Copyright © 2012 Elsevier B.V. All rights reserved.

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 + .

Mercury(II) removal from aqueous solutions and wastewaters using a novel cation exchanger derived from coconut coir pith and its recovery.

PubMed

Anirudhan, T S; Divya, L; Ramachandran, M

2008-09-15

A new adsorbent (PGCP-COOH) having carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto coconut coir pith, CP (a coir industry-based lignocellulosic residue), using potassium peroxydisulphate as an initiator and in the presence of N,N'-methylenebisacrylamide as a cross-linking agent. The adsorbent was characterized with the help of infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and potentiometric titrations. The ability of PGCP-COOH to remove Hg(II) from aqueous solutions was assessed using batch adsorption technique under kinetic and equilibrium conditions. Adsorbent exhibits very high adsorption potential for Hg(II) and more than 99.0% removal was achieved in the pH range 5.5-8.0. Adsorption process was found to follow first-order-reversible kinetics. An increase of ionic strength of the medium caused a decrease in metal removal, indicating the occurrence of outer-sphere surface complex mechanism. The equilibrium data were fitted well by the Freundlich isotherm model (R(2)=0.99; chi(2)=1.81). The removal efficiency was tested using chlor-alkali industry wastewater. Adsorption isotherm experiments were also conducted for comparison using a commercial carboxylate-functionalized ion exchanger, Ceralite IRC-50. Regeneration experiments were tried for four cycles and results indicate a capacity loss of <9.0%.

Energy-dependent dynamics of keV to MeV electrons in the inner zone, outer zone, and slot regions.

PubMed

Reeves, Geoffrey D; Friedel, Reiner H W; Larsen, Brian A; Skoug, Ruth M; Funsten, Herbert O; Claudepierre, Seth G; Fennell, Joseph F; Turner, Drew L; Denton, Mick H; Spence, Harlan E; Blake, J Bernard; Baker, Daniel N

2016-01-01

We present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are more common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of "slot filling" events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy- and L shell-dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions.

Energy-dependent dynamics of keV to MeV electrons in the inner zone, outer zone, and slot regions

DOE PAGES

Reeves, Geoffrey D.; Friedel, Reiner H. W.; Larsen, Brian A.; ...

2016-01-28

Here, we present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are moremore » common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of “slot filling” events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy- and L shell-dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions.« less

Energy‐dependent dynamics of keV to MeV electrons in the inner zone, outer zone, and slot regions

PubMed Central

Friedel, Reiner H. W.; Larsen, Brian A.; Skoug, Ruth M.; Funsten, Herbert O.; Claudepierre, Seth G.; Fennell, Joseph F.; Turner, Drew L.; Denton, Mick H.; Spence, Harlan E.; Blake, J. Bernard; Baker, Daniel N.

2016-01-01

Abstract We present observations of the radiation belts from the Helium Oxygen Proton Electron and Magnetic Electron Ion Spectrometer particle detectors on the Van Allen Probes satellites that illustrate the energy dependence and L shell dependence of radiation belt enhancements and decays. We survey events in 2013 and analyze an event on 1 March in more detail. The observations show the following: (a) at all L shells, lower energy electrons are enhanced more often than higher energies; (b) events that fill the slot region are more common at lower energies; (c) enhancements of electrons in the inner zone are more common at lower energies; and (d) even when events do not fully fill the slot region, enhancements at lower energies tend to extend to lower L shells than higher energies. During enhancement events the outer zone extends to lower L shells at lower energies while being confined to higher L shells at higher energies. The inner zone shows the opposite with an outer boundary at higher L shells for lower energies. Both boundaries are nearly straight in log(energy) versus L shell space. At energies below a few 100 keV, radiation belt electron penetration through the slot region into the inner zone is commonplace, but the number and frequency of “slot filling” events decreases with increasing energy. The inner zone is enhanced only at energies that penetrate through the slot. Energy‐ and L shell‐dependent losses (that are consistent with whistler hiss interactions) return the belts to more quiescent conditions. PMID:27818855

Self-assembly approach toward magnetic silica-type nanoparticles of different shapes from reverse block copolymer mesophases.

PubMed

Garcia, Carlos B W; Zhang, Yuanming; Mahajan, Surbhi; DiSalvo, Francis; Wiesner, Ulrich

2003-11-05

In the present study poly(isoprene-block-ethylene oxide), PI-b-PEO, block copolymers are used to structure iron oxide and silica precursors into reverse mesophases, which upon dissolution of the organic matrix lead to well-defined nanoparticles of spheres, cylinders, and plates based on the original structure of the mesophase prepared. The hybrid mesophases with sphere, cylinder, and lamellar morphologies containing the inorganic components in the minority phases are characterized through a combination of small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). After heat treatments the respective nanoparticles on mica surfaces are characterized by scanning force microscopy (SFM). X-ray diffraction (XRD) and superconducting quantum interference device (SQUID) magnetometer measurements are performed to demonstrate that the heat treatment leads to the formation of a magnetic gamma-Fe2O3 crystalline phase within the amorphous aluminosilicate. The results pave the way to functional, i.e., magnetic nanoparticles where the size, shape, and iron oxide concentration can be controlled opening a range of possible applications.

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.

Simulation of perturbation produced by an absorbing spherical body in collisionless plasma

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

Krasovsky, V. L., E-mail: vkrasov@iki.rssi.ru; Kiselyov, A. A., E-mail: alexander.kiselyov@stonehenge-3.net.ru; Dolgonosov, M. S.

2017-01-15

A steady plasma state reached in the course of charging of an absorbing spherical body is found using computational methods. Numerical simulations provide complete information on this process, thereby allowing one to find the spatiotemporal dependences of the physical quantities and observe the kinetic phenomena accompanying the formation of stable electron and ion distributions in phase space. The distribution function of trapped ions is obtained, and their contribution to the screening of the charged sphere is determined. The sphere charge and the charge of the trapped-ion cloud are determined as functions of the unperturbed plasma parameters.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

PubMed Central

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

2017-01-01

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

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

Trends in Ionization Energy of Transition-Metal Elements

ERIC Educational Resources Information Center

Matsumoto, Paul S.

2005-01-01

A rationale for the difference in the periodic trends in the ionization energy of the transition-metal elements versus the main-group elements is presented. The difference is that in the transition-metal elements, the electrons enter an inner-shell electron orbital, while in the main-group elements, the electrons enter an outer-shell electron…

Relativistic electron dynamics produced by azimuthally localized poloidal mode ULF waves: Boomerang-shaped pitch angle evolutions

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

Hao, Y. X.; Zong, Q. -G.; Zhou, X. -Z.

Here, we present an analysis of “boomerang-shaped” pitch angle evolutions of outer radiation belt relativistic electrons observed by the Van Allen Probes after the passage of an interplanetary shock on 7 June 2014. The flux at different pitch angles is modulated by Pc5 waves, with equatorially mirroring electrons reaching the satellite first. For 90° pitch angle electrons, the phase change of the flux modulations across energy exceeds 180° and increasingly tilts with time. Using estimates of the arrival time of particles of different pitch angles at the spacecraft location, a scenario is investigated in which shock-induced ULF waves interact withmore » electrons through the drift resonance mechanism in a localized region westward of the spacecraft. Numerical calculations on particle energy gain with the modified ULF wavefield reproduce the observed boomerang stripes and modulations in the electron energy spectrogram. The study of boomerang stripes and their relationship to drift resonance taking place at a location different from the observation point adds new understanding of the processes controlling the dynamics of the outer radiation belt.« less

Forecasting and remote sensing outer belt relativistic electrons from low Earth orbit

DOE PAGES

Chen, Yue; Reeves, Geoffrey D.; Cunningham, Gregory S.; ...

2016-02-15

Our study demonstrates the feasibility and reliability of using observations from low Earth orbit (LEO) to forecast and nowcast relativistic electrons in the outer radiation belt. Furthermore, we first report a high cross-energy, cross-pitch-angle coherence discovered between the trapped MeV electrons and precipitating approximately hundreds (~100s) of keV electrons—observed by satellites with very different altitudes—with correlation coefficients as high as ≳ 0.85. We then tested the feasibility of applying linear prediction filters to LEO data to predict the arrival of new MeV electrons during geomagnetic storms, as well as their evolving distributions afterward, based on the coherence. Reliability of thesemore » predictive filters is quantified by the performance efficiency with values as high as 0.74 when driven merely by LEO observations (or up to 0.94 with the inclusion of in situ MeV electron measurements). Finally, a hypothesis based upon the wave-particle resonance theory is proposed to explain the coherence, and a first-principle electron tracing model yields supporting evidence.« less

Relativistic electron dynamics produced by azimuthally localized poloidal mode ULF waves: Boomerang-shaped pitch angle evolutions

NASA Astrophysics Data System (ADS)

Hao, Y.; Zong, Q.; Zhou, X.; Rankin, R.; Chen, X.; Liu, Y.; Fu, S.; Spence, H. E.; Blake, J. B.; Reeves, G. D.

