WorldWideScience

Sample records for oxidation dioxygen transport

  1. Molecular Recognition in the Oxidation of Catechols by Dicobalt-BISDIEN Dioxygen Complexes

    Science.gov (United States)

    1992-01-30

    Recognition in the Oxidation of Catechols by Dicobalt-RISDIEN Dioxygen Complexes Lizete F S Cezar and Bruno Szpoganicz Departamento de Quimica ...bridged bi- nuclear Co(II)-BISDIEN dioxygen complexes; Co20 2 LCat2 + is the bivalent form, and Co20 2 (OH)LCat + and Co 20 2 (OH)2 Cat° are hydroxo

  2. The cathodic reduction of dioxygen on uranium oxide in dilute alkaline aqueous solution

    International Nuclear Information System (INIS)

    Hocking, W.H.; Betteridge, J.S.; Shoesmith, D.W.

    1991-09-01

    The cathodic reduction of dioxygen on uranium oxide in dilute alkaline aqueous solutions has been investigated within the context of a program to develop a comprehensive model to predict the behaviour of used CANDU (Canada Deuterium Uranium) nuclear fuel under disposal-vault conditions. Two different kinds of ceramic UO 2 were studied: reactor-grade CANDU fuel with normal p-type electrical conductivity and low-resistance material that exhibits n-type photoelectrochemical behaviour. The transport of electroactive species in solution was controlled by varying the rotation rate of rotating disc electrodes (RDE) and rotating ring-disc electrodes (RRDE). Steady-state polarization measurements were made using the current-interrupt method to compensate for the potential drop caused by ohmic resistance. Any release of peroxide to solution from the UO 2 (disc) surface could be monitored by oxidizing it at the Au ring of an RRDE. The existing theory for the cathodic 0 2 -reduction process as applied to RDE and RRDE experiments has been reviewed as a starting point for the interpretation of the results obtained in our work. (37 figs., 2 tabs., 170 refs.)

  3. Determination of binding-dioxygen in dioxygen complexes by headspace gas chromatography.

    Science.gov (United States)

    Wang, Wei; Feng, Shun; Li, Ya-ni; Wu, Meiying; Wang, Jide

    2008-06-06

    Dioxygen complexes play important roles in organisms' bodies, so the determination of binding-dioxygen has practical significance. A simple and robust method based on headspace gas chromatography was proposed to determine the binding-dioxygen in dioxygen complexes. By measuring the content change of nitrogen gas in a vial, the amount of oxygen released from dixoygen complexes can be determined. The method was validated using potassium chlorate as model sample, and the results exhibited good recoveries (90-99%) with the relative standard deviation less than 8%. It was also used to analyze dioxygen complex of cobalt bis(salicylaldehyde) ethylenediimine and polyamine cobalt complexes prepared by solid-phase reaction.

  4. Visible-Light-Driven Oxidation of Organic Substrates with Dioxygen Mediated by a [Ru(bpy)3 ](2+) /Laccase System.

    Science.gov (United States)

    Schneider, Ludovic; Mekmouche, Yasmina; Rousselot-Pailley, Pierre; Simaan, A Jalila; Robert, Viviane; Réglier, Marius; Aukauloo, Ally; Tron, Thierry

    2015-09-21

    Oxidation reactions are highly important chemical transformations that still require harsh reaction conditions and stoichiometric amounts of chemical oxidants that are often toxic. To circumvent these issues, olefins oxidation is achieved in mild conditions upon irradiation of an aqueous solution of the complex [Ru(bpy)3 ](2+) and the enzyme laccase. Epoxide formation is coupled to the light-driven reduction of O2 by [Ru(bpy)3 ](2+) /laccase system. The reactivity can be explained by dioxygen acting both as an oxidative agent and as renewable electron acceptor, avoiding the use of a sacrificial electron acceptor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. The Cytochrome bd Oxidase of Porphyromonas gingivalis Contributes to Oxidative Stress Resistance and Dioxygen Tolerance.

    Directory of Open Access Journals (Sweden)

    Julia Leclerc

    Full Text Available Porphyromonas gingivalis is an etiologic agent of periodontal disease in humans. The disease is associated with the formation of a mixed oral biofilm which is exposed to oxygen and environmental stress, such as oxidative stress. To investigate possible roles for cytochrome bd oxidase in the growth and persistence of this anaerobic bacterium inside the oral biofilm, mutant strains deficient in cytochrome bd oxidase activity were characterized. This study demonstrated that the cytochrome bd oxidase of Porphyromonas gingivalis, encoded by cydAB, was able to catalyse O2 consumption and was involved in peroxide and superoxide resistance, and dioxygen tolerance.

  6. Synthetic heme/copper assemblies: toward an understanding of cytochrome c oxidase interactions with dioxygen and nitrogen oxides.

    Science.gov (United States)

    Hematian, Shabnam; Garcia-Bosch, Isaac; Karlin, Kenneth D

    2015-08-18

    Our long-time niche in synthetic biological inorganic chemistry has been to design ligands and generate coordination complexes of copper or iron ions or both, those reacting with dioxygen (O2) or nitrogen oxides (e.g., nitric oxide (NO(g)) and nitrite (NO2(-))) or both. As inspiration for this work, we turn to mitochondrial cytochrome c oxidase, which is responsible for dioxygen consumption and is also the predominant target for NO(g) and nitrite within mitochondria. In this Account, we highlight recent advances in studying synthetic heme/Cu complexes in two respects. First, there is the design, synthesis, and characterization of new O2 adducts whose further study will add insights into O2 reductive cleavage chemistry. Second, we describe how related heme/Cu constructs reduce nitrite ion to NO(g) or the reverse, oxidize NO(g) to nitrite. The reactions of nitrogen oxides occur as part of CcO's function, which is intimately tied to cellular O2 balance. We had first discovered that reduced heme/Cu compounds react with O2 giving μ-oxo heme-Fe(III)-O-Cu(II)(L) products; their properties are discussed. The O-atom is derived from dioxygen, and interrogations of these systems led to the construction and characterization of three distinctive classes of heme-peroxo complexes, two high-spin and one low-spin species. Recent investigations include a new approach to the synthesis of low-spin heme-peroxo-Cu complexes, employing a "naked" synthon, where the copper ligand denticity and geometric types can be varied. The result is a collection of such complexes; spectroscopic and structural features (by DFT calculations) are described. Some of these compounds are reactive toward reductants/protons effecting subsequent O-O cleavage. This points to how subtle improvements in ligand environment lead to a desired local structure and resulting optimized reactivity, as known to occur at enzyme active sites. The other sector of research is focused on heme/Cu assemblies mediating the redox

  7. $MNO_2$ catalyzed carbon electrodes for dioxygen reduction in concentrated alkali

    OpenAIRE

    Manoharan, R; Shulka, AK

    1984-01-01

    A process to deposit $\\gamma-MnO_2$ catalytic oxide onto coconut-shell charcoal substrate is described. Current-potential curves for electroreduction of dioxygen with electrodes fabricated from this catalyzed substrate are obtained in 6M KOH under ambient conditions. The performance of these electrodes is competitive with platinized carbon electrodes.

  8. Immobilized unfolded cytochrome c acts as a catalyst for dioxygen reduction.

    Science.gov (United States)

    Tavagnacco, Claudio; Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia; Borsari, Marco

    2011-10-21

    Unfolding turns immobilized cytochrome c into a His-His ligated form endowed with catalytic activity towards O(2), which is absent in the native protein. Dioxygen could be used by naturally occurring unfolded cytochrome c as a substrate for the production of partially reduced oxygen species (PROS) contributing to the cell oxidative stress.

  9. Dioxygen Binding by Cobalt(II Complexes of 8,8'-bis(aminomethyl-2,2'-biquinoline

    Directory of Open Access Journals (Sweden)

    Muhammad S. Khan

    2015-02-01

    Full Text Available A new series of Co(II complexes of the type CoLX2 , where Lis a tetra-dentate ligand 8,8'-bis(aminomethyl-2,2'-biquinoline  and X= SCN–, BF4–, I– or NO3– ,  have been synthesized and characterized. The complexes have magnetic moments in the range typical of a low-spin d7 Co(II center. The interaction of these Co(II complexes with dioxygen was studied by E.S.R. spectroscopy. A dicobalt(III peroxo-bridged complex was formed in DMF solution, associated with the formation of an E.S.R.-silent solution compatible with the formation of low-spin d6 Co(III species. Similar behavior was also observed for the interaction of these Co(II complexes with dioxygen in the presence of ancillary ligands such as pyridine and 2-methylimidazole. The dioxygen complexes proved successful as oxygen carrier oxidation catalysts for tripehnylphosphine and 2,6-bis(t-butylphenol.

  10. Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

    International Nuclear Information System (INIS)

    Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige; Sakurai, Takeshi

    2014-01-01

    Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The single turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase

  11. Study on dioxygen reduction by mutational modifications of the hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Morishita, Hirotoshi; Kurita, Daisuke; Kataoka, Kunishige; Sakurai, Takeshi, E-mail: tsakurai@se.kanazawa-u.ac.jp

    2014-07-18

    Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The single turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase.

  12. Mediatorless bioelectrocatalysis of dioxygen reduction at indium-doped tin oxide (ITO) and ITO nanoparticulate film electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rozniecka, Ewa; Jonsson-Niedziolka, Martin; Sobczak, Janusz W. [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa (Poland); Opallo, Marcin, E-mail: mopallo@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa (Poland)

    2011-10-01

    Highlights: > We introduced ITO nanoparticulate films for enzyme immobilization. > The material promotes mediatorless bioelectrocatalysis towards dioxygen reduction. > The electrocatalytical current increase with the thickness of nanoparticulate film. > There is no difference in electrocatalytic current in the presence or absence of mediator. > The stability of the electrode can be improved by crosslinking of the enzyme with bovine serum albumin and glutaraldehyde. - Abstract: Bilirubin oxidase was immobilised on ITO electrodes: bare or covered by ITO nanoparticulate film. The latter material was obtained by immersion and withdrawal of the substrate into ITO nanoparticles suspension. Formation of a protein deposit was confirmed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The electrode surface is covered by a protein film in the form of globular aggregates and it exhibits mediatorless electrocatalytic activity towards dioxygen reduction to water at pH 4.8. Modification of the electrode with ITO particles increases its catalytic activity about ten times up to 110 {mu}A cm{sup -2} seen for electrodes prepared by twelve immersion and withdrawal steps into ITO nanoparticle suspension. The catalytic activity is almost unaffected by addition of mediator to solution. The stability of the electrodes is increased by cross-linking of the enzyme with bovine serum albumin and glutaraldehyde. This electrode was applied as biocathode in a zinc-dioxygen battery operating in 0.1 mol dm{sup -3} McIlvaine buffer (pH 4.8).