2017-12-01

We present an analysis of "boomerang-shaped" pitch angle evolutions of outer radiation belt relativistic electrons observed by the Van Allen Probes after the passage of an interplanetary shock on June 7th, 2014. The flux at different pitch angles is modulated by Pc5 waves, with equatorially mirroring electrons reaching the satellite first. For 90º pitch angle electrons, the phase change of the flux modulations across energy exceeds 180º, and increasingly tilts with time. Using estimates of the arrival time of particles of different pitch angles at the spacecraft location, a scenario is investigated in which shock-induced ULF waves interact with electrons through the drift resonance mechanism in a localized region westward of the spacecraft. Numerical calculations on particle energy gain with the modified ULF wave field reproduce the observed boomerang stripes and modulations in the electron energy spectrogram. The study of boomerang stripes and their relationship to drift-resonance taking place at a location different from the observation point adds new understanding of the processes controlling the dynamics of the outer radiation belt.

Relativistic electron dynamics produced by azimuthally localized poloidal mode ULF waves: Boomerang-shaped pitch angle evolutions

NASA Astrophysics Data System (ADS)

Hao, Y. X.; Zong, Q.-G.; Zhou, X.-Z.; Rankin, R.; Chen, X. R.; Liu, Y.; Fu, S. Y.; Spence, H. E.; Blake, J. B.; Reeves, G. D.

2017-08-01

We present an analysis of "boomerang-shaped" pitch angle evolutions of outer radiation belt relativistic electrons observed by the Van Allen Probes after the passage of an interplanetary shock on 7 June 2014. The flux at different pitch angles is modulated by Pc5 waves, with equatorially mirroring electrons reaching the satellite first. For 90° pitch angle electrons, the phase change of the flux modulations across energy exceeds 180° and increasingly tilts with time. Using estimates of the arrival time of particles of different pitch angles at the spacecraft location, a scenario is investigated in which shock-induced ULF waves interact with electrons through the drift resonance mechanism in a localized region westward of the spacecraft. Numerical calculations on particle energy gain with the modified ULF wavefield reproduce the observed boomerang stripes and modulations in the electron energy spectrogram. The study of boomerang stripes and their relationship to drift resonance taking place at a location different from the observation point adds new understanding of the processes controlling the dynamics of the outer radiation belt.

Relativistic electron dynamics produced by azimuthally localized poloidal mode ULF waves: Boomerang-shaped pitch angle evolutions

DOE PAGES

Hao, Y. X.; Zong, Q. -G.; Zhou, X. -Z.; ...

2017-07-10

Here, we present an analysis of “boomerang-shaped” pitch angle evolutions of outer radiation belt relativistic electrons observed by the Van Allen Probes after the passage of an interplanetary shock on 7 June 2014. The flux at different pitch angles is modulated by Pc5 waves, with equatorially mirroring electrons reaching the satellite first. For 90° pitch angle electrons, the phase change of the flux modulations across energy exceeds 180° and increasingly tilts with time. Using estimates of the arrival time of particles of different pitch angles at the spacecraft location, a scenario is investigated in which shock-induced ULF waves interact withmore » electrons through the drift resonance mechanism in a localized region westward of the spacecraft. Numerical calculations on particle energy gain with the modified ULF wavefield reproduce the observed boomerang stripes and modulations in the electron energy spectrogram. The study of boomerang stripes and their relationship to drift resonance taking place at a location different from the observation point adds new understanding of the processes controlling the dynamics of the outer radiation belt.« less

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.

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.

Graphene-Wrapped Ni(OH)2 Hollow Spheres as Novel Electrode Material for Supercapacitors.

PubMed

Sun, Jinfeng; Wang, Jinqing; Li, Zhangpeng; Ou, Junfei; Niu, Lengyuan; Wang, Honggang; Yang, Shengrong

2015-09-01

Graphene-wrapped Ni(OH)2 hollow spheres were prepared via electrostatic interaction between poly(diallyldimethylammonium chloride) (PDDA) modified Ni(OH)2 and graphene oxide (GO) in an aqueous dispersion, followed by the reduction of GO. Morphological and structural analysis by field-emission scanning electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis confirmed the successful coating of graphene on Ni(OH)2 hollow spheres with a content of 3.8 wt%. And then its application as electrode material for supercapacitor has been investigated by cyclic voltammetry (CV) and galvanostatic charge-discharge tests. Results show that the sample displays a high capacitance of 1368 F g(-1) at a current density of 1 A g(-1), much better than that of pure Ni(OH)2, illustrating that such composite is a promising candidate as electrode material for supercapacitors.

A Unique 3D Nitrogen-Doped Carbon Composite as High-Performance Oxygen Reduction Catalyst

PubMed Central

Karunagaran, Ramesh; Tung, Tran Thanh; Tran, Diana; Coghlan, Campbell; Doonan, Christian

2017-01-01

The synthesis and properties of an oxygen reduction catalyst based on a unique 3-dimensional (3D) nitrogen doped (N-doped) carbon composite are described. The composite material is synthesised via a two-step hydrothermal and pyrolysis method using bio-source low-cost materials of galactose and melamine. Firstly, the use of iron salts and galactose to hydrothermally produceiron oxide (Fe2O3) magnetic nanoparticle clusters embedded carbon spheres. Secondly, magnetic nanoparticles diffused out of the carbon sphere when pyrolysed in the presence of melamine as nitrogen precursor. Interestingly, many of these nanoparticles, as catalyst-grown carbon nanotubes (CNTs), resulted in the formation of N-doped CNTs and N-doped carbon spheres under the decomposition of carbon and a nitrogen environment. The composite material consists of integrated N-doped carbon microspheres and CNTs show high ORR activity through a predominantly four-electron pathway. PMID:28792432

Self sterilization of bodies during outer planet entry. [atmospheric temperature effects

NASA Technical Reports Server (NTRS)

Hoffman, A. R.; Jaworski, W.; Taylor, D. M.

1975-01-01

As a body encounters the atmosphere of an outer planet, whether accidentally or by plan, it will be subjected to heat loads which could result in high temperature conditions that render terrestrial organisms on or within the body non-viable. To determine whether an irregularly shaped entering body, consisting of several different materials, would be sterilized during inadvertent entry at high velocity, the thermal response of a typical outer planet spacecraft instrument was studied. The results indicate that the Teflon-insulated cable and electronic circuit boards may not experience sterilizing temperatures during a Jupiter, Saturn, or Titan entry. Another conclusion of the study is that small plastic particles entering Saturn from outer space have wider survival corridors than do those at Jupiter.

Is the Magnetic Field in the Heliosheath Sector Region and in the Outer Heliosheath Laminar?

NASA Astrophysics Data System (ADS)

Opher, M.; Drake, J. F.; Swisdak, M. M.; Toth, G.

2010-12-01

All the current global models of the heliosphere are based on the assumption that the magnetic field in the outer heliosheath close to the heliopause is laminar. We argue that in the outer heliosheath the heliospheric magnetic field is not laminar but instead consists of nested magnetic islands. Recently, we proposed (Drake et al. 2009) that the annihilation of the ``sectored'' magnetic field within the heliosheath as it is compressed on its approach to the heliopause produces the anomalous cosmic rays (ACRs) and also energetic electrons. As a product of the annihilation of the sectored magnetic field, densly-packed magnetic islands are produced. These magnetic islands will be convected with the ambient flows as the sector boundary is carried to higher latitudes filling the outer heliosheath. We further argue that the magnetic islands will develop upstream (but still within the heliosheath) where collisionless reconnection is unfavorable -- large perturbations of the sector structure near the heliopause will cause compressions of the current sheet upstream, triggering reconnection. As a result, the magnetic field in the heliosheath sector region will be disordered well upstream of the heliopause. We present a 3D MHD simulation with unprecedent numerical resolution that captures the sector boundary. We show that due to the high pressure of the interstellar magnetic field the disordered sectored region fills a large portion of the northern part of the heliosphere with a smaller extension in the southern hemisphere. We test these ideas with observations of energetic electrons, which because of their high velocity are most sensitive to the structure of the magnetic field. We suggest that within our scenario we can explain two significant anomalies in the observations of energetic electrons in the outer heliosphere: the sudden decrease in the intensity of low energy electrons (0.02-1.5MeV) from the LECP instrument on Voyager 2 in 2008 (Decker 2010); and the dramatic differences in intensity trends between Galactic Cosmic Ray Electrons (3.8-59MeV) at Voyager 1 and 2 (McDonald 2010). We argue that these observations are a consequence of Voyager 2 leaving the sector region of disordered field in mid 2008 and crossing into a region of unipolar laminar field.

Development and Evaluation of an Externally Air-Cooled Low-Flow torch and the Attenuation of Space Charge and Matrix Effects in Inductively Coupled Plasma Mass Spectrometry

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

Praphairaksit, Narong

2000-09-12

An externally air-cooled low-flow torch has been constructed and successfully demonstrated for applications in inductively coupled plasma mass spectrometry (ICP-MS). The torch is cooled by pressurized air flowing at ~70 L/min through a quartz air jacket onto the exterior of the outer tube. The outer gas flow rate and operating RF forward power are reduced considerably. Although plasmas can be sustained at the operating power as low as 400 W with a 2 L/min of outer gas flow, somewhat higher power and outer gas flows are advisable. A stable and analytical useful plasma can be obtained at 850 W withmore » an outer gas flow rate of ~4 L/min. Under these conditions, the air-cooled plasma produces comparable sensitivities, doubly charged ion ratios, matrix effects and other analytical merits as those produced by a conventional torch while using significantly less argon and power requirements. Metal oxide ion ratios are slightly higher with the air-cooled plasma but can be mitigated by reducing the aerosol gas flow rate slightly with only minor sacrifice in analyte sensitivity. A methodology to alleviate the space charge and matrix effects in ICP-MS has been developed. A supplemental electron source adapted from a conventional electron impact ionizer is added to the base of the skimmer. Electrons supplied from this source downstream of the skimmer with suitable amount and energy can neutralize the positive ions in the beam extracted from the plasma and diminish the space charge repulsion between them. As a result, the overall ion transmission efficiency and consequent analyte ion sensitivities are significantly improved while other important analytical aspects, such as metal oxide ion ratio, doubly charged ion ratio and background ions remain relatively unchanged with the operation of this electron source. This technique not only improves the ion transmission efficiency but also minimizes the matrix effects drastically. The matrix-induced suppression of signal for even the most troublesome combination of light analyte and heavy matrix elements can be attenuated from 90-99% to only 2-10% for 2 mM matrix solutions with an ultrasonic nebulizer. The supplemental electron current can be adjusted to ''titrate'' out the matrix effects as desired.« less

Resonant scattering of energetic electrons in the outer radiation belt by HAARP-induced ELF/VLF waves

NASA Astrophysics Data System (ADS)

Chang, Shanshan; Zhu, Zhengping; Ni, Binbin; Cao, Xing; Luo, Weihua

2016-10-01

Several extremely low-frequency (ELF)/very low-frequency (VLF) wave generation experiments have been performed successfully at High-Frequency Active Auroral Research Program (HAARP) heating facility and the artificial ELF/VLF signals can leak into the outer radiation belt and contribute to resonant interactions with energetic electrons. Based on the artificial wave properties revealed by many of in situ observations, we implement test particle simulations to evaluate the effects of energetic electron resonant scattering driven by the HAARP-induced ELF/VLF waves. The results indicate that for both single-frequency/monotonic wave and multi-frequency/broadband waves, the behavior of each electron is stochastic while the averaged diffusion effect exhibits temporal linearity in the wave-particle interaction process. The computed local diffusion coefficients show that, the local pitch-angle scattering due to HARRP-induced single-frequency ELF/VLF whistlers with an amplitude of ∼10 pT can be intense near the loss cone with a rate of ∼10-2 rad2 s-1, suggesting the feasibility of HAARP-induced ELF/VLF waves for removal of outer radiation belt energetic electrons. In contrast, the energy diffusion of energetic electrons is relatively weak, which confirms that pitch-angle scattering by artificial ELF/VLF waves can dominantly lead to the precipitation of energetic electrons. Moreover, diffusion rates of the discrete, broadband waves, with the same amplitude of each discrete frequency as the monotonic waves, can be much larger, which suggests that it is feasible to trigger a reasonable broadband wave instead of the monotonic wave to achieve better performance of controlled precipitation of energetic electrons. Moreover, our test particle scattering simulation show good agreement with the predictions of the quasi-linear theory, confirming that both methods are applied to evaluate the effects of resonant interactions between radiation belt electrons and artificially generated discrete ELF/VLF waves.

Evaluating the Role and Effects of Precipitation on Relativistic Electron Losses during Storms

NASA Astrophysics Data System (ADS)

Chen, Y.; Fu, X.

2016-12-01

Theoretic studies have suggested that during storm times various waves (e.g., whistler-mode chorus and electromagnetic ion cyclotron waves) can cause significant precipitation of relativistic ( MeV) electrons that are originally trapped inside the outer radiation belt. However, the role of precipitation and its quantitative contribution to the losses of outer-belt electrons remain open questions. In this study, we tackle these questions by systemically examining the latest wave and electron in-situ, simultaneous observations made at different altitudes by Van Allen Probes from near equator, NOAA POES at low Earth orbits near/across electron loss cone, and BARREL under the mesosphere. After calibrating with DEMTER observations, we first confirm and quantify the response of POES MEPED proton channels to MeV electrons. Next, we identify a list of precipitation events from BARREL and POES measurements, examine the temporal adn spatial relation between the two data sets, and estimate the intensities of electron precipitation with ascertained uncertainties. Then, from Van Allen Probes data, we select another list of dropout events during storms. By cross checking the above two lists, we are able to determine the causal relation between precipitation and dropouts through individual case as well as statistical studies so as to quantify the contributions from precipitation. This study mainly focuses on the relatively small L-shells with positive phase space density radial gradient in order to alleviate the impacts from outward radial diffusion and adiabatic effects. Based upon the recent discovery of cross-energy cross-pitch angle coherence, we pay particular attention to the cross-term diffusions which may account for the extra "loss" needed by observed MeV electron dropouts. Results from this observational study will advance our knowledge on the loss mechanism of outer-belt electrons, and thus lay down another stepping stone towards high-fidelity physics-based models for radiation belts.

Seeded Fault Bearing Experiments: Methodology and Data Acquisition

DTIC Science & Technology

2011-06-01

electronics piezoelectric ( IEPE ) transducer. Constant current biased transducers require AC coupling for the output signal. The ICP-Type Signal...the outer race I/O input/output IEPE integral electronics piezoelectric LCD liquid crystal display P&D Prognostics and Diagnostics RMS root

Dynamical models to explain observations with SPHERE in planetary systems with double debris belts

NASA Astrophysics Data System (ADS)

Lazzoni, C.; Desidera, S.; Marzari, F.; Boccaletti, A.; Langlois, M.; Mesa, D.; Gratton, R.; Kral, Q.; Pawellek, N.; Olofsson, J.; Bonnefoy, M.; Chauvin, G.; Lagrange, A. M.; Vigan, A.; Sissa, E.; Antichi, J.; Avenhaus, H.; Baruffolo, A.; Baudino, J. L.; Bazzon, A.; Beuzit, J. L.; Biller, B.; Bonavita, M.; Brandner, W.; Bruno, P.; Buenzli, E.; Cantalloube, F.; Cascone, E.; Cheetham, A.; Claudi, R. U.; Cudel, M.; Daemgen, S.; De Caprio, V.; Delorme, P.; Fantinel, D.; Farisato, G.; Feldt, M.; Galicher, R.; Ginski, C.; Girard, J.; Giro, E.; Janson, M.; Hagelberg, J.; Henning, T.; Incorvaia, S.; Kasper, M.; Kopytova, T.; LeCoroller, H.; Lessio, L.; Ligi, R.; Maire, A. L.; Ménard, F.; Meyer, M.; Milli, J.; Mouillet, D.; Peretti, S.; Perrot, C.; Rouan, D.; Samland, M.; Salasnich, B.; Salter, G.; Schmidt, T.; Scuderi, S.; Sezestre, E.; Turatto, M.; Udry, S.; Wildi, F.; Zurlo, A.