  13. Mediatorless bioelectrocatalysis of dioxygen reduction at indium-doped tin oxide (ITO) and ITO nanoparticulate film electrodes

    International Nuclear Information System (INIS)

    Rozniecka, Ewa; Jonsson-Niedziolka, Martin; Sobczak, Janusz W.; Opallo, Marcin

    2011-01-01

    Highlights: → We introduced ITO nanoparticulate films for enzyme immobilization. → The material promotes mediatorless bioelectrocatalysis towards dioxygen reduction. → The electrocatalytical current increase with the thickness of nanoparticulate film. → There is no difference in electrocatalytic current in the presence or absence of mediator. → The stability of the electrode can be improved by crosslinking of the enzyme with bovine serum albumin and glutaraldehyde. - Abstract: Bilirubin oxidase was immobilised on ITO electrodes: bare or covered by ITO nanoparticulate film. The latter material was obtained by immersion and withdrawal of the substrate into ITO nanoparticles suspension. Formation of a protein deposit was confirmed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The electrode surface is covered by a protein film in the form of globular aggregates and it exhibits mediatorless electrocatalytic activity towards dioxygen reduction to water at pH 4.8. Modification of the electrode with ITO particles increases its catalytic activity about ten times up to 110 μA cm -2 seen for electrodes prepared by twelve immersion and withdrawal steps into ITO nanoparticle suspension. The catalytic activity is almost unaffected by addition of mediator to solution. The stability of the electrodes is increased by cross-linking of the enzyme with bovine serum albumin and glutaraldehyde. This electrode was applied as biocathode in a zinc-dioxygen battery operating in 0.1 mol dm -3 McIlvaine buffer (pH 4.8).

  14. Recent Developments of Nanostructured Electrodes for Bioelectrocatalysis of Dioxygen Reduction

    Directory of Open Access Journals (Sweden)

    Marcin Opallo

    2011-01-01

    Full Text Available The recent development of nanostructured electrodes for bioelectrocatalytic dioxygen reduction catalysed by two copper oxidoreductases, laccase and bilirubin oxidase, is reviewed. Carbon-based nanomaterials as carbon nanotubes or carbon nanoparticles are frequently used for electrode modification, whereas there are only few examples of biocathodes modified with metal or metal oxide nanoparticles. These nanomaterials are adsorbed on the electrode surface or embedded in multicomponent film. The nano-objects deposited act as electron shuttles between the enzyme and the electrode substrate providing favourable conditions for mediatorless bioelectrocatalysis.

  15. Toward understanding macrocycle specificity of iron on the dioxygen-binding ability: a theoretical study.

    Science.gov (United States)

    Sun, Yong; Chen, Kexian; Jia, Lu; Li, Haoran

    2011-08-14

    In an effort to examine the interaction between dioxygen and iron-macrocyclic complexes, and to understand how this interaction was affected by those different macrocyclic ligands, dioxygen binding with iron-porphyrin, iron-phthalocyanine, iron-dibenzotetraaza[14]annulene, and iron-salen complexes is investigated by means of quantum chemical calculations utilizing Density Functional Theory (DFT). Based on the analysis of factors influencing the corresponding dioxygen binding process, it showed that different macrocyclic ligands possess different O-O bond distances, and different electronic configurations for the bound O(2) and non-aromatic macrocyclic ligands favor dioxygen activation. Furthermore, the smaller the energy gap between the HOMO of iron-macrocyclic complexes and the LUMO of dioxygen, the more active the bound O(2) becomes, with a longer O-O bond distance and a shorter Fe-O bond length.

  16. Proton transport facilitating water-oxidation: the role of second sphere ligands surrounding the catalytic metal cluster.

    Science.gov (United States)

    Bao, Han; Dilbeck, Preston L; Burnap, Robert L

    2013-10-01

    The ability of PSII to extract electrons from water, with molecular oxygen as a by-product, is a remarkable biochemical and evolutionary innovation. From an evolutionary perspective, the invention of PSII approximately 2.7 Ga led to the accelerated accumulation of biomass in the biosphere and the accumulation of oxygen in the atmosphere, a combination that allowed for the evolution of a much more complex and extensive biosphere than would otherwise have been possible. From the biochemical and enzymatic perspective, PSII is remarkable because of the thermodynamic and kinetic obstacles that needed to have been overcome to oxidize water as the ultimate photosynthetic electron donor. This article focuses on how proton release is an integral part of how these kinetic and thermodynamic obstacles have been overcome: the sequential removal of protons from the active site of H2O-oxidation facilitates the multistep oxidation of the substrate water at the Mn4CaOx, the catalytic heart of the H2O-oxidation reaction. As noted previously, the facilitated deprotonation of the Mn4CaOx cluster exerts a redox-leveling function preventing the accumulation of excess positive charge on the cluster, which might otherwise hinder the already energetically difficult oxidation of water. Using recent results, including the characteristics of site-directed mutants, the role of the second sphere of amino acid ligands and the associated network of water molecules surrounding the Mn4CaOx is discussed in relation to proton transport in other systems. In addition to the redox-leveling function, a trapping function is assigned to the proton release step occurring immediately prior to the dioxygen chemistry. This trapping appears to involve a yet-to-be clarified gating mechanism that facilitates to coordinated release of a proton from the neighborhood of the active site thereby insuring that the backward charge-recombination reaction does not out-compete the forward reaction of dioxygen chemistry

  17. Voltammetry and single-molecule in situ scanning tunneling microscopy of laccases and bilirubin oxidase in electrocatalytic dioxygen reduction on Au(111) single-crystal electrodes

    DEFF Research Database (Denmark)

    Climent, Victor; Zhang, Jingdong; Friis, Esben Peter

    2012-01-01

    Laccases (E.C. 1.10.3.2) are multicopper oxidases catalytically active in the oxidation of diphenolics and related compounds by molecular dioxygen. The laccases contain a single-copper type I center and a trinuclear cluster of a single-copper type II and a dinuclear type III center. The oxidation...

  18. Experimental and Computational Evidence for the Mechanism of Intradiol Catechol Dioxygenation by Non- Heme Iron(III) Complexes

    NARCIS (Netherlands)

    Jastrzebski, Robin; Quesne, Matthew G.; Weckhuysen, Bert M.; de Visser, Sam P.; Bruijnincx, Pieter C. A.

    2014-01-01

    Catechol intradiol dioxygenation is a unique reaction catalyzed by iron-dependent enzymes and nonheme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational

  19. A kinetic and ESR investigation of iron(II) oxalate oxidation by hydrogen peroxide and dioxygen as a source of hydroxyl radicals

    DEFF Research Database (Denmark)

    Park, J S; Wood, P M; Davies, Michael Jonathan

    1997-01-01

    The reaction of Fe(II) oxalate with hydrogen peroxide and dioxygen was studied for oxalate concentrations up to 20 mM and pH 2-5, under which conditions mono- and bis-oxalate complexes (Fe[II](ox) and Fe[II](ox)2[2-]) and uncomplexed Fe2+ must be considered. The reaction of Fe(II) oxalate...... with hydrogen peroxide (Fe2+ + H2O2 --> Fe3+ + .OH + OH-) was monitored in continuous flow by ESR with t-butanol as a radical trap. The reaction is much faster than for uncomplexed Fe2+ and a rate constant, k = 1 x 10(4) M(-1) s(-1) is deduced for Fe(II)(ox). The reaction of Fe(II) oxalate with dioxygen...... by oxalate. Further ESR studies with DMPO as spin trap reveal that reaction of Fe(II) oxalate with hydrogen peroxide can also lead to formation of the carboxylate radical anion (CO2-), an assignment confirmed by photolysis of Fe(II) oxalate in the presence of DMPO....

  20. Supramolecular tetracluster-cobalt porphyrin: a four-electron transfer catalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Winnischofer, Herbert; Otake, Vesper Yoshiyuki; Dovidauskas, Sergio; Nakamura, Marcelo; Toma, Henrique Eisi; Araki, Koiti

    2004-01-01

    Electrocatalysis by CoTCP {CoTCP meso-tetrakis(4-pyridyl)porphynatocobalt(III)} coordinated to four [Ru 3 (μ 3 -O)(μ 2 -CH 3 CO 2 ) 6 (py) 2 ] + complexes in the four-electron reduction of dioxygen, has been unequivocally demonstrated in this work by using two types of electrostatically assembled films of CoTCP and anionic zinc or free-base meso-tetrakis(4-sulfonatophenyl)porphyrins (ZnTPPS or H 2 TPPS), as well as, by employing different electrode materials. An enhanced electrocatalytic activity has been observed, in spite of the fact that the typical bis-coordination of dioxygen to two cobalt porphyrin sites is precluded in such CoTCP/ZnTPPS or CoTCP/H 2 TPPS bilayered films. In addition, negligible ring currents have been observed in ring-disk voltammetry measurements, yielding straight Levich and Koutecky-Levich plots, whose slopes approached the theoretical 4e - curve in air, or in O 2 saturated solutions (pH 3-5). The use of gold instead of glassy carbon (GC) electrodes has not also significantly perturbed the mechanism. By ruling out any influence from the electrode materials, a well known critical point in the catalysis by cobalt porphyrins, the results have shown that CoTCP is acting as a four-electron transfer catalyst for dioxygen reduction. Also, by excluding the possibility of bis-coordination of dioxygen, it was shown that the electronic and supramolecular effects exerted by the peripheral ruthenium cluster complexes should be triggering the four-electron catalytic activity of the cobalt porphyrin center

  1. Electrocatalytic reduction of dioxygen by cobalt porphyrin-modified glassy carbon electrode with single-walled carbon nanotubes and nafion in aqueous solutions

    International Nuclear Information System (INIS)

    Choi, Ayoung; Jeong, Haesang; Kim, Songmi; Jo, Suhee; Jeon, Seungwon

    2008-01-01

    Cobalt porphyrin (CoP)-modified glassy carbon electrode (GCE) with single-walled carbon nanotubes (SWNTs) and Nafion demonstrated a higher electrocatalytic activity for the reduction of dioxygen in 0.1 M H 2 SO 4 solution. Cyclic and hydrodynamic voltammetry at the CoP-SWNTs/GCE-modified electrodes in O 2 -saturated aqueous solutions was used to study the electrocatalytic pathway. Compared with the CoP/GCE-modified electrodes, the reduction potential of dioxygen at the CoP-SWNTs/GCE-modified electrodes was shifted to the positive direction and the limiting current was greatly increased. Especially, the Co(TMPP)-SWNTs/GCE-modified electrode was catalyzed effectively by the 4e - reduction of dioxygen to water, because hydrodynamic voltammetry revealed the transference of approximately four electrons for dioxygen reduction and the minimal generation of hydrogen peroxide in the process of dioxygen reduction

  2. Evolutionary ecology during the rise of dioxygen in the Earth's atmosphere.

    Science.gov (United States)

    Sleep, Norman H; Bird, Dennis K

    2008-08-27

    Pre-photosynthetic niches were meagre with a productivity of much less than 10(-4) of modern photosynthesis. Serpentinization, arc volcanism and ridge-axis volcanism reliably provided H(2). Methanogens and acetogens reacted CO(2) with H(2) to obtain energy and make organic matter. These skills pre-adapted a bacterium for anoxygenic photosynthesis, probably starting with H(2) in lieu of an oxygen 'acceptor'. Use of ferrous iron and sulphide followed as abundant oxygen acceptors, allowing productivity to approach modern levels. The 'photobacterium' proliferated rooting much of the bacterial tree. Land photosynthetic microbes faced a dearth of oxygen acceptors and nutrients. A consortium of photosynthetic and soil bacteria aided weathering and access to ferrous iron. Biologically enhanced weathering led to the formation of shales and, ultimately, to granitic rocks. Already oxidized iron-poor sedimentary rocks and low-iron granites provided scant oxygen acceptors, as did freshwater in their drainages. Cyanobacteria evolved dioxygen production that relieved them of these vicissitudes. They did not immediately dominate the planet. Eventually, anoxygenic and oxygenic photosynthesis oxidized much of the Earth's crust and supplied sulphate to the ocean. Anoxygenic photosynthesis remained important until there was enough O(2) in downwelling seawater to quantitatively oxidize massive sulphides at mid-ocean ridge axes.

  3. Photorelease of triplet and singlet oxygen from dioxygen complexes

    Czech Academy of Sciences Publication Activity Database

    Wagnerová, Dana Marie; Lang, Kamil

    2011-01-01

    Roč. 255, 23-24 (2011), s. 2904-2911 ISSN 0010-8545 R&D Projects: GA ČR GAP207/10/1447; GA ČR GAP208/10/1678 Institutional research plan: CEZ:AV0Z40320502 Keywords : singlet oxygen * triplet oxygen * photochemical elimination * photorelease * Dioxygen complex Subject RIV: CA - Inorganic Chemistry Impact factor: 12.110, year: 2011

  4. Modifications on the hydrogen bond network by mutations of Escherichia coli copper efflux oxidase affect the process of proton transfer to dioxygen leading to alterations of enzymatic activities

    Energy Technology Data Exchange (ETDEWEB)

    Kajikawa, Takao; Kataoka, Kunishige [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192 (Japan); Sakurai, Takeshi, E-mail: tsakurai@se.kanazawa-u.ac.jp [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192 (Japan)

    2012-05-25

    Highlights: Black-Right-Pointing-Pointer Proton transfer pathway to dioxygen in CueO was identified. Black-Right-Pointing-Pointer Glu506 is the key amino acid to transport proton. Black-Right-Pointing-Pointer The Ala mutation at Glu506 formed a compensatory proton transfer pathway. Black-Right-Pointing-Pointer The Ile mutation at Glu506 shut down the hydrogen bond network. -- Abstract: CueO has a branched hydrogen bond network leading from the exterior of the protein molecule to the trinuclear copper center. This network transports protons in the four-electron reduction of dioxygen. We replaced the acidic Glu506 and Asp507 residues with the charged and uncharged amino acid residues. Peculiar changes in the enzyme activity of the mutants relative to the native enzyme indicate that an acidic amino acid residue at position 506 is essential for effective proton transport. The Ala mutation resulted in the formation of a compensatory hydrogen bond network with one or two extra water molecules. On the other hand, the Ile mutation resulted in the complete shutdown of the hydrogen bond network leading to loss of enzymatic activities of CueO. In contrast, the hydrogen bond network without the proton transport function was constructed by the Gln mutation. These results exerted on the hydrogen bond network in CueO are discussed in comparison with proton transfers in cytochrome oxidase.

  5. Degradation of dibenzofuran via multiple dioxygenation by a newly isolated Agrobacterium sp. PH-08.

    Science.gov (United States)

    Le, T T; Murugesan, K; Nam, I-H; Jeon, J-R; Chang, Y-S

    2014-03-01

    To demonstrate the biodegradation of dibenzofuran (DF) and its structural analogs by a newly isolated Agrobacterium sp. PH-08. To assess the biodegradation potential of newly isolated Agrobacterium sp. PH-08, various substrates were evaluated as sole carbon sources in growth and biotransformation experiments. ESI LC-MS/MS analysis revealed the presence of angular degrading by-products as well as lateral dioxygenation metabolites in the upper pathway. The metabolites in the lower pathway also were detected. In addition, the cometabolically degraded daughter compounds of DF-related compounds such as BP and dibenzothiophene (DBT) in dual substrate degradation were observed. Strain PH-08 exhibited the evidence of meta-cleavage pathway as confirmed by the activity and gene expression of catechol-2,3-dioxygenase. Newly isolated bacterial strain, Agrobacterium sp. PH-08, grew well with and degraded DF via both angular and lateral dioxygenation as demonstrated by metabolites identified through ESI LC-MS/MS and GC-MS analyses. The other heterocyclic pollutants were also cometabolically degraded. Few reports have described the complete degradation of DF by a cometabolic lateral pathway. Our study demonstrates the novel results that the newly isolated strain utilized the DF as a sole carbon source and mineralized it via multiple dioxygenation. © 2013 The Society for Applied Microbiology.

  6. Where Water is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster from X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yano, Junko; Yano, Junko; Yachandra, Vittal K.

    2007-10-24

    Light-driven oxidation of water to dioxygen in plants, algae and cyanobacteria iscatalyzed within photosystem II (PS II) by a Mn4Ca cluster. Although the cluster has been studied by many different methods, the structure and the mechanism have remained elusive. X-ray absorption and emission spectroscopy and EXAFS studies have been particularly useful in probing the electronic and geometric structure, and the mechanism of the water oxidation reaction. Recent progress, reviewed here, includes polarized X-ray absorption spectroscopy measurements of PS II single crystals. Analysis of those results has constrained the Mn4Ca cluster geometry to a setof three similar high-resolution structures. The structure of the cluster from the present study is unlike either the 3.0 or 3.5 Angstrom-resolution X-ray structures or other previously proposed models. The differences between the models derived from X-rayspectroscopy and crystallography are predominantly because of damage to the Mn4Ca cluster by X-rays under the conditions used for structure determination by X-ray crystallography. X-ray spectroscopy studies are also used for studying the changes in the structure of the Mn4Ca catalytic center as it cycles through the five intermediate states known as the Si-states (i=0-4). The electronic structure of the Mn4Ca cluster has been studied more recently using resonant inelastic X-ray scattering spectroscopy (RIXS), in addition to the earlier X-ray absorption and emission spectroscopy methods. These studies are revealing that the assignment of formaloxidation states is overly simplistic. A more accurate description should consider the charge density on the Mn atoms that includes the covalency of the bonds and delocalization of the charge over the cluster. The geometric and electronic structure of the Mn4Ca cluster in the S-states derived from X-ray spectroscopy are leading to a detailed understanding of the mechanism of the O-O bond formation during the photosynthetic water

  7. Crystallization of purple nitrous oxide reductase from Pseudomonas stutzeri

    International Nuclear Information System (INIS)

    Pomowski, Anja; Zumft, Walter G.; Kroneck, Peter M. H.; Einsle, Oliver

    2010-01-01

    The physiologically active form of nitrous oxide reductase was isolated and crystallized under strict exclusion of dioxygen and diffraction data were collected from crystals belonging to two different space groups. Nitrous oxide reductase (N 2 OR) from Pseudomonas stutzeri catalyzes the final step in denitrification: the two-electron reduction of nitrous oxide to molecular dinitrogen. Crystals of the enzyme were grown under strict exclusion of dioxygen by sitting-drop vapour diffusion using 2R,3R-butanediol as a cryoprotectant. N 2 OR crystallized in either space group P1 or P6 5 . Interestingly, the key determinant for the resulting space group was the crystallization temperature. Crystals belonging to space group P1 contained four 130 kDa dimers in the asymmetric unit, while crystals belonging to space group P6 5 contained a single dimer in the asymmetric unit. Diffraction data were collected to resolutions better than 2 Å

  8. Experimental and Computational Evidence for the Mechanism of Intradiol Catechol Dioxygenation by Non-Heme Iron(III) Complexes

    Science.gov (United States)

    Jastrzebski, Robin; Quesne, Matthew G; Weckhuysen, Bert M; de Visser, Sam P; Bruijnincx, Pieter C A

    2014-01-01

    Catechol intradiol dioxygenation is a unique reaction catalyzed by iron-dependent enzymes and non-heme iron(III) complexes. The mechanism by which these systems activate dioxygen in this important metabolic process remains controversial. Using a combination of kinetic measurements and computational modelling of multiple iron(III) catecholato complexes, we have elucidated the catechol cleavage mechanism and show that oxygen binds the iron center by partial dissociation of the substrate from the iron complex. The iron(III) superoxide complex that is formed subsequently attacks the carbon atom of the substrate by a rate-determining C=O bond formation step. PMID:25322920

  9. Selective identification of specialized pro-resolving lipid mediators from their biosynthetic double di-oxygenation isomers.

    Science.gov (United States)

    Hansen, Trond V; Dalli, Jesmond; Serhan, Charles N

    The n-3 polyunsaturated fatty acids are substrates for lipoxygenases and cyclooxygenases. During inflammatory processes, these enzymes form several distinct families of oxygenated polyunsaturated fatty acids coined specialized pro-resolving lipid mediators. Structural elucidation of these natural products using LC-MS/MS based metabololipidomics with the pico- to nanogram amounts of biosynthetic material available have been performed. The specialized pro-resolving lipid mediators display stereospecific and potent anti-inflammatory and pro-resolving actions. Most often the different families among these mediators are chemically characterized by two or three chiral, secondary alcohols, separated by either an E,E,Z -triene or an E,Z,E,E -tetraenemoiety. The lipoxygenases also form other oxygenated polyunsaturated natural products, coined double di-oxygenation products, that are constitutional isomers of the protectin and maresin families of specialized pro-resolving lipid mediators. Very often these products exhibit similar chromatographic properties and mass spectrometrical fragment ions as the pro-resolving mediators. In addition, the double di-oxygenation products are sometimes formed in larger amounts than the specialized pro-resolving lipid mediators. Thus, it is not always possible to distinguish between the specialized pro-resolving mediators and their double di-oxygenation isomers in biological systems, using LC/MS-based techniques. Herein, a convenient and easy-to-use protocol to meet this challenge is presented.

  10. Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

  11. Bioelectrocatalytic mediatorless dioxygen reduction at carbon ceramic electrodes modified with bilirubin oxidase

    International Nuclear Information System (INIS)

    Nogala, Wojciech; Celebanska, Anna; Szot, Katarzyna; Wittstock, Gunther; Opallo, Marcin

    2010-01-01

    Carbon ceramic electrodes were prepared by sol-gel processing of a hydrophobic precursor - methyltrimethoxysilane (MTMOS) - together with dispersed graphite microparticles according to a literature procedure. Bilirubin oxidase (BOx) was adsorbed on this electrode from buffer solution and this process was followed by atomic force microscopy (AFM). The electrodes exhibited efficient mediatorless electrocatalytic activity towards dioxygen reduction. The activity depends on the time of adsorption of the enzyme and the pH. The electrode remains active in neutral solution. The bioelectrocatalytic activity is further increased when a fraction of the carbon microparticles is replaced by sulfonated carbon nanoparticles (CNPs). This additive enhances the electrical communication between the enzyme and the electronic conductor. At pH 7 the carbon ceramic electrode modified with bilirubin oxidase retains ca. half of its highest activity. The role of the modified nanoparticles is confirmed by experiments in which a film embedded in a hydrophobic silicate matrix also exhibited efficient mediatorless biocatalytic dioxygen reduction. Scanning electrochemical microscopy (SECM) of the studied electrodes indicated a rather even distribution of the catalytic activity over the electrode surface.