2018-03-01

Context. A large number of systems harboring a debris disk show evidence for a double belt architecture. One hypothesis for explaining the gap between the debris belts in these disks is the presence of one or more planets dynamically carving it. For this reason these disks represent prime targets for searching planets using direct imaging instruments, like the Spectro-Polarimetric High-constrast Exoplanet Research (SPHERE) at the Very Large Telescope. Aim. The goal of this work is to investigate this scenario in systems harboring debris disks divided into two components, placed, respectively, in the inner and outer parts of the system. All the targets in the sample were observed with the SPHERE instrument, which performs high-contrast direct imaging, during the SHINE guaranteed time observations. Positions of the inner and outer belts were estimated by spectral energy distribution fitting of the infrared excesses or, when available, from resolved images of the disk. Very few planets have been observed so far in debris disks gaps and we intended to test if such non-detections depend on the observational limits of the present instruments. This aim is achieved by deriving theoretical predictions of masses, eccentricities, and semi-major axes of planets able to open the observed gaps and comparing such parameters with detection limits obtained with SPHERE. Methods: The relation between the gap and the planet is due to the chaotic zone neighboring the orbit of the planet. The radial extent of this zone depends on the mass ratio between the planet and the star, on the semi-major axis, and on the eccentricity of the planet, and it can be estimated analytically. We first tested the different analytical predictions using a numerical tool for the detection of chaotic behavior and then selected the best formula for estimating a planet's physical and dynamical properties required to open the observed gap. We then apply the formalism to the case of one single planet on a circular or eccentric orbit. We then consider multi-planetary systems: two and three equal-mass planets on circular orbits and two equal-mass planets on eccentric orbits in a packed configuration. As a final step, we compare each couple of values (Mp, ap), derived from the dynamical analysis of single and multiple planetary models, with the detection limits obtained with SPHERE. Results: For one single planet on a circular orbit we obtain conclusive results that allow us to exclude such a hypothesis since in most cases this configuration requires massive planets which should have been detected by our observations. Unsatisfactory is also the case of one single planet on an eccentric orbit for which we obtained high masses and/or eccentricities which are still at odds with observations. Introducing multi planetary architectures is encouraging because for the case of three packed equal-mass planets on circular orbits we obtain quite low masses for the perturbing planets which would remain undetected by our SPHERE observations. The case of two equal-mass planets on eccentric orbits is also of interest since it suggests the possible presence of planets with masses lower than the detection limits and with moderate eccentricity. Our results show that the apparent lack of planets in gaps between double belts could be explained by the presence of a system of two or more planets possibly of low mass and on eccentric orbits whose sizes are below the present detection limits. Based on observations collected at Paranal Observatory, ESO (Chile) Program ID: 095.C-0298, 096.C-0241, 097.C-0865, and 198.C-0209.

Contribution of the ULF wave activity to the global recovery of the outer radiation belt during the passage of a high-speed solar wind stream observed in September 2014

NASA Astrophysics Data System (ADS)

Dal Lago, A.; Da Silva, L. A.; Alves, L. R.; Dallaqua, R.; Marchezi, J.; Medeiros, C.; Souza, V. M. C. E. S.; Koga, D.; Jauer, P. R.; Vieira, L.; Rockenbach, M.; Mendes, O., Jr.; De Nardin, C. M.; Sibeck, D. G.

2016-12-01

The interaction of the solar wind with the Earth's magnetosphere can either increase or decrease the relativistic electron population in the outer radiation belt. In order to investigate the contribution of the ULF wave activity to the global recovery of the outer radiation belt relativistic electron population, we searched the Van Allen data for a period in which we can clearly distinguish the enhancement of the fluxes from the background. The complex solar wind structure observed from September 12-24, 2014, which resulted from the interaction of two coronal mass ejections (CMEs) and a high-speed stream, presented such a scenario. The CMEs are related to the dropout of the relativistic electron population followed by several days of low fluxes. The global recovery started during the passage of the high-speed stream that was associated with the occurrence of substorms that persisted for several days. Here we estimate the contribution of ULF wave-particle interactions to the enhancement of the relativistic electron fluxes. Our approach is based on estimates of the ULF wave radial diffusion coefficients employing two models: (a) an analytic expression presented by Ozeke et al. (2014); and (b) a simplified model based on the solar wind parameters. The preliminary results, uncertainties and future steps are discussed in details.

GRAVITATIONAL ACCRETION OF PARTICLES ONTO MOONLETS EMBEDDED IN SATURN's RINGS

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

Yasui, Yuki; Ohtsuki, Keiji; Daisaka, Hiroshi, E-mail: y.yasui@whale.kobe-u.ac.jp, E-mail: ohtsuki@tiger.kobe-u.ac.jp

2014-12-20

Using a local N-body simulation, we examine gravitational accretion of ring particles onto moonlet cores in Saturn's rings. We find that gravitational accretion of particles onto moonlet cores is unlikely to occur in the C ring and probably difficult in the inner B ring as well provided that the cores are rigid water ice. Dependence of particle accretion on ring thickness changes when the radial distance from the planet and/or the density of particles is varied: the former determines the size of the core's Hill radius relative to its physical size, while the latter changes the effect of self-gravity ofmore » accreted particles. We find that particle accretion onto high-latitude regions of the core surface can occur even if the rings' vertical thickness is much smaller than the core radius, although redistribution of particles onto the high-latitude regions would not be perfectly efficient in outer regions of the rings such as the outer A ring, where the size of the core's Hill sphere in the vertical direction is significantly larger than the core's physical radius. Our results suggest that large boulders recently inferred from observations of transparent holes in the C ring are not formed locally by gravitational accretion, while propeller moonlets in the A ring would be gravitational aggregates formed by particle accretion onto dense cores. Our results also imply that the main bodies of small satellites near the outer edge of Saturn's rings may have been formed in rather thin rings.« less

RESOLVING THE PLANET-HOSTING INNER REGIONS OF THE LkCa 15 DISK

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

Thalmann, C.; Garufi, A.; Quanz, S. P.

2016-09-10

LkCa 15 hosts a pre-transitional disk as well as at least one accreting protoplanet orbiting in its gap. Previous disk observations have focused mainly on the outer disk, which is cleared inward of ∼50 au. The planet candidates, on the other hand, reside at orbital radii around 15 au, where disk observations have been unreliable until recently. Here, we present new J -band imaging polarimetry of LkCa 15 with SPHERE IRDIS, yielding the most accurate and detailed scattered-light images of the disk to date down to the planet-hosting inner regions. We find what appear to be persistent asymmetric structures inmore » the scattering material at the location of the planet candidates, which could be responsible at least for parts of the signals measured with sparse-aperture masking. These images further allow us to trace the gap edge in scattered light at all position angles and search the inner and outer disks for morphological substructure. The outer disk appears smooth with slight azimuthal variations in polarized surface brightness, which may be due to shadowing from the inner disk or a two-peaked polarized phase function. We find that the near-side gap edge revealed by polarimetry matches the sharp crescent seen in previous ADI imaging very well. Finally, the ratio of polarized disk to stellar flux is more than six times larger in the J -band than in the RI bands.« less

Beta-Tin Grain Formation in Aluminum-Modified Lead-Free Solder Alloys

NASA Astrophysics Data System (ADS)

Reeve, Kathlene N.; Handwerker, Carol A.

2018-01-01

The limited number of independent β-Sn grain orientations that typically form during solidification of Sn-based solders and the resulting large β-Sn grain size have major effects on overall solder performance and reliability. This study analyzes whether additions of Al to Sn-Cu and Sn-Cu-Ag alloys can be used to change the grain size, morphology, and twinning structures of atomized (as-solidified) and re-melted (reflowed) β-Sn dendrites as determined using scanning electron microscopy and electron backscatter diffraction for as-solidified and reflow cycled (20-250°C, 1-5 cycles) Sn-Cu-Al and Sn-Ag-Cu-Al drip atomized spheres (260 μm diameter). The resulting microstructures were compared to as-solidified and reflow cycled Sn-Ag-Cu spheres (450 μm diameter) as well as as-solidified Sn-Ag-Cu, Sn-Cu, and Sn-Ag microstructures from the literature. Previous literature observations reporting reductions in undercooling and β-Sn grain size with Al micro-alloying additions could not be correlated to the presence of the Cu9Al4 phase or Al solute. The as-solidified spheres displayed no change in β-Sn dendrite structure or grain size when compared to non-Al-modified alloys, and the reflow cycled spheres produced high undercoolings (22-64°C), indicating a lack of potent nucleation sites. The current findings highlighted the role of Ag in the formation of the interlaced twinning structure and demonstrated that with deliberate compositional choices, formation of the alloy's β-Sn grain structure (cyclical twinning versus interlaced twinning) could be influenced, in both the as-solidified and reflow cycled states, though still not producing the fine-grain sizes and multiple orientations desired for improved thermomechanical properties.

WE-AB-204-11: Development of a Nuclear Medicine Dosimetry Module for the GPU-Based Monte Carlo Code ARCHER

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

Liu, T; Lin, H; Xu, X

Purpose: To develop a nuclear medicine dosimetry module for the GPU-based Monte Carlo code ARCHER. Methods: We have developed a nuclear medicine dosimetry module for the fast Monte Carlo code ARCHER. The coupled electron-photon Monte Carlo transport kernel included in ARCHER is built upon the Dose Planning Method code (DPM). The developed module manages the radioactive decay simulation by consecutively tracking several types of radiation on a per disintegration basis using the statistical sampling method. Optimization techniques such as persistent threads and prefetching are studied and implemented. The developed module is verified against the VIDA code, which is based onmore » Geant4 toolkit and has previously been verified against OLINDA/EXM. A voxelized geometry is used in the preliminary test: a sphere made of ICRP soft tissue is surrounded by a box filled with water. Uniform activity distribution of I-131 is assumed in the sphere. Results: The self-absorption dose factors (mGy/MBqs) of the sphere with varying diameters are calculated by ARCHER and VIDA respectively. ARCHER’s result is in agreement with VIDA’s that are obtained from a previous publication. VIDA takes hours of CPU time to finish the computation, while it takes ARCHER 4.31 seconds for the 12.4-cm uniform activity sphere case. For a fairer CPU-GPU comparison, more effort will be made to eliminate the algorithmic differences. Conclusion: The coupled electron-photon Monte Carlo code ARCHER has been extended to radioactive decay simulation for nuclear medicine dosimetry. The developed code exhibits good performance in our preliminary test. The GPU-based Monte Carlo code is developed with grant support from the National Institute of Biomedical Imaging and Bioengineering through an R01 grant (R01EB015478)« less

Re-accumulation Scenarios Governing Final Global Shapes of Rubble-Pile Asteroids

NASA Astrophysics Data System (ADS)

Hestroffer, Daniel; Tanga, P.; Comito, C.; Paolicchi, P.; Walsh, K.; Richardson, D. C.; Cellino, A.