  12. The effect of linker of electrodes prepared from sol–gel ionic liquid precursor and carbon nanoparticles on dioxygen electroreduction bioelectrocatalysis

    International Nuclear Information System (INIS)

    Szot, Katarzyna; Lynch, Robert P.; Lesniewski, Adam; Majewska, Ewa; Sirieix-Plenet, Juliette; Gaillon, Laurent; Opallo, Marcin

    2011-01-01

    The effect of linker of three-dimensional, hydrophilic-carbon-nanoparticle film-electrodes prepared by layer-by-layer method on redox probe accumulation and bioelectrocatalytic dioxygen reduction was studied and compared for two different electrode scaffolds. The linker in both of these scaffolds was based on the same ionic liquid sol–gel precursor, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium bis(trifluoromethyl-sulfonyl)imide. The first electrode type was prepared by alternative immersion of tin doped indium oxide substrate in an aqueous suspension of carbon nanoparticles modified with phenyl sulphonic groups and a sol composed of ionic liquid sol–gel precursor and tetramethoxysilane. For the second electrode type sol was replaced by a methanolic suspension of silicate submicroparticles with appended imidazolium functional groups. In both films 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) anions accumulate irreversibly. In the case of the first electrode electrostatic attraction plays the more important role in comparison to the case of the second where stable adsorption of the redox probe takes place. After adsorption of bilirubin oxidase, electrodes obtained from sol and carbon nanoparticles exhibit modest bioelectrocatalytic activity towards dioxygen reduction at pH 4.8, however those obtained from oppositely charged particles are much more efficient. The magnitude of the associated catalytic current in both cases depends on the number of immersion and withdrawal steps. Interestingly, mediatorless catalysis at electrodes obtained from oppositely charged particles is more efficient than mediated catalysis.

  13. Unique catalytic properties of a butoxy chain-containing ruthenated porphyrin towards oxidation of uric acid and reduction of dioxygen for visible light-enhanced fuel cells

    International Nuclear Information System (INIS)

    Liu, Junchen; Wang, Yi; Deng, Qiang; Zhu, Licai; Chao, Hui; Li, Hong

    2016-01-01

    Highlights: • Ru(II)PTPP/CdS shows two Ru(II)-based oxidation peaks at 0.296 V and 0.830 V. • Photoelectrocatalytic oxidation of UA exhibits good linear responses. • The butoxy chain endows Ru(II)PTPP with multifunctional catalytic properties. • Ru(II)PTPP on CF electrode can remarkably promote the reduction of oxygen. • The assembled cell has I_S_C of 0.136 mA cm"−"2 and P_m_a_x of 31.50 μW cm"−"2. - Abstract: This paper reports the photoelectrocatalytic activities of a ruthenated porphyrin [Ru(phen)_2(IP-C_4O-TPP)]"2"+ (denoted as Ru(II)PTPP, phen = 1,10-phenanthroline, IP = imidazo[4,5-f][1,10]phenanthroline and TPP = 5,10,15,20-tetraphenylporphyrin) containing a covalently-linked butoxy chain (-C_4O-) between IP and TPP moieties by means of various electrochemical techniques in combination with absorption spectroscopy and scanning electronic microscopy. Ru(II)PTPP is assembled on the surface of CdS nanoparticles, showing two Ru(II)-based peaks at 0.296 V and 0.830 V, where uric acid (UA) can be photoelectrocatalytically oxidized in a linear range of 0.01-10.0 mmol L"−"1. The −C_4O- chain endows the Ru(II)PTPP/carbon felt (CF) electrode with favorable dioxygen (O_2) binding sites to achieve a couple of new redox peaks at −0.213 V, where O_2 involves electrocatalytic reduction reactions. While employing 5.0 mmol L"−"1 UA as fuel, and 60 mL min"−"1 O_2 as oxidant, the proposed photoelectrochemical fuel cell shows open-circuit photovoltage of 0.656 V, short-circuit photocurrent density of 0.136 mA cm"−"2, and maximum power density of 31.50 μW cm"−"2 at 0.497 V under visible-light illumination of 0.18 mW cm"−"2. The present study provides an interesting platform for the utilization of renewable energy sources.

  14. Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

    Science.gov (United States)

    Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

    2018-04-06

    Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Charge transport in metal oxide nanocrystal-based materials

    Science.gov (United States)

    Runnerstrom, Evan Lars

    There is probably no class of materials more varied, more widely used, or more ubiquitous than metal oxides. Depending on their composition, metal oxides can exhibit almost any number of properties. Of particular interest are the ways in which charge is transported in metal oxides: devices such as displays, touch screens, and smart windows rely on the ability of certain metal oxides to conduct electricity while maintaining visible transparency. Smart windows, fuel cells, and other electrochemical devices additionally rely on efficient transport of ionic charge in and around metal oxides. Colloidal synthesis has enabled metal oxide nanocrystals to emerge as a relatively new but highly tunable class of materials. Certain metal oxide nanocrystals, particularly highly doped metal oxides, have been enjoying rapid development in the last decade. As in myriad other materials systems, structure dictates the properties of metal oxide nanocrystals, but a full understanding of how nanocrystal synthesis, the processing of nanocrystal-based materials, and the structure of nanocrystals relate to the resulting properties of nanocrystal-based materials is still nascent. Gaining a fundamental understanding of and control over these structure-property relationships is crucial to developing a holistic understanding of metal oxide nanocrystals. The unique ability to tune metal oxide nanocrystals by changing composition through the introduction of dopants or by changing size and shape affords a way to study the interplay between structure, processing, and properties. This overall goal of this work is to chemically synthesize colloidal metal oxide nanocrystals, process them into useful materials, characterize charge transport in materials based on colloidal metal oxide nanocrystals, and develop ways to manipulate charge transport. In particular, this dissertation characterizes how the charge transport properties of metal oxide nanocrystal-based materials depend on their processing and

  16. Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

    2009-01-01

    The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

  17. Transport Physics Mechanisms in Thin-Film Oxides.

    Science.gov (United States)

    Tierney, Brian D.; Hjalmarson, Harold P.; Jacobs-Gedrim, Robin B.; James, Conrad D.; Marinella, Matthew M.

    A physics-based model of electron transport mechanisms in metal-insulating oxide-metal (M-I-M) systems is presented focusing on transport through the metal-oxide interfaces and in the bulk of the oxide. Interface tunneling, such as electron tunneling between the metal and the conduction band, or to oxide defect states, is accounted for via a WKB model. The effects of thermionic emission are also included. In the bulk of the oxide, defect-site hopping is dominant. Corresponding continuum calculations are performed for Ta2O5 M-I-M systems utilizing two different metal electrodes, e.g., platinum and tantalum. Such an asymmetrical M-I-M structure, applicable to resistive memory applications or oxide-based capacitors, reveals that the current can be either bulk or interface limited depending on the bias polarity and concentration of oxygen vacancy defects. Also, the dominance of some transport mechanisms over others is shown to be due to a complex interdependence between the vacancy concentration and bias polarity. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  18. Novel metalloporphyrin catalysts for the oxidation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Showalter, M.C.; Nenoff, T.M.; Shelnutt, J.A.

    1996-11-01

    Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

  19. Unified computational model of transport in metal-insulating oxide-metal systems

    Science.gov (United States)

    Tierney, B. D.; Hjalmarson, H. P.; Jacobs-Gedrim, R. B.; Agarwal, Sapan; James, C. D.; Marinella, M. J.

    2018-04-01

    A unified physics-based model of electron transport in metal-insulator-metal (MIM) systems is presented. In this model, transport through metal-oxide interfaces occurs by electron tunneling between the metal electrodes and oxide defect states. Transport in the oxide bulk is dominated by hopping, modeled as a series of tunneling events that alter the electron occupancy of defect states. Electron transport in the oxide conduction band is treated by the drift-diffusion formalism and defect chemistry reactions link all the various transport mechanisms. It is shown that the current-limiting effect of the interface band offsets is a function of the defect vacancy concentration. These results provide insight into the underlying physical mechanisms of leakage currents in oxide-based capacitors and steady-state electron transport in resistive random access memory (ReRAM) MIM devices. Finally, an explanation of ReRAM bipolar switching behavior based on these results is proposed.

  20. Cu-catalyzed aerobic oxidative esterification of acetophenones with alcohols to α-ketoesters.

    Science.gov (United States)

    Xu, Xuezhao; Ding, Wen; Lin, Yuanguang; Song, Qiuling

    2015-02-06

    Copper-catalyzed aerobic oxidative esterification of acetophenones with alcohols using molecular oxygen has been developed to form a broad range of α-ketoesters in good yields. In addition to reporting scope and limitations of our new method, mechanism studies are reported that reveal that the carbonyl oxygen in the ester mainly originated from dioxygen.

  1. A Further Study of the Products of Sc and Dioxygen Reactions

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Zhou, Mingfei; Andrews, Lester; Johnson, J. R. Tobias; Panas, Itai; Snis, Anders; Roos, Bjoern O.; Arnold, James O. (Technical Monitor)

    1999-01-01

    The products of the reaction of Sc and dioxygen have been reinvestigated. By adding the electron-trapping molecule CC14, additional information about the IR spectra has been obtained, as well as the observation of new bands. New ab initio calculations are also performed on possible products of the Sc plus O2 reaction. The previously observed band at 722.5 per cm is assigned as the b2 mode of ScO2(-). Bands arising from ScO(+), Sc(O2)(+), and(O2)ScO are also assigned. We are still unable to assign any bands to OScO. The problems associated with the computational study of ScO2 are discussed.

  2. Formation of imines by selective gold-catalysed aerobic oxidative coupling of alcohols and amines under ambient conditions

    DEFF Research Database (Denmark)

    Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie

    2010-01-01

    with excellent selectivity (above 98%) at moderate conversion under optimized conditions. The effect of catalytic amounts of different bases was studied, along with reaction temperature and time. Utilisation of a selective catalyst system that uses dioxygen as an oxidant and only produces water as by...

  3. Electron transport properties of indium oxide - indium nitride metal-oxide-semiconductor heterostructures

    International Nuclear Information System (INIS)

    Wang, C.Y.; Hauguth, S.; Polyakov, V.; Schwierz, F.; Cimalla, V.; Kups, T.; Himmerlich, M.; Schaefer, J.A.; Krischok, S.; Ambacher, O.; Morales, F.M.; Lozano, J.G.; Gonzalez, D.; Lebedev, V.

    2008-01-01

    The structural, chemical and electron transport properties of In 2 O 3 /InN heterostructures and oxidized InN epilayers are reported. It is shown that the accumulation of electrons at the InN surface can be manipulated by the formation of a thin surface oxide layer. The epitaxial In 2 O 3 /InN heterojunctions show an increase in the electron concentration due to the increasing band banding at the heterointerface. The oxidation of InN results in improved transport properties and in a reduction of the sheet carrier concentration of the InN epilayer very likely caused by a passivation of surface donors. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. Mechanistic insights into dioxygen activation, oxygen atom exchange and substrate epoxidation by AsqJ dioxygenase from quantum mechanical/molecular mechanical calculations.

    Science.gov (United States)

    Song, Xudan; Lu, Jiarui; Lai, Wenzhen

    2017-08-02

    Herein, we use in-protein quantum mechanical/molecular mechanical (QM/MM) calculations to elucidate the mechanism of dioxygen activation, oxygen atom exchange and substrate epoxidation processes by AsqJ, an Fe II /α-ketoglutarate-dependent dioxygenase (α-KGD) using a 2-His-1-Asp facial triad. Our results demonstrated that the whole reaction proceeds through a quintet surface. The dioxygen activation by AsqJ leads to a quintet penta-coordinated Fe IV -oxo species, which has a square pyramidal geometry with the oxo group trans to His134. This penta-coordinated Fe IV -oxo species is not the reactive one in the substrate epoxidation reaction since its oxo group is pointing away from the target C[double bond, length as m-dash]C bond. Instead, it can undergo the oxo group isomerization followed by water binding or the water binding followed by oxygen atom exchange to form the reactive hexa-coordinated Fe IV -oxo species with the oxo group trans to His211. The calculated parameters of Mössbauer spectra for this hexa-coordinated Fe IV -oxo intermediate are in excellent agreement with the experimental values, suggesting that it is most likely the experimentally trapped species. The calculated energetics indicated that the rate-limiting step is the substrate C[double bond, length as m-dash]C bond activation. This work improves our understanding of the dioxygen activation by α-KGD and provides important structural information about the reactive Fe IV -oxo species.

  5. Gas transport in solid oxide fuel cells

    CERN Document Server

    He, Weidong; Dickerson, James

    2014-01-01

    This book provides a comprehensive overview of contemporary research and emerging measurement technologies associated with gas transport in solid oxide fuel cells. Within these pages, an introduction to the concept of gas diffusion in solid oxide fuel cells is presented. This book also discusses the history and underlying fundamental mechanisms of gas diffusion in solid oxide fuel cells, general theoretical mathematical models for gas diffusion, and traditional and advanced techniques for gas diffusivity measurement.

  6. Oxygen transport by oxygen potential gradient in dense ceramic oxide membranes

    Energy Technology Data Exchange (ETDEWEB)

    Maiya, P.S.; Balachandran, U.; Dusek, J.T.; Mieville, R.L. [Argonne National Lab., IL (United States). Energy Technology Div.; Kleefisch, M.S.; Udovich, C.A. [Amoco Exploration/Production, Naperville, IL (United States)

    1996-05-01

    Numerous studies have been conducted in recent years on the partial oxidation of methane to synthesis gas (syngas: CO + H{sub 2}) with air as the oxidant. In partial oxidation, a mixed-oxide ceramic membrane selectively transports oxygen from the air; this transport is driven by the oxygen potential gradient. Of the several ceramic materials the authors have tested, a mixed oxide based on the Sr-Fe-Co-O system has been found to be very attractive. Extensive oxygen permeability data have been obtained for this material in methane conversion experiments carried out in a reactor. The data have been analyzed by a transport equation based on the phenomenological theory of diffusion under oxygen potential gradients. Thermodynamic calculations were used to estimate the driving force for the transport of oxygen ions. The results show that the transport equation deduced from the literature describes the permeability data reasonably well and can be used to determine the diffusion coefficients and the associated activation energy of oxygen ions in the ceramic membrane material.

  7. Nonheme oxoiron(IV) complexes of pentadentate N5 ligands: spectroscopy, electrochemistry, and oxidative reactivity

    OpenAIRE

    Wang, Dong; Ray, Kallol; Collins, Michael J.; Farquhar, Erik R.; Frisch, Jonathan R.; Gomez, Laura; Jackson, Timothy A.; Kerscher, Marion; Waleska, Arkadius; Comba, Peter; Costas, Miquel; Que, Lawrence, Jr.

    2013-01-01

    Oxoiron(IV) species have been found to act as the oxidants in the catalytic cycles of several mononuclear nonheme iron enzymes that activate dioxygen. To gain insight into the factors that govern the oxidative reactivity of such complexes, a series of five synthetic S = 1 [FeIV(O)(LN5)]2+ complexes has been characterized with respect to their spectroscopic and electrochemical properties as well as their relative abilities to carry out oxo transfer and hydrogen atom abstraction. The Fe=O units...

  8. Mechanism-Based Design of Green Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

    2015-03-16

    In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

  9. A Broad Spectrum Catalytic System for Removal of Toxic Organics from Water by Deep Oxidation - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ayusman

    2000-12-01

    A most pressing need for the DOE environmental management program is the removal of toxic organic compounds present in groundwater and soil at specific DOE sites. While several remediation procedures have been proposed, they suffer from one or more drawbacks. The objective of the present research was to develop new catalytic procedures for the removal of toxic organic compounds from the environment through their deep oxidation to harmless products. In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of toxic organic compounds by dioxygen at 80-90 C in the presence of carbon monoxide or dihydrogen. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, nitro and halo organics, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 hour period. For substrates susceptible to hydrogenation, the conversions were generally high with dihydrogen than with carbon monoxide. It is clear from the results obtained that we have discovered an exceptionally versatile catalytic system for the deep oxidation of toxic organic compounds in water. This system possesses several attractive features not found simultaneously in other reported systems. These are (a) the ability to directly utilize dioxygen as the oxidant, (b) the ability to carry out the deep oxidation of a particularly wide range of functional organics, and (c) the ease of recovery of the catalyst by simple filtration.

  10. Effects of interfacial Fe electronic structures on magnetic and electronic transport properties in oxide/NiFe/oxide heterostructures

    International Nuclear Information System (INIS)

    Liu, Qianqian; Chen, Xi; Zhang, Jing-Yan; Yang, Meiyin; Li, Xu-Jing; Jiang, Shao-Long; Liu, Yi-Wei; Cao, Yi; Wu, Zheng-Long; Feng, Chun; Ding, Lei; Yu, Guang-Hua

    2015-01-01

    Highlights: • The magnetic and transport properties of oxide/NiFe/oxide films were studied. • The oxide (SiO 2 , MgO and HfO 2 ) has different elemental electronegativity. • Redox reaction at different NiFe/oxide interface is dependent on the oxide layer. • Different interfacial electronic structures shown by XPS influence the properties. - Abstract: We report that the magnetic and electronic transport properties in oxide/NiFe(2 nm)/oxide film (oxide = SiO 2 , MgO or HfO 2 ) are strongly influenced by the electronic structure of NiFe/oxide interface. Magnetic measurements show that there exist magnetic dead layers in the SiO 2 sandwiched film and MgO sandwiched film, whereas there is no magnetic dead layer in the HfO 2 sandwiched film. Furthermore, in the ultrathin SiO 2 sandwiched film no magnetoresistance (MR) is detected, while in the ultrathin MgO sandwiched film and HfO 2 sandwiched film the MR ratios reach 0.35% and 0.88%, respectively. The investigation by X-ray photoelectron spectroscopy reveals that the distinct interfacial redox reactions, which are dependent on the oxide layers, lead to the variation of magnetic and transport properties in different oxide/NiFe/oxide heterostructures

  11. Enhanced dimethyl phthalate biodegradation by accelerating phthalic acid di-oxygenation.

    Science.gov (United States)

    Tang, Yingxia; Zhang, Yongming; Jiang, Ling; Yang, Chao; Rittmann, Bruce E

    2017-12-01

    The aerobic biodegradation of dimethyl phthalate (DMP) is initiated with two hydrolysis reactions that generate an intermediate, phthalic acid (PA), that is further biodegraded through a two-step di-oxygenation reaction. DMP biodegradation is inhibited when PA accumulates, but DMP's biodegradation can be enhanced by adding an exogenous electron donor. We evaluated the effect of adding succinate, acetate, or formate as an exogenous electron donor. PA removal rates were increased by 15 and 30% for initial PA concentrations of 0.3 and 0.6 mM when 0.15 and 0.30 mM succinate, respectively, were added as exogenous electron donor. The same electron-equivalent additions of acetate and formate had the same acceleration impacts on PA removal. Consequently, the DMP-removal rate, even PA coexisting with DMP simultaneously, was accelerated by 37% by simultaneous addition of 0.3 mM succinate. Thus, lowering the accumulation of PA by addition of an electron increased the rate of DMP biodegradation.

  12. Uranium Oxide Aerosol Transport in Porous Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Blanchard, Jeremy; Gerlach, David C.; Scheele, Randall D.; Stewart, Mark L.; Reid, Bruce D.; Gauglitz, Phillip A.; Bagaasen, Larry M.; Brown, Charles C.; Iovin, Cristian; Delegard, Calvin H.; Zelenyuk, Alla; Buck, Edgar C.; Riley, Brian J.; Burns, Carolyn A.

    2012-01-23

    The objective of this paper is to investigate the transport of uranium oxide particles that may be present in carbon dioxide (CO2) gas coolant, into the graphite blocks of gas-cooled, graphite moderated reactors. The transport of uranium oxide in the coolant system, and subsequent deposition of this material in the graphite, of such reactors is of interest because it has the potential to influence the application of the Graphite Isotope Ratio Method (GIRM). The GIRM is a technology that has been developed to validate the declared operation of graphite moderated reactors. GIRM exploits isotopic ratio changes that occur in the impurity elements present in the graphite to infer cumulative exposure and hence the reactor’s lifetime cumulative plutonium production. Reference Gesh, et. al., for a more complete discussion on the GIRM technology.

  13. On the Dynamical Behavior of the Cysteine Dioxygenase-l-Cysteine Complex in the Presence of Free Dioxygen and l-Cysteine.

    Science.gov (United States)

    Pietra, Francesco

    2017-11-01

    In this work, viable models of cysteine dioxygenase (CDO) and its complex with l-cysteine dianion were built for the first time, under strict adherence to the crystal structure from X-ray diffraction studies, for all atom molecular dynamics (MD). Based on the CHARMM36 FF, the active site, featuring an octahedral dummy Fe(II) model, allowed us observing water exchange, which would have escaped attention with the more popular bonded models. Free dioxygen (O 2 ) and l-cysteine, added at the active site, could be observed being expelled toward the solvating medium under Random Accelerated Molecular Dynamics (RAMD) along major and minor pathways. Correspondingly, free dioxygen (O 2 ), added to the solvating medium, could be observed to follow the same above pathways in getting to the active site under unbiased MD. For the bulky l-cysteine, 600 ns of trajectory were insufficient for protein penetration, and the molecule was stuck at the protein borders. These models pave the way to free energy studies of ligand associations, devised to better clarify how this cardinal enzyme behaves in human metabolism. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

  14. Electronic structure and charge transport in nonstoichiometric tantalum oxide

    Science.gov (United States)

    Perevalov, T. V.; Gritsenko, V. A.; Gismatulin, A. A.; Voronkovskii, V. A.; Gerasimova, A. K.; Aliev, V. Sh; Prosvirin, I. A.

    2018-06-01

    The atomic and electronic structure of nonstoichiometric oxygen-deficient tantalum oxide TaO x<2.5 grown by ion beam sputtering deposition was studied. The TaO x film content was analyzed by x-ray photoelectron spectroscopy and by quantum-chemistry simulation. TaO x is composed of Ta2O5, metallic tantalum clusters and tantalum suboxides. A method for evaluating the stoichiometry parameter of TaO x from the comparison of experimental and theoretical photoelectron valence band spectra is proposed. The charge transport properties of TaO x were experimentally studied and the transport mechanism was quantitatively analyzed with four theoretical dielectric conductivity models. It was found that the charge transport in almost stoichiometric and nonstoichiometric tantalum oxide can be consistently described by the phonon-assisted tunneling between traps.

  15. Oxygen chemistry in biology: Vibrational spectroscopy, stable isotopes, and future applications

    Energy Technology Data Exchange (ETDEWEB)

    Babcock, G.T. [Michigan State Univ., East Lansing, MI (United States)

    1994-12-01

    Dioxygen is an ideally suited substrate for enzymatic manipulation in oxidation-reduction chemistry and in substrate transformation. It is a powerful oxidant with a midpoint potential of 0.815 at neutral pH; at the same time, however, it exists in a triplet state in its most stable electronic configuration. This latter property confers kinetic inertness as a result of spin-conservation restrictions on reaction chemistry. If these restrictions can be overcome and controlled, dioxygen`s high redox potential can be used to maximize efficiency in free-energy conversion processes and to effect activation of relatively inert substrates.