2009-05-01

Asteroids, since the formation of the solar system, are known to have experienced catastrophic collisions, which---depending on the impact energy---can produce a major disruption of the parent body and possibly give birth to asteroid families or binaries [1]. We present a general study of the final shape and dynamical state of asteroids produced by the re-accumulation process following a catastrophic disruption. Starting from a cloud of massive particles (mono-disperse spheres) with given density and velocity distributions, we analyse the final shape, spin state, and angular momentum of the system from numerical integration of a N-body gravitational system (code pkdgrav [2]). The re-accumulation process itself is relatively fast, with a dynamical time corresponding to the spin-period of the final body (several hours). The final global shapes---which are described as tri-axial ellipsoids---exhibit slopes consistent with a degree of shear stress sustained by interlocking particles. We point out a few results: -the final shapes are close to those of hydrostatic equilibrium for incompressible fluids, preferably Maclaurin spheroid rather than Jacobi ellipsoids -for bodies closest to the sequence of hydrostatic equilibrium, there is a direct relation between spin, density and outer shape, suggesting that the outer surface is nearly equipotential -the evolution of the shape during the process follows a track along a gradient of potential energy, without necessarily reaching its minimum -the loose random packing of the particles implies low friction angle and hence fluid-like behaviour, which extends the results of [3]. Future steps of our analysis will include feature refinements of the model initial conditions and re-accumulation process, including impact shakings, realistic velocity distributions, and non equal-sized elementary spheres. References [1] Michel P. et al. 2001. Science 294, 1696 [2] Leinhardt Z.M. et al. 2000. Icarus 146, 133 [3] Richardson D.C. et al. 2005. Icarus 173, 349

A Large Program to derive the shape, cratering history and density of the largest main-belt asteroids

NASA Astrophysics Data System (ADS)

Marchis, Franck; Vernazza, Pierre; Marsset, Michael; Hanus, Josef; Carry, Benoit; Birlan, Mirel; Santana-Ros, Toni; Yang, Bin; and the Large Asteroid Survey with SPHERE (LASS)

2017-10-01

Asteroids in our solar system are metallic, rocky and/or icy objects, ranging in size from a few meters to a few hundreds of kilometers. Whereas we now possess constraints for the surface composition, albedo and rotation rate for all D≥100 km main-belt asteroids, the 3-D shape, the crater distribution, and the density have only been measured for a very limited number of these bodies (N≤10 for the first two). Characterizing these physical properties would allow us to address entirely new questions regarding the earliest stages of planetesimal formation and their subsequent collisional and dynamical evolution.ESO allocated to our program 152 hours of observations over 4 semesters to carry out disk-resolved observations of 38 large (D≥100 km) main-belt asteroids (sampling the four main compositional classes) at high angular-resolution with VLT/SPHERE throughout their rotation in order to derive their 3-D shape, the size distribution of the largest craters, and their density (PI: P. Vernazza). These measurements will allow investigating for the first time and for a modest amount of observing time the following fundamental questions: (A) Does the asteroid belt effectively hosts a large population of small bodies formed in the outer solar system? (B) Was the collisional environment in the inner solar system (at 2-3 AU) more intense than in the outer solar system (≥5AU)? (C) What was the shape of planetesimals at the end of the accretion process?We will present the goals and objectives of our program in the context of NASA 2014 Strategic Plan and the NSF decadal survey "Vision and Voyages" as well as the first observations and results collected with the SPHERE Extreme AO system. A detailed analysis of the shape modeling will be presented by Hanuš et al. in this session.

Detailed characteristics of radiation belt electrons revealed by CSSWE/REPTile measurements: Geomagnetic activity response and precipitation observation

NASA Astrophysics Data System (ADS)

Zhang, K.; Li, X.; Schiller, Q.; Gerhardt, D.; Zhao, H.; Millan, R.

2017-08-01

Earth's outer radiation belt electrons are highly dynamic. We study the detailed characteristics of relativistic electrons in the outer belt using measurements from the Colorado Student Space Weather Experiment (CSSWE) mission, a low Earth orbit (LEO) CubeSat, which traverses the radiation belt four times in one orbit ( 1.5 h) and has the advantage of measuring the dynamic activities of the electrons including their rapid precipitation. We focus on the measured electron response to geomagnetic activity for different energies to show that there are abundant sub-MeV electrons in the inner belt and slot region. These electrons are further enhanced during active times, while there is a lack of >1.63 MeV electrons in these regions. We also show that the variation of measured electron flux at LEO is strongly dependent on the local magnetic field strength, which is far from a dipole approximation. Moreover, a specific precipitation band, which happened on 19 January 2013, is investigated based on the conjunctive measurement of CSSWE, the Balloon Array for Radiation belt Relativistic Electron Losses, and one of the Polar Operational Environmental Satellites. In this precipitation band event, the net loss of the 0.58-1.63 MeV electrons (L = 3.5-6) is estimated to account for 6.8% of the total electron content.

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

Two Step Acceleration Process of Electrons in the Outer Van Allen Radiation Belt by Time Domain Electric Field Bursts and Large Amplitude Chorus Waves

NASA Astrophysics Data System (ADS)

Agapitov, O. V.; Mozer, F.; Artemyev, A.; Krasnoselskikh, V.; Lejosne, S.

2014-12-01

A huge number of different non-linear structures (double layers, electron holes, non-linear whistlers, etc) have been observed by the electric field experiment on the Van Allen Probes in conjunction with relativistic electron acceleration in the Earth's outer radiation belt. These structures, found as short duration (~0.1 msec) quasi-periodic bursts of electric field in the high time resolution electric field waveform, have been called Time Domain Structures (TDS). They can quite effectively interact with radiation belt electrons. Due to the trapping of electrons into these non-linear structures, they are accelerated up to ~10 keV and their pitch angles are changed, especially for low energies (˜1 keV). Large amplitude electric field perturbations cause non-linear resonant trapping of electrons into the effective potential of the TDS and these electrons are then accelerated in the non-homogeneous magnetic field. These locally accelerated electrons create the "seed population" of several keV electrons that can be accelerated by coherent, large amplitude, upper band whistler waves to MeV energies in this two step acceleration process. All the elements of this chain acceleration mechanism have been observed by the Van Allen Probes.

Hydrothermal Synthesis of TiO2 Porous Hollow Nanospheres for Coating on the Photoelectrode of Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Madhu Mohan, Varishetty; Murakami, Kenji

2012-02-01

Various sizes of TiO2 hollow nanosphers were synthesized by a hydrolysis followed by the hydrothermal treatment using different water content and titanium isopropoxide (TTIP) while the remaining components such as methylamine, ethanol and acetonitrile were kept as a constant. We synthesized the various sizes of spheres, 150, 250, 400, 450, and 600 nm in diameter; those are represented as SP150, SP250, SP400, SP450, and SP600. The prepared spheres diameters were confirmed by scanning electron microscopy (SEM). These spheres were coated by using a simple spray technique with the TiO2 colloidal solution as a scattering layer for the TiO2 photoelectrode of dye-sensitized solar cells. Optical absorption measurements did not find a difference in the dye adsorption amount with and without the scattering layer. The scattering effect was observed by incident photon to current conversion efficiency (IPCE) measurements especially in the wavelength region of 550-700 nm. The current-voltage (I-V) measurements show that the scattering layer with 450 nm spheres coated on the photoelectrode gave the improved photovoltaic performances compared to other diameters of the spheres. In the present study, the best energy conversion efficiency of 9.56% was obtained for the photoelectrode with the scattering layer, while the pure photoelectrode without the layer gave 8.4%.

Hydrothermal synthesis and afterglow luminescence properties of hollow SnO{sub 2}:Sm{sup 3+},Zr{sup 4+} spheres for potential application in drug delivery

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

Feng, Pengfei; Zhang, Jiachi, E-mail: zhangjch@lzu.edu.cn; Qin, Qingsong

2014-02-01

Highlights: • We designed a novel afterglow labeling material SnO{sub 2}:Sm{sup 3+},Zr{sup 4+} for the first time. • Hollow SnO{sub 2}:Sm{sup 3+},Zr{sup 4+} spheres with afterglow were prepared by hydrothermal method. • Hollow SnO{sub 2}:Sm{sup 3+},Zr{sup 4+} is a potential afterglow labeling medium for drug delivery. - Abstract: A novel afterglow labeling material SnO{sub 2}:Sm{sup 3+},Zr{sup 4+} with hollow sphere shape and intense afterglow luminescence is prepared by hydrothermal method at 180 °C for the first time. The morphology and the sphere growth process of this material are investigated by scanning electron microscopy in detail. The afterglow measurement shows thatmore » this hydrothermal obtained material exhibits obvious red afterglow luminescence (550–700 nm) of Sm{sup 3+} which can last for 542 s (0.32 mcd/m{sup 2}). The depth of traps in this hydrothermal obtained material is calculated to be as shallow as 0.58 eV. The results demonstrate that although it is necessary to further improve the afterglow performance of the hydrothermal derived hollow SnO{sub 2}:Sm{sup 3+},Zr{sup 4+} spheres, it still can be regarded as a potential afterglow labeling medium for drug delivery.« 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.

Proximity functions for electrons up to 10 keV

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

Chmelevsky, D.; Kellerer, A.M.; Terrissol, M.

1980-11-01

Proximity functions for electrons up to 10 keV in water are computed from simulated particle tracks. Numerical results are given for the differential functions t(x) and the integral functions T(x). Basic characteristics of these functions and their connections to other microdosimetric quantities are considered. As an example of the applicability of the proximity functions, the quantity y/sub D/ for spheres is derived from t(x).

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

L-shell bifurcation of electron outer belt at the recovery phase of geomagnetic storm as observed by STEP-F and SphinX instruments onboard the CORONAS-Photon satellite

NASA Astrophysics Data System (ADS)

Dudnik, Oleksiy; Sylwester, Janusz; Kowalinski, Miroslaw; Podgorski, Piotr

2016-07-01

Radiation belts and sporadically arising volumes comprising enhanced charged particle fluxes in the Earth's magnetosphere are typically studied by space-borne telescopes, semiconductor, scintillation, gaseous and other types of detectors. Ambient and internal electron bremsstrahlung in hard X-ray arises as a result of interaction of precipitating particles with the atmosphere (balloon experiments) and with the satellite's housings and instrument boxes (orbital experiments). Theses emissions provide a number of new information on the physics of radiation belts. The energies of primary electrons and their spectra responsible for measured X-ray emissions remain usually unknown. Combined measurements of particle fluxes, and their bremsstrahlung by individual satellite instruments placed next to each other provide insight to respective processes. The satellite telescope of electrons and protons STEP-F and the solar X-ray spectrophotometer SphinX were placed in close proximity to each other aboard CORONAS-Photon, the low, circular and highly inclined orbit satellite. Based on joint analysis of the data we detected new features in the high energy particle distributions of the Earth's magnetosphere during deep minimum of solar activity [1-3]. In this research the bifurcation of Van Allen outer electron radiation belt during the weak geomagnetic storm and during passage of interplanetary shock are discussed. Outer belt bifurcation and growth of electron fluxes in a wide energy range were recorded by both instruments during the recovery phase of May 8, 2009 substorm. STEP-F recorded also barely perceptible outer belt splitting on August 5, 2009, after arrival of interplanetary shock to the Earth's magnetosphere bowshock. The STEP-F and SphinX data are compared with the space weather indexes, and with relativistic electron fluxes observed at geostationary orbit. We discuss possible mechanism of the phenomena consisting in the splitting of drift shells because of Earth's magnetic field asymmetry and/or fast radial and pitch-angle particle diffusion from the outer edge of the magnetosphere. 1. P.Podgórski, O.V.Dudnik, J.Sylwester, S.Gburek, M.Kowaliński, M.Siarkowski, S.Plocieniak, J.Bąkala. Joint analysis of SphinX and STEP-F instruments data on magnetospheric electron flux dynamics at low Earth orbit / in: Abstracts of 39th Scientific Assembly of COSPAR, Mysore, India, July 14-22, 2012, Panel PSW.3: "Space Weather Data: Observations and Exploitation for Research and Applications", STW-C-119 PSW.3-0028-12, P.112. 2. O.V.Dudnik, P.Podgórski, J.Sylwester, S.Gburek, M.Kowalinski, M.Siarkowski, S.Plocieniak, and J.Bakala. X-Ray Spectrophotometer SphinX and Particle Spectrometer STEP-F of the Satellite Experiment CORONAS-PHOTON. Preliminary Results of the Joint Data Analysis / Solar System Research, 2012, V.46, No.2, P.160-169, doi:10.1134/S0038094612020025. 3. O.V.Dudnik, P.Podgórski, J.Sylwester. New perspectives to study the splitting of drift shells at the outer magnetosphere by using STEP-F and SphinX instruments on board the CORONAS-Photon satellite / in: Abstract Book of the Conference "Progress on EUV&X-ray spectroscopy and imaging II", Wroclaw, Poland, November 17-19, 2015, P.8, doi:10.13140/RG.2.1.1872.4889.

Insight into mitochondrial structure and function from electron tomography.

PubMed

Frey, T G; Renken, C W; Perkins, G A

2002-09-10

In recent years, electron tomography has provided detailed three-dimensional models of mitochondria that have redefined our concept of mitochondrial structure. The models reveal an inner membrane consisting of two components, the inner boundary membrane (IBM) closely apposed to the outer membrane and the cristae membrane that projects into the matrix compartment. These two components are connected by tubular structures of relatively uniform size called crista junctions. The distribution of crista junction sizes and shapes is predicted by a thermodynamic model based upon the energy of membrane bending, but proteins likely also play a role in determining the conformation of the inner membrane. Results of structural studies of mitochondria during apoptosis demonstrate that cytochrome c is released without detectable disruption of the outer membrane or extensive swelling of the mitochondrial matrix, suggesting the formation of an outer membrane pore large enough to allow passage of holo-cytochrome c. The possible compartmentation of inner membrane function between the IBM and the cristae membrane is also discussed.

The Global Statistical Response of the Outer Radiation Belt During Geomagnetic Storms

NASA Astrophysics Data System (ADS)

Murphy, K. R.; Watt, C. E. J.; Mann, I. R.; Jonathan Rae, I.; Sibeck, D. G.; Boyd, A. J.; Forsyth, C. F.; Turner, D. L.; Claudepierre, S. G.; Baker, D. N.; Spence, H. E.; Reeves, G. D.; Blake, J. B.; Fennell, J.

2018-05-01

Using the total radiation belt electron content calculated from Van Allen Probe phase space density, the time-dependent and global response of the outer radiation belt during storms is statistically studied. Using phase space density reduces the impacts of adiabatic changes in the main phase, allowing a separation of adiabatic and nonadiabatic effects and revealing a clear modality and repeatable sequence of events in storm time radiation belt electron dynamics. This sequence exhibits an important first adiabatic invariant (μ)-dependent behavior in the seed (150 MeV/G), relativistic (1,000 MeV/G), and ultrarelativistic (4,000 MeV/G) populations. The outer radiation belt statistically shows an initial phase dominated by loss followed by a second phase of rapid acceleration, while the seed population shows little loss and immediate enhancement. The time sequence of the transition to the acceleration is also strongly μ dependent and occurs at low μ first, appearing to be repeatable from storm to storm.

Ice-Templated Bimodal-Porous Silver Nanowire/PDMS Nanocomposites for Stretchable Conductor.

PubMed

Oh, Jae Young; Lee, Dongju; Hong, Soon Hyung

2018-06-27

A three-dimensional (3D) bimodal-porous silver nanowire (AgNW) nanostructure with superior electrical properties is fabricated by freeze drying of AgNW aqueous dispersion with macrosized ice spheres for bimodal-porous structure. The ice sphere dispersed AgNW solution yields a 3D AgNW network at the surface of ice sphere and formation of macropores by removal of ice sphere during freeze-drying process. The resulting nanostructures exhibit excellent electrical properties due to their low electrical percolation threshold by the formation of macropores, which results in an efficient and dense 3D AgNW network with a small amount of AgNWs. The highly conductive and stretchable AgNW/poly(dimethylsiloxane) (PDMS) nanocomposites are made by impregnating the 3D porous conductive network with highly stretchable poly(dimethylsiloxane) (PDMS) matrix. The AgNW/PDMS nanocomposites exhibit a high conductivity of 42 S/cm with addition of relatively small amount of 2 wt %. The high conductivity is retained when stretched up to 120% elongation even after 100 stretching-releasing cycles. Due to high electrical conductivity and superior stretchability of AgNW/PDMS nanocomposites, these are expected to be used in stretchable electronic devices.

Rapid and selective detection of acetone using hierarchical ZnO gas sensor for hazardous odor markers application.