  16. New transport phenomena probed by dielectric spectroscopy of oxidized and non-oxidized porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Urbach, B.; Axelrod, E.; Sa' ar, A. [Racah Institute of Physics and the Center for Nanoscience and Nanotechnology, the Hebrew University of Jerusalem, Jerusalem 91904 (Israel)

    2007-05-15

    Dielectric spectroscopy accompanied by infrared (IR) and photoluminescence (PL) spectroscopy have been utilized to reveal the correlation between transport, optical and structural properties of oxidized porous silicon (PS). Three relaxation processes at low-, mid- and high-temperatures were observed, including dc-conductivity at high-temperatures. Both the low-T relaxation and the dc conductivity were found to be thermally activated processes that involve tunneling and hopping in between the nanocrystals in oxidized PS. We have found that the dc-conductivity is limited by geometrical constrictions along the transport channels, which are not effected by the oxidation process and are characterized by activation energies of about {proportional_to}0.85 eV. The low-T relaxation process involves thermal activation followed by tunneling in between neighbor nanocrystals, with somewhat lower activation energies. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  17. Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

    International Nuclear Information System (INIS)

    Smirnov, Vladimir M.; Povarov, Vladimir G.; Voronkov, Gennadii P.; Semenov, Valentin G.; Murin, Igor' V.; Gittsovich, Viktor N.; Sinel'nikov, Boris M.

    2001-01-01

    The Fe 2+ /Fe 3+ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3-1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species ≡-O-Fe(OH) 2 and (≡Si-O-) 2 -FeOH forming the surface monolayer are not reduced at 400-600 deg. C because of their covalent bonding to the silica surface, as demonstrated by Moessbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T ≥ 500 deg. C with formation of metallic iron in the form of α-Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T ≥ 600 deg. C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves

  18. Metal Oxides as Efficient Charge Transporters in Perovskite Solar Cells

    KAUST Repository

    Haque, Mohammed; Sheikh, Arif D.; Guan, Xinwei; Wu, Tao

    2017-01-01

    . In this comprehensive review, we focus on the synthesis and applications of metal oxides as electron and hole transporters in efficient PSCs with both mesoporous and planar architectures. Metal oxides and their doped variants with proper energy band alignment

  19. A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. Annual progress report, September 15, 1996 - September 14, 1997

    International Nuclear Information System (INIS)

    Sen, A.

    1997-01-01

    'During the first year, the palladium-catalyzed deep oxidation of toxic organics by dioxygen in aqueous solution was examined in some detail. The research performed has established the viability of the catalytic system to effect the deep (and complete) oxidation of a very wide range of organic substrates under mild conditions. One significant observation was that chemical warfare agent models containing phosphorus-carbon and sulfur-carbon bonds could be eliminated by using this procedure.'

  20. Curcumin Protects -SH Groups and Sulphate Transport after Oxidative Damage in Human Erythrocytes

    Directory of Open Access Journals (Sweden)

    Rossana Morabito

    2015-05-01

    Full Text Available Background/Aims: Erythrocytes, continuously exposed to oxygen pressure and toxic compounds, are sensitive to oxidative stress, namely acting on integral Band 3 protein, with consequences on cell membranes deformability and anion transport efficiency. The aim of the present investigation, conducted on human erythrocytes, is to verify whether curcumin (1 or 10µM, a natural compound with proved antioxidant properties, may counteract Band 3-mediated anion transport alterations due to oxidative stress. Methods: Oxidative conditions were induced by exposure to, alternatively, either 2 mM N-ethylmaleimide (NEM or pH-modified solutions (6.5 and 8.5. Rate constant for SO4= uptake and -SH groups estimation were measured to verify the effect of oxidative stress on anion transport efficiency and erythrocyte membranes. Results: After the exposure of erythrocytes to, alternatively, NEM or pH-modified solutions, a significant decrease in both rate constant for SO4= uptake and -SH groups was observed, which was prevented by curcumin, with a dose-dependent effect. Conclusions: Our results show that: i the decreased efficiency of anion transport may be due to changes in Band 3 protein structure caused by cysteine -SH groups oxidation, especially after exposure to NEM and pH 6.5; ii 10 µM Curcumin is effective in protecting erythrocytes from oxidative stress events at level of cell membrane transport.

  1. Unconventional aspects of electronic transport in delafossite oxides

    Science.gov (United States)

    Daou, Ramzy; Frésard, Raymond; Eyert, Volker; Hébert, Sylvie; Maignan, Antoine

    2017-12-01

    The electronic transport properties of the delafossite oxides ? are usually understood in terms of two well-separated entities, namely the triangular ? and (? layers. Here, we review several cases among this extensive family of materials where the transport depends on the interlayer coupling and displays unconventional properties. We review the doped thermoelectrics based on ? and ?, which show a high-temperature recovery of Fermi-liquid transport exponents, as well as the highly anisotropic metals ?, ?, and ?, where the sheer simplicity of the Fermi surface leads to unconventional transport. We present some of the theoretical tools that have been used to investigate these transport properties and review what can and cannot be learned from the extensive set of electronic structure calculations that have been performed.

  2. Nanocomposite films containing Au nanoparticles formed by electrochemical reduction of metal ions in the multilayer films as electrocatalyst for dioxygen reduction

    International Nuclear Information System (INIS)

    Huang Minghua; Shen Yan; Cheng Wenlong; Shao Yong; Sun Xuping; Liu Baifeng; Dong Shaojun

    2005-01-01

    Through electrostatic layer-by-layer assembly, AuCl 4 - anions and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) cations were alternately deposited on indium tin oxide (ITO) substrates, and 4-aminobenzoic acid modified glassy carbon electrode. Electrochemical reduction of AuCl 4 - anions sandwiched between CoTMPyP layers leads to the in situ formation of Au nanoparticles in the multilayer films. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. UV-vis spectroscopy, X-ray photoelectron spectroscopy and cyclic voltammetry confirm the formation of Au nanoparticles in the multilayer films after electrochemical reduction of AuCl 4 - anions. Atomic force spectroscopy verifies that the as-prepared Au nanoparticles are uniformly distributed with average particles diameters of 20-25 nm. The resulting composite films containing Au nanoparticles with high stability exhibit high electrocatalytic activity for the reduction of dioxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry demonstrate the Au nanoparticles-containing films can catalyze two-electron reduction of O 2 to H 2 O 2 in O 2 -saturated 0.1 M H 2 SO 4 solution

  3. Electrocatalytic oxidation of organic substrates with molecular oxygen using tetradentate ruthenium(III)-Schiff base complexes as catalysts

    International Nuclear Information System (INIS)

    Ourari, Ali; Khelafi, Mostefa; Aggoun, Djouhra; Jutand, Anny; Amatore, Christian

    2012-01-01

    Three complexes Ru(III)ClL n involving different tetradentate Schiff base ligands L n (see L 1 , L 2 and L 3 in ) were used as catalysts in the oxidation of cyclooctene and tetraline in the presence of molecular dioxygen associated with benzoic anhydride. The efficiency of this oxidation reaction was tested in the presence of two apical bases: 1- or 2-methylimidazole. All complexes exhibit a quasi-reversible redox system. The electrolysis experiments were carried out at controlled potential for each complex, using different substrates such as cyclooctene and tetraline. The oxidized products are cyclooctene oxide (turnover 6.7), a mixture of 1-tetralol and 1-tetralone (turnover 7.6) respectively.

  4. Heterojunction PbS nanocrystal solar cells with oxide charge-transport layers.

    Science.gov (United States)

    Hyun, Byung-Ryool; Choi, Joshua J; Seyler, Kyle L; Hanrath, Tobias; Wise, Frank W

    2013-12-23

    Oxides are commonly employed as electron-transport layers in optoelectronic devices based on semiconductor nanocrystals, but are relatively rare as hole-transport layers. We report studies of NiO hole-transport layers in PbS nanocrystal photovoltaic structures. Transient fluorescence experiments are used to verify the relevant energy levels for hole transfer. On the basis of these results, planar heterojunction devices with ZnO as the photoanode and NiO as the photocathode were fabricated and characterized. Solution-processed devices were used to systematically study the dependence on nanocrystal size and achieve conversion efficiency as high as 2.5%. Optical modeling indicates that optimum performance should be obtained with thinner oxide layers than can be produced reliably by solution casting. Room-temperature sputtering allows deposition of oxide layers as thin as 10 nm, which enables optimization of device performance with respect to the thickness of the charge-transport layers. The best devices achieve an open-circuit voltage of 0.72 V and efficiency of 5.3% while eliminating most organic material from the structure and being compatible with tandem structures.

  5. Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory

    DEFF Research Database (Denmark)

    Valdes, Alvaro; Brillet, Jeremie; Graetzel, Michael

    2012-01-01

    An overview of a collaborative experimental and theoretical effort toward efficient hydrogen production via photoelectrochemical splitting of water into di-hydrogen and di-oxygen is presented here. We present state-of-the-art experimental studies using hematite and TiO2 functionalized with gold n...... nanoparticles as photoanode materials, and theoretical studies on electro and photo-catalysis of water on a range of metal oxide semiconductor materials, including recently developed implementation of self-interaction corrected energy functionals....

  6. A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. 1998 annual progress report

    International Nuclear Information System (INIS)

    Sen, A.

    1998-01-01

    'Toxic organics and polymers pose a serious threat to the environment, especially when they are present in aquatic systems. The objective of the research is the design of practical procedures for the removal and/or recycling of such pollutants by oxidation. This report summarizes the work performed in the first one and half years of a three year project. The authors had earlier described a catalytic system for the deep oxidation of toxic organics, such as benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds [1]. In this system, metallic palladium was found to catalyze the oxidation of the substrate by dioxygen in aqueous medium at 80--100 C in the presence of carbon monoxide. For all the substrates examined, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 h period. Because of a pressing need for new procedures for the destruction of chemical warfare agents, the authors have examined in detail the deep oxidation of appropriate model compounds containing phosphorus-carbon and sulfur-carbon bonds using the same catalytic system. The result is the first observation of the efficient catalytic oxidative cleavage of phosphorus-carbon and sulfur-carbon bonds under mild conditions, using dioxygen as the oxidant [2]. In addition to the achievements described above, they have unpublished results in several other areas. For example, they have investigated the possibility of using dihydrogen rather than carbon monoxide as a coreductant in the catalytic deep oxidation of substrates. Even more attractive from a practical standpoint is the possibility of using a mixture of carbon monoxide and dihydrogen (synthesis gas). Indeed, experiments indicated that it is possible to substitute carbon monoxide by dihydrogen or synthesis gas. Significantly, in the case of nitro compounds, the deep oxidation in fact proceeded

  7. Solution processed metal oxide thin film hole transport layers for high performance organic solar cells

    Science.gov (United States)

    Steirer, K. Xerxes; Berry, Joseph J.; Chesin, Jordan P.; Lloyd, Matthew T.; Widjonarko, Nicodemus Edwin; Miedaner, Alexander; Curtis, Calvin J.; Ginley, David S.; Olson, Dana C.

    2017-01-10

    A method for the application of solution processed metal oxide hole transport layers in organic photovoltaic devices and related organic electronics devices is disclosed. The metal oxide may be derived from a metal-organic precursor enabling solution processing of an amorphous, p-type metal oxide. An organic photovoltaic device having solution processed, metal oxide, thin-film hole transport layer.

  8. Gold nanoparticles in oxidation catalysis [Les nanoparticules d'or en catalyse d'oxydation

    KAUST Repository

    Caps, Valerie

    2010-01-01

    On the other hand, it seems to catalyze the formation of reduced and active dioxygen species in the presence of a reductant (hydrogen or hydrocarbon) and the decomposition of organic hydroperoxides. It thus allows using an alkane as a promoter of the epoxidation of an alkene. In the liquid phase, this translates into an ultra-selective radical mechanism, initiated and controlled by gold particles, which uses oxygen from the air at atmospheric pressure as oxidant and which can be generalized to other types of oxidations. This unique activity at low temperature, which can be optimized upon a thorough control of the surface chemistry of the material, makes gold a catalyst of choice to reconsider the oxidative transformations of petrochemicals in an eco-efficient way.

  9. Ni-based electrocatalyst for water oxidation developed In-situ in a HCO3 -/CO2 system at near-neutral pH

    KAUST Repository

    Joya, Khurram Saleem

    2014-03-10

    Electrochemically generated NiOx nanoworms from a neutral bicarbonate system split water into dioxygen and protons with tremendous efficiency and stability. The NiOx electrocatalyst follows a pH-potential dependence, revealing a PCET (proton coupled electron transfer) mechanism of one electron and one proton oxidation. It does not require proton abstracting phosphate or borate buffers for electrogeneration and catalysis, and shows promising activity for anodic oxidation of water in phosphate, borate, and carbonate buffers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ni-based electrocatalyst for water oxidation developed In-situ in a HCO3 -/CO2 system at near-neutral pH

    KAUST Repository

    Joya, Khurram Saleem; Joya, Yasir F.; De Groot, Huub J M

    2014-01-01

    Electrochemically generated NiOx nanoworms from a neutral bicarbonate system split water into dioxygen and protons with tremendous efficiency and stability. The NiOx electrocatalyst follows a pH-potential dependence, revealing a PCET (proton coupled electron transfer) mechanism of one electron and one proton oxidation. It does not require proton abstracting phosphate or borate buffers for electrogeneration and catalysis, and shows promising activity for anodic oxidation of water in phosphate, borate, and carbonate buffers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Heterojunction PbS Nanocrystal Solar Cells with Oxide Charge-Transport Layers

    KAUST Repository

    Hyun, Byung-Ryool

    2013-12-23

    Oxides are commonly employed as electron-transport layers in optoelectronic devices based on semiconductor nanocrystals, but are relatively rare as hole-transport layers. We report studies of NiO hole-transport layers in PbS nanocrystal photovoltaic structures. Transient fluorescence experiments are used to verify the relevant energy levels for hole transfer. On the basis of these results, planar heterojunction devices with ZnO as the photoanode and NiO as the photocathode were fabricated and characterized. Solution-processed devices were used to systematically study the dependence on nanocrystal size and achieve conversion efficiency as high as 2.5%. Optical modeling indicates that optimum performance should be obtained with thinner oxide layers than can be produced reliably by solution casting. Roomerature sputtering allows deposition of oxide layers as thin as 10 nm, which enables optimization of device performance with respect to the thickness of the charge-transport layers. The best devices achieve an open-circuit voltage of 0.72 V and efficiency of 5.3% while eliminating most organic material from the structure and being compatible with tandem structures. © 2013 American Chemical Society.

  12. Metal Oxides as Efficient Charge Transporters in Perovskite Solar Cells

    KAUST Repository

    Haque, Mohammed

    2017-07-10

    Over the past few years, hybrid halide perovskites have emerged as a highly promising class of materials for photovoltaic technology, and the power conversion efficiency of perovskite solar cells (PSCs) has accelerated at an unprecedented pace, reaching a record value of over 22%. In the context of PSC research, wide-bandgap semiconducting metal oxides have been extensively studied because of their exceptional performance for injection and extraction of photo-generated carriers. In this comprehensive review, we focus on the synthesis and applications of metal oxides as electron and hole transporters in efficient PSCs with both mesoporous and planar architectures. Metal oxides and their doped variants with proper energy band alignment with halide perovskites, in the form of nanostructured layers and compact thin films, can not only assist with charge transport but also improve the stability of PSCs under ambient conditions. Strategies for the implementation of metal oxides with tailored compositions and structures, and for the engineering of their interfaces with perovskites will be critical for the future development and commercialization of PSCs.

  13. Efficient oxidation of alcohols to carbonyl compounds with molecular oxygen catalyzed by N-hydroxyphthalimide combined with a Co species

    Science.gov (United States)

    Iwahama; Yoshino; Keitoku; Sakaguchi; Ishii

    2000-10-06

    Highly efficient catalytic oxidation of alcohols with molecular oxygen by N-hydroxyphthalimide (NHPI) combined with a Co species was developed. The oxidation of 2-octanol in the presence of catalytic amounts of NHPI and Co(OAc)2 under atmospheric dioxygen in AcOEt at 70 degrees C gave 2-octanone in 93% yield. The oxidation was significantly enhanced by adding a small amount of benzoic acid to proceed smoothly even at room temperature. Primary alcohols were oxidized by NHPI in the absence of any metal catalyst to form the corresponding carboxylic acids in good yields. In the oxidation of terminal vic-diols such as 1,2-butanediol, carbon-carbon bond cleavage was induced to give one carbon less carboxylic acids such as propionic acid, while internal vic-diols were selectively oxidized to 1,2-diketones.

  14. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-01-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

  15. Catalytic Water Oxidation by a Bio-inspired Nickel Complex with Redox Active Ligand

    Science.gov (United States)

    Wang, Dong; Bruner, Charlie O.

    2017-01-01

    The oxidation of water to dioxygen is important in natural photosynthesis. One of nature’s strategies for managing such multi-electron transfer reactions is to employ redox active metal-organic cofactor arrays. One prototype example is the copper-tyrosinate active site found in galactose oxidase. In this work, we have implemented such a strategy to develop a bio-inspired nickel-phenolate complex capable of catalyzing the oxidation of water to O2 electrochemically at neutral pH with a modest overpotential. The employment of the redox-active ligand turned out to be a useful strategy to avoid the formation of high-valent nickel intermediates while a reasonable turnover rate (0.15 s−1) is retained. PMID:29099176

  16. Insights into organic carbon oxidation potential during fluvial transport from laboratory and field experiments

    Science.gov (United States)

    Scheingross, J. S.; Dellinger, M.; Eglinton, T. I.; Fuchs, M. C.; Golombek, N.; Hilton, R. G.; Hovius, N.; Lupker, M.; Repasch, M. N.; Sachse, D.; Turowski, J. M.; Vieth-Hillebrand, A.; Wittmann, H.

    2017-12-01

    Over geologic timescales, the exchange of organic carbon (OC) between the atmosphere, hydropshere, biosphere and geosphere can be a major control on atmospheric carbon dioxide concentrations. The carbon fluxes from the oxidation of rock-derived OC (a CO2 source) and erosion, transport, and burial of biospheric OC (a potential CO2 sink) during fluvial transit are approximately the same order of magnitude or larger than those from silicate weathering. Despite field data showing increasing oxidation of OC moving downstream in lowland rivers, it is unclear if losses occur primarily during active fluvial transport, where OC is in continual motion within an aerated river, or during periods of temporary storage in river floodplains which may be anoxic. The unknown location of OC oxidation (i.e., river vs. floodplain) limits our ability to mechanistically link geochemical and geomorphic processes which are required to develop models capable of predicting OC losses, constrain carbon budgets, and unravel links between climate, tectonics, and erosion. To fill this knowledge gap, we investigated OC oxidation in controlled laboratory experiments and a simplified field setting. We performed experiments in annular flumes that simulate fluvial transport without floodplain storage, allowing mixtures of OC-rich and siliciclastic sediment to be transported for distances of 1000 km. Preliminary experiments exploring both rock-derived and biospheric OC sources show minimal OC oxidation during active river transport, consistent with the idea that the majority of OC loss occurs during transient floodplain storage. These results are also consistent with new field data collected in the Rio Bermejo, Argentina, a lowland river traversing 800 km with no tributary inputs, where aged floodplain deposits have 3 to 10 times lower OC concentrations compared to modern river sediments. Together our field data and experiments support the hypothesis that oxidation of OC occurs primarily during

  17. Nitrogen-doped graphene interpenetrated 3D Ni-nanocages: efficient and stable water-to-dioxygen electrocatalysts

    Science.gov (United States)

    Dhavale, Vishal M.; Gaikwad, Sachin S.; George, Leena; Devi, R. Nandini; Kurungot, Sreekumar

    2014-10-01

    Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well.Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N

  18. Micromechanism of oxygen transport during initial stage oxidation in Si(100) surface: A ReaxFF molecular dynamics simulation study

    International Nuclear Information System (INIS)

    Sun, Yu; Liu, Yilun; Chen, Xuefeng; Zhai, Zhi; Xu, Fei; Liu, Yijun

    2017-01-01

    Highlights: • A competition mechanism between thermal actuation and compressive stress blocking was found for the oxygen transport. • At low temperature, a compressive stress was generated in the oxide layer which blocked oxygen transport into the deeper region. • O atoms gained larger possibility to go deeper inward as temperature increase. • The related film quality was well explained by the competition mechanism. - Abstract: The early stage oxidation in Si(100) surface has been investigated in this work by a reactive force field molecular dynamics (ReaxFF MD) simulation, manifesting that the oxygen transport acted as a dominant issue for initial oxidation process. Due to the oxidation, a compressive stress was generated in the oxide layer which blocked the oxygen transport perpendicular to the Si(100) surface and further prevented oxidation in the deeper layer. In contrast, thermal actuation was beneficial to the oxygen transport into deeper layer as temperature increases. Therefore, a competition mechanism was found for the oxygen transport during early stage oxidation in Si(100) surface. At room temperature, the oxygen transport was governed by the blocking effect of compressive stress, so a better quality oxide film with more uniform interface and more stoichiometric oxide structure was obtained. Indeed, the mechanism presented in this work is also applicable for other self-limiting oxidation (e.g. metal oxidation) and is helpful for the design of high-performance electronic devices.