PubMed

Jia, Qianqian; Ji, Huiming; Zhang, Ying; Chen, Yalu; Sun, Xiaohong; Jin, Zhengguo

2014-07-15

Hierarchical nanostructured ZnO dandelion-like spheres were synthesized via solvothermal reaction at 200°C for 4h. The products were pure hexagonal ZnO with large exposure of (002) polar facet. Side-heating gas sensor based on hierarchical ZnO spheres was prepared to evaluate the acetone gas sensing properties. The detection limit to acetone for the ZnO sensor is 0.25ppm. The response (Ra/Rg) toward 100ppm acetone was 33 operated at 230°C and the response time was as short as 3s. The sensor exhibited remarkable acetone selectivity with negligible response toward other hazardous gases and water vapor. The high proportion of electron depletion region and oxygen vacancies contributed to high gas response sensitivity. The hollow and porous structure of dandelion-like ZnO spheres facilitated the diffusion of gas molecules, leading to a rapid response speed. The largely exposed (002) polar facets could adsorb acetone gas molecules easily and efficiently, resulting in a rapid response speed and good selectivity of hierarchical ZnO spheres gas sensor at low operating temperature. Copyright © 2014 Elsevier B.V. All rights reserved.

Examining Relativistic Electron Loss in the Outer Radiation Belt

NASA Astrophysics Data System (ADS)

Green, J. C.; Onsager, T. G.; O'Brien, P.

2003-12-01

Since the discovery of earth's radiation belts researchers have sought to identify the mechanisms that dictate the seemingly erratic relativistic electron flux levels in the outer belt. Contrary to intuition, relativistic electron flux levels do not always increase during geomagnetic storms even though these storms signify enhanced energy input from the solar wind to the magnetosphere [Reeves et al., 2003; O'Brien et al., 2001]. The fickle response of the radiation belt electrons to geomagnetic activity suggests that flux levels are determined by the outcome of a continuous competition between acceleration and loss. Some progress has been made developing and testing acceleration mechanisms but little is known about how relativistic electrons are lost. We examine relativistic electron losses in the outer belt focusing our attention on flux decrease events of the type first described by Onsager et al. [2002]. The study showed a sudden decrease of geosynchronous >2MeV electron flux occurring simultaneously with local stretching of the magnetic field. The decrease was first observed near 15:00 MLT and progressed to all local times after a period of ˜10 hours. Expanding on the work of Onsager et al. [2002], we have identified ˜ 51 such flux decrease events in the GOES and LANL data and present the results of a superposed epoch analysis of solar wind data, geomagnetic activity indicators, and locally measured magnetic field and plasma data. The analysis shows that flux decreases occur after 1-2 days of quiet condition. They begin when either the solar wind dynamic pressure increases or Bz turns southward pushing hot dense plasma earthward to form a partial ring current and stretched magnetic field at dusk. Adiabatic electron motion in response to the stretched magnetic field may explain the initial flux reduction; however, often the flux does not recover with the magnetic field recovery, indicating that true loss from the magnetosphere is occurring. Using Polar and SAMPEX data, we examine whether precipitation to the atmosphere or magnetopause encounters can account for the additional loss.

Anatomical mapping of choline acetyltransferase (ChAT)-like and glutamate decarboxylase (GAD)-like immunoreactivity in outer hair cell efferents in adult rats.

PubMed

Dannhof, B J; Roth, B; Bruns, V

1991-10-01

The distribution of choline acetyltransferase (ChAT)-like and glutamate decarboxylase (GAD)-like immunoreactivity in the cochleae of 15 adult Wistar white rats was investigated using the peroxidase-antiperoxidase (PAP) technique. A monoclonal antibody to ChAT and a polyclonal antiserum to GAD were used. Immunoreaction was investigated quantitatively, in the electron microscope, on tangential sections of the tunnel of Corti and the rows of outer hair cells. ChAT-like and GAD-like immunoreactivity was found in all efferent nerve fibres in the tunnel of Corti and in all efferent synapses on the outer hair cells. A coexistence of ChAT and GAD in the efferent system to the outer hair cells of the rat is therefore assumed.

Biologically-compatible gadolinium(at)(carbon nanostructures) as advanced contrast agents for magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Sitharaman, Balaji

2005-11-01

Paramagnetic gadolinium-based carbon nanostructures are introduced as a new paradigm in high-performance magnetic resonance imaging (MRI) contrast agent (CA) design. Two Gd C60-based nanomaterials, Gd C60 [C(COOH)2]10 and Gd C60(OH)x are shown to have MRI efficacies (relaxivities) 5 to 20 times larger than any current Gd3+-based CA in clinical use. The first detailed and systematic physicochemical characterization was performed on these materials using the same experimental techniques usually applied to traditional Gd 3+-based CAs. Water-proton relaxivities were measured for the first time on these materials, as a function of magnetic field (5 x 10-4--9.4 T) to elucidate the different interaction mechanisms and dynamic processes influencing the relaxation behavior. These studies attribute the observed enhanced relaxivities completely to the "outer sphere" proton relaxation mechanism. These "outer sphere" relaxation effects are the largest reported for any Gd3+-based agent without inner-sphere water molecules. The proton relaxivities displayed a remarkable pH-dependency, increasing dramatically with decreasing pH (pH: 3--12). The increase in relaxivity resulted mainly from aggregation and subsequent three-order-of-magnitude increase in tauR, the rotational correlation time. Water-soluble fullerene materials (such as the neuroprotective fullerene drug, C3) readily cross cell membranes, suggesting an application for these gadofullerenes as the first intracellular, as well as pH-responsive MRI CAs. Studies performed at 60 MHz in the presence of phosphate-buffered saline (PBS, mice serum pH: 7.4) to mimic physiological conditions demonstrated that the aggregates can be disrupted by addition of salts, leading to a decrease in relaxivity. Biological fluids present a high salt concentration and should strongly modify the behavior of any fullerenes/metallofullerene-based drug in vivo. Gd C60[C(COOH)2]10 also showed enhanced relaxivity (23% increase) in the presence of the blood protein, human serum albumin (HSA). This result suggests a strong non-covalent interaction between Gd C60[C(COOH)2]10 and HSA leading to slower rotation and a subsequent increase in relaxivity. This also suggests Gd C 60[C(COOH)2]10 as a promising candidate for non-invasive MR angiographic applications to image the "blood pool." Finally, the various important factors or parameters discussed in this work provide valuable insight that can, in general, be used not only for the development of other carbon nanostructure-based MRI contrast agents, but also for any fullerene-based biomedical application.

Semi-Numerical Studies of the Three-Meter Spherical Couette Experiment Utilizing Data Assimilation

NASA Astrophysics Data System (ADS)

Burnett, S. C.; Rojas, R.; Perevalov, A.; Lathrop, D. P.

2017-12-01

The model of the Earth's magnetic field has been investigated in recent years through experiments and numerical models. At the University of Maryland, experimental studies are implemented in a three-meter spherical Couette device filled with liquid sodium. The inner and outer spheres of this apparatus mimic the planet's inner core and core-mantle boundary, respectively. These experiments incorporate high velocity flows with Reynolds numbers 108. In spherical Couette geometry, the numerical scheme applied to this work features finite difference methods in the radial direction and pseudospectral spherical harmonic transforms elsewhere [Schaeffer, N. G3 (2013)]. Adding to the numerical model, data assimilation integrates the experimental outer-layer magnetic field measurements. This semi-numerical model can then be compared to the experimental results as well as forecasting magnetic field changes. Data assimilation makes it possible to get estimates of internal motions of the three-meter experiment that would otherwise be intrusive or impossible to obtain in experiments or too computationally expensive with a purely numerical code. If we can provide accurate models of the three-meter device, it is possible to attempt to model the geomagnetic field. We gratefully acknowledge the support of NSF Grant No. EAR1417148 & DGE1322106.

Semi-Numerical Studies of the Three-Meter Spherical Couette Experiment Utilizing Data Assimilation

NASA Astrophysics Data System (ADS)

Burnett, Sarah; Rojas, Ruben; Perevalov, Artur; Lathrop, Daniel; Ide, Kayo; Schaeffer, Nathanael

2017-11-01

The model of the Earth's magnetic field has been investigated in recent years through experiments and numerical models. At the University of Maryland, experimental studies are implemented in a three-meter spherical Couette device filled with liquid sodium. The inner and outer spheres of this apparatus mimic the planet's inner core and core-mantle boundary, respectively. These experiments incorporate high velocity flows with Reynolds numbers 108 . In spherical Couette geometry, the numerical scheme applied to this work features finite difference methods in the radial direction and pseudospectral spherical harmonic transforms elsewhere. Adding to the numerical model, data assimilation integrates the experimental outer-layer magnetic field measurements. This semi-numerical model can then be compared to the experimental results as well as forecasting magnetic field changes. Data assimilation makes it possible to get estimates of internal motions of the three-meter experiment that would otherwise be intrusive or impossible to obtain in experiments or too computationally expensive with a purely numerical code. If we can provide accurate models of the three-meter device, it is possible to attempt to model the geomagnetic field. We gratefully acknowledge the support of NSF Grant No. EAR1417148 & DGE1322106.

Measurement and modelization of silica opal optical properties

NASA Astrophysics Data System (ADS)

Avoine, Amaury; Hong, Phan Ngoc; Frederich, Hugo; Aregahegn, Kifle; Bénalloul, Paul; Coolen, Laurent; Schwob, Catherine; Thu Nga, Pham; Gallas, Bruno; Maître, Agnès

2014-03-01

We present the synthesis process and optical characterization of artificial silica opals. The specular reflection spectra are analyzed and compared to band structure calculations and finite difference time domain (FDTD) simulations. The silica optical index is a key parameter to correctly describe an opal and is usually not known and treated as a free parameter. Here we propose a method to infer the silica index, as well as the silica spheres diameter, from the reflection spectra and we validate it by comparison with two independent infrared methods for the index and, scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements for the spheres diameter.

SU-F-T-67: Correction Factors for Monitor Unit Verification of Clinical Electron Beams

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

Haywood, J

Purpose: Monitor units calculated by electron Monte Carlo treatment planning systems are often higher than TG-71 hand calculations for a majority of patients. Here I’ve calculated tables of geometry and heterogeneity correction factors for correcting electron hand calculations. Method: A flat water phantom with spherical volumes having radii ranging from 3 to 15 cm was created. The spheres were centered with respect to the flat water phantom, and all shapes shared a surface at 100 cm SSD. D{sub max} dose at 100 cm SSD was calculated for each cone and energy on the flat phantom and for the spherical volumesmore » in the absence of the flat phantom. The ratio of dose in the sphere to dose in the flat phantom defined the geometrical correction factor. The heterogeneity factors were then calculated from the unrestricted collisional stopping power for tissues encountered in electron beam treatments. These factors were then used in patient second check calculations. Patient curvature was estimated by the largest sphere that aligns to the patient contour, and appropriate tissue density was read from the physical properties provided by the CT. The resulting MU were compared to those calculated by the treatment planning system and TG-71 hand calculations. Results: The geometry and heterogeneity correction factors range from ∼(0.8–1.0) and ∼(0.9–1.01) respectively for the energies and cones presented. Percent differences for TG-71 hand calculations drop from ∼(3–14)% to ∼(0–2)%. Conclusion: Monitor units calculated with the correction factors typically decrease the percent difference to under actionable levels, < 5%. While these correction factors work for a majority of patients, there are some patient anatomies that do not fit the assumptions made. Using these factors in hand calculations is a first step in bringing the verification monitor units into agreement with the treatment planning system MU.« less

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.

Analysis of drift effects on the tokamak power scrape-off width using SOLPS-ITER

NASA Astrophysics Data System (ADS)

Meier, E. T.; Goldston, R. J.; Kaveeva, E. G.; Makowski, M. A.; Mordijck, S.; Rozhansky, V. A.; Senichenkov, I. Yu; Voskoboynikov, S. P.

2016-12-01

SOLPS-ITER, a comprehensive 2D scrape-off layer modeling package, is used to examine the physical mechanisms that set the scrape-off width ({λq} ) for inter-ELM power exhaust. Guided by Goldston’s heuristic drift (HD) model, which shows remarkable quantitative agreement with experimental data, this research examines drift effects on {λq} in a DIII-D H-mode magnetic equilibrium. As a numerical expedient, a low target recycling coefficient of 0.9 is used in the simulations, resulting in outer target plasma that is sheath limited instead of conduction limited as in the experiment. Scrape-off layer (SOL) particle diffusivity (D SOL) is scanned from 1 to 0.1 m2 s-1. Across this diffusivity range, outer divertor heat flux is dominated by a narrow (˜3-4 mm when mapped to the outer midplane) electron convection channel associated with thermoelectric current through the SOL from outer to inner divertor. An order-unity up-down ion pressure asymmetry allows net ion drift flux across the separatrix, facilitated by an artificial mechanism that mimics the anomalous electron transport required for overall ambipolarity in the HD model. At {{D}\\text{SOL}}=0.1 m2 s-1, the density fall-off length is similar to the electron temperature fall-off length, as predicted by the HD model and as seen experimentally. This research represents a step toward a deeper understanding of the power scrape-off width, and serves as a basis for extending fluid modeling to more experimentally relevant, high-collisionality regimes.

Analysis of drift effects on the tokamak power scrape-off width using SOLPS-ITER

DOE PAGES

Meier, E. T.; Goldston, R. J.; Kaveeva, E. G.; ...

2016-11-02

SOLPS-ITER, a comprehensive 2D scrape-off layer modeling package, is used to examine the physical mechanisms that set the scrape-off width (more » $${{\\lambda}_{q}}$$ ) for inter-ELM power exhaust. Guided by Goldston's heuristic drift (HD) model, which shows remarkable quantitative agreement with experimental data, this research examines drift effects on $${{\\lambda}_{q}}$$ in a DIII-D H-mode magnetic equilibrium. As a numerical expedient, a low target recycling coefficient of 0.9 is used in the simulations, resulting in outer target plasma that is sheath limited instead of conduction limited as in the experiment. Scrape-off layer (SOL) particle diffusivity (D SOL) is scanned from 1 to 0.1 m2 s –1. Across this diffusivity range, outer divertor heat flux is dominated by a narrow (~3–4mm when mapped to the outer midplane) electron convection channel associated with thermoelectric current through the SOL from outer to inner divertor. An order-unity up–down ion pressure asymmetry allows net ion drift flux across the separatrix, facilitated by an artificial mechanism that mimics the anomalous electron transport required for overall ambipolarity in the HD model. At $${{D}_{\\text{SOL}}}=0.1$$ m2 s –1, the density fall-off length is similar to the electron temperature fall-off length, as predicted by the HD model and as seen experimentally. Furthermore, this research represents a step toward a deeper understanding of the power scrape-off width, and serves as a basis for extending fluid modeling to more experimentally relevant, high-collisionality regimes.« less

Ultra-low-frequency wave-driven diffusion of radiation belt relativistic electrons

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

Su, Zhenpeng; Zhu, Hui; Xiao, Fuliang

The Van Allen radiation belts are typically two zones of energetic particles encircling the Earth separated by the slot region. How the outer radiation belt electrons are accelerated to relativistic energies remains an unanswered question. Recent studies have presented compelling evidence for the local acceleration by very-low-frequency (VLF) chorus waves. However, there has been a competing theory to the local acceleration, radial diffusion by ultra-low-frequency (ULF) waves, whose importance has not yet been determined definitively. Here we report a unique radiation belt event with intense ULF waves but no detectable VLF chorus waves. So, our results demonstrate that the ULFmore » waves moved the inner edge of the outer radiation belt earthward 0.3 Earth radii and enhanced the relativistic electron fluxes by up to one order of magnitude near the slot region within about 10 h, providing strong evidence for the radial diffusion of radiation belt relativistic electrons.« less

Ultra-low-frequency wave-driven diffusion of radiation belt relativistic electrons

DOE PAGES

Su, Zhenpeng; Zhu, Hui; Xiao, Fuliang; ...

2015-12-22

The Van Allen radiation belts are typically two zones of energetic particles encircling the Earth separated by the slot region. How the outer radiation belt electrons are accelerated to relativistic energies remains an unanswered question. Recent studies have presented compelling evidence for the local acceleration by very-low-frequency (VLF) chorus waves. However, there has been a competing theory to the local acceleration, radial diffusion by ultra-low-frequency (ULF) waves, whose importance has not yet been determined definitively. Here we report a unique radiation belt event with intense ULF waves but no detectable VLF chorus waves. So, our results demonstrate that the ULFmore » waves moved the inner edge of the outer radiation belt earthward 0.3 Earth radii and enhanced the relativistic electron fluxes by up to one order of magnitude near the slot region within about 10 h, providing strong evidence for the radial diffusion of radiation belt relativistic electrons.« 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.

The turbulent plasmasphere boundary layer and the outer radiation belt boundary

NASA Astrophysics Data System (ADS)

Mishin, Evgeny; Sotnikov, Vladimir

2017-12-01

We report on observations of enhanced plasma turbulence and hot particle distributions in the plasmasphere boundary layer formed by reconnection-injected hot plasma jets entering the plasmasphere. The data confirm that the electron pressure peak is formed just outward of the plasmapause in the premidnight sector. Free energy for plasma wave excitation comes from diamagnetic ion currents near the inner edge of the boundary layer due to the ion pressure gradient, electron diamagnetic currents in the entry layer near the electron plasma sheet boundary, and anisotropic (sometimes ring-like) ion distributions revealed inside, and further inward of, the inner boundary. We also show that nonlinear parametric coupling between lower oblique resonance and fast magnetosonic waves significantly contributes to the VLF whistler wave spectrum in the plasmasphere boundary layer. These emissions represent a distinctive subset of substorm/storm-related VLF activity in the region devoid of substorm injected tens keV electrons and could be responsible for the alteration of the outer radiation belt boundary during (sub)storms.