  19. Micromechanism of oxygen transport during initial stage oxidation in Si(100) surface: A ReaxFF molecular dynamics simulation study

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yu, E-mail: yu.sun@xjtu.edu.cn [State Key Laboratory for Manufacturing Systems Engineering, School of Mechanical Engineering, Xi’an Jiaotong University, Xi’an 710049 (China); Institute for Computational Mechanics and Its Applications, Northwestern Polytechnical University, Xi’an 710072 (China); Liu, Yilun [State Key Laboratory for Strength and Vibration of Mechanical Structures, School of Aerospace Engineering, Xi’an Jiaotong University, Xi’an 710049 (China); Chen, Xuefeng; Zhai, Zhi [State Key Laboratory for Manufacturing Systems Engineering, School of Mechanical Engineering, Xi’an Jiaotong University, Xi’an 710049 (China); Xu, Fei [Institute for Computational Mechanics and Its Applications, Northwestern Polytechnical University, Xi’an 710072 (China); Liu, Yijun [Institute for Computational Mechanics and Its Applications, Northwestern Polytechnical University, Xi’an 710072 (China); Mechanical Engineering, University of Cincinnati, Cincinnati, OH 45221-0072 (United States)

    2017-06-01

    Highlights: • A competition mechanism between thermal actuation and compressive stress blocking was found for the oxygen transport. • At low temperature, a compressive stress was generated in the oxide layer which blocked oxygen transport into the deeper region. • O atoms gained larger possibility to go deeper inward as temperature increase. • The related film quality was well explained by the competition mechanism. - Abstract: The early stage oxidation in Si(100) surface has been investigated in this work by a reactive force field molecular dynamics (ReaxFF MD) simulation, manifesting that the oxygen transport acted as a dominant issue for initial oxidation process. Due to the oxidation, a compressive stress was generated in the oxide layer which blocked the oxygen transport perpendicular to the Si(100) surface and further prevented oxidation in the deeper layer. In contrast, thermal actuation was beneficial to the oxygen transport into deeper layer as temperature increases. Therefore, a competition mechanism was found for the oxygen transport during early stage oxidation in Si(100) surface. At room temperature, the oxygen transport was governed by the blocking effect of compressive stress, so a better quality oxide film with more uniform interface and more stoichiometric oxide structure was obtained. Indeed, the mechanism presented in this work is also applicable for other self-limiting oxidation (e.g. metal oxidation) and is helpful for the design of high-performance electronic devices.

  20. Chemical transport of niobium(V) oxide and of lithium niobate with sulphur

    International Nuclear Information System (INIS)

    Schaefer, H.

    1988-01-01

    Niobium(V) oxide is transported by means of sulphur (calculated for 10 bar at 1223 K) from 1273 → 1173 K. The same applies for lithium niobate. Similar experiments of lithium oxide lead to turbidity of the quartz ampoule. (author)

  1. Solute transport and the prediction of breakaway oxidation in gamma + beta Ni-Cr-Al alloys

    Science.gov (United States)

    Nesbitt, J. A.; Heckel, R. W.

    1984-01-01

    The Al transport and the condition leading to breakaway oxidation during the cyclic oxidation of gamma + beta NiCrAl alloys have been studied. The Al concentration/distance profiles were measured after various cyclic oxidation exposures at 1200 C. It was observed that cyclic oxidation results in a decreasing Al concentration at the oxide/metal interface, maintaining a constant flux of Al to the Al2O3 scale. It was also observed that breakaway oxidation occurs when the Al concentration at the oxide/metal interface approaches zero. A numerical model was developed to simulate the diffusional transport of Al and to predict breakaway oxidation in gamma + beta NiCrAl alloys undergoing cyclic oxidation. In a comparison of two alloys with similar oxide spalling characteristics, the numerical model was shown to predict correctly the onset of breakaway oxidation in the higher Al-content alloy.

  2. Chemical Transport Knockout for Oxidized Vitamin C, Dehydroascorbic Acid, Reveals Its Functions in vivo

    Directory of Open Access Journals (Sweden)

    Hongbin Tu

    2017-09-01

    Full Text Available Despite its transport by glucose transporters (GLUTs in vitro, it is unknown whether dehydroascorbic acid (oxidized vitamin C, DHA has any in vivo function. To investigate, we created a chemical transport knockout model using the vitamin C analog 6-bromo-ascorbate. This analog is transported on sodium-dependent vitamin C transporters but its oxidized form, 6-bromo-dehydroascorbic acid, is not transported by GLUTs. Mice (gulo−/− unable to synthesize ascorbate (vitamin C were raised on 6-bromo-ascorbate. Despite normal survival, centrifugation of blood produced hemolysis secondary to near absence of red blood cell (RBC ascorbate/6-bromo-ascorbate. Key findings with clinical implications were that RBCs in vitro transported dehydroascorbic acid but not bromo-dehydroascorbic acid; RBC ascorbate in vivo was obtained only via DHA transport; ascorbate via DHA transport in vivo was necessary for RBC structural integrity; and internal RBC ascorbate was essential to maintain ascorbate plasma concentrations in vitro/in vivo.

  3. Experimental insights into organic carbon oxidation potential during fluvial transport without floodplain storage

    Science.gov (United States)

    Scheingross, J. S.; Hovius, N.; Sachse, D.; Vieth-Hillebrand, A.; Turowski, J. M.; Hilton, R. G.

    2016-12-01

    Over geologic timescales, the exchange of organic carbon (OC) between the atmosphere, rock, and biosphere is thought to be a major control on global climate. CO2 flux estimates from oxidation of rock-derived OC and sequestration of biospheric OC during fluvial transit from source to sink are approximately the same order of magnitude or larger than those from silicate weathering. Despite field data showing loss of OC moving downstream in lowland rivers, it is unclear if losses occur primarily during active fluvial transport within the river, where OC is in continual motion within an aerated environment, or during longer periods when OC is temporarily stored in river floodplains which may be anoxic. This represents a major knowledge gap, as the unknown location of OC oxidation (i.e., river vs. floodplain) limits our ability to develop process-based models that can be employed to predict OC losses, constrain carbon budgets, and unravel links between climate, tectonics, and erosion. To fill this gap, we investigated the potential for OC oxidation in laboratory experiments simulating fluvial transport without floodplain storage. Mixtures of OC-rich and siliciclastic sediment were transported for distances of 2000 km in annular flumes while making time-series measurements of sediment TOC and water DOC concentrations. Initial results for transport of OC-rich soil show increasing DOC with transport distance to levels that represent a transfer of 2% of the total OC from the solid to the dissolved phase; however, we observed no detectable change in the solid-phase TOC. Similar results were obtained in a control experiment with identical sediment in still water. These preliminary results suggest minimal OC oxidation within our experiment, and, to the extent that such experiments represent natural transport through river systems, are consistent with the hypothesis that OC losses may occur primarily during floodplain storage rather than fluvial transport.

  4. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Complexes 1 and 2 react with dioxygen at ambient condition to form the corresponding hydroxo- or oxo-bridged dinuclear cobalt(III) or iron(III) complexes. On the other hand, the iron(III)-catecholate complex (3) activate dioxygen to undergo oxidative C-C bond cleavage of catechol. The selective formation of extradiol ...

  5. Insights into organic carbon oxidation potential during fluvial transport from controlled laboratory and natural field experiments

    Science.gov (United States)

    Scheingross, Joel S.; Dellinger, Mathieu; Golombek, Nina; Hilton, Robert G.; Hovius, Niels; Sachse, Dirk; Turowski, Jens M.; Vieth-Hillebrand, Andrea; Wittmann, Hella

    2017-04-01

    Over geologic timescales, the exchange of organic carbon (OC) between the atmosphere, biosphere and geosphere is thought to be a major control on atmospheric carbon dioxide (CO2) concentrations, and hence global climate. The carbon fluxes from the oxidation of rock-derived OC (a CO2 source) and erosion and transport of biospheric OC (a potential CO2 sink) during fluvial transit are approximately the same order of magnitude or larger than those from silicate weathering (France-Lanord and Derry, 1997; Bouchez et al., 2010). Despite field data showing oxidation of OC moving downstream in lowland rivers, it is unclear if losses occur primarily during active fluvial transport within the river, where OC is in continual motion within an aerated environment, or during longer periods when OC is temporarily stored in river floodplains which may be anoxic. This represents a major knowledge gap, as the unknown location of OC oxidation (i.e., river vs. floodplain) limits our ability to develop process-based models that can be employed to predict OC losses, constrain carbon budgets, and unravel links between climate, tectonics, and erosion. To fill this gap, we investigated the potential for OC oxidation in both controlled laboratory experiments and a simplified field setting. We consider both rock-derived and biospheric OC. Our experiments simulated fluvial transport without floodplain storage, allowing mixtures of OC-rich and siliciclastic sediment to be transported for distances of 1000 km in annular flumes while making time-series measurements of OC concentration in both the solid (POC) and dissolved (DOC) loads, as well as measurements of rhenium concentration, which serves as a proxy for the oxidation of rock-derived OC. These transport experiments were compared to static, control experiments where water and sediment in the same proportion were placed in still water. Initial results for transport of OC-rich soil show similar behavior between the transport and static

  6. Transport of electrons in lead oxide studied by CELIV technique

    International Nuclear Information System (INIS)

    Semeniuk, O; Juska, G; Oelerich, J O; Jandieri, K; Baranovskii, S D; Reznik, A

    2017-01-01

    Although polycrystalline lead oxide (PbO) has a long history of application in optoelectronics and imaging, the transport mechanism for electrons in this material has not yet been clarified. Using the photo-generated charge extraction by linear increasing voltage (photo-CELIV) technique, we provide the temperature- and field-dependences of electron mobility in poly-PbO. It is found that electrons undergo dispersive transport, i.e. their mobility decreases in the course of time. Multiple trapping of electrons from the conduction band into the developed band tail is revealed as the dominant transport mechanism. This differs dramatically from the dispersive transport of holes in the same material, dominated by topological factors and not by energy disorder. (paper)

  7. Oxygen transport and GeO2 stability during thermal oxidation of Ge

    Science.gov (United States)

    da Silva, S. R. M.; Rolim, G. K.; Soares, G. V.; Baumvol, I. J. R.; Krug, C.; Miotti, L.; Freire, F. L.; da Costa, M. E. H. M.; Radtke, C.

    2012-05-01

    Oxygen transport during thermal oxidation of Ge and desorption of the formed Ge oxide are investigated. Higher oxidation temperatures and lower oxygen pressures promote GeO desorption. An appreciable fraction of oxidized Ge desorbs during the growth of a GeO2 layer. The interplay between oxygen desorption and incorporation results in the exchange of O originally present in GeO2 by O from the gas phase throughout the oxide layer. This process is mediated by O vacancies generated at the GeO2/Ge interface. The formation of a substoichiometric oxide is shown to have direct relation with the GeO desorption.

  8. Evaluation of the participation of ferredoxin in oxygen reduction in the photosynthetic electron transport chain of isolated pea thylakoids.

    Science.gov (United States)

    Kozuleva, Marina A; Ivanov, Boris N

    2010-07-01

    The contribution to reduction of oxygen by ferredoxin (Fd) to the overall reduction of oxygen in isolated pea thylakoids was studied in the presence of Fd versus Fd + NADP(+). The overall rate of electron transport was measured using a determination of Photosystem II quantum yield from chlorophyll fluorescence parameters, and the rate of oxidation of Fd was measured from the light-induced redox changes of Fd. At low light intensity, increasing Fd concentration from 5 to 30 microM in the absence of NADP(+) increased the proportion of oxygen reduction by Fd from 25-35 to 40-60% in different experiments. This proportion decreased with increasing light intensity. When NADP(+) was added in the presence of 15 microM Fd, which was optimal for the NADP(+) reduction rate, the participation of Fd in the reduction of oxygen was low, no more than 10%, and it also decreased with increasing light intensity. At high light intensity, the overall oxygen reduction rates in the presence of Fd + NADP(+) and in the presence of Fd alone were comparable. The significance of reduction of dioxygen either by water-soluble Fd or by the membrane-bound carriers of the photosynthetic electron transport chain for redox signaling under different light intensities is discussed.

  9. Catalytic Water Oxidation by a Bio-inspired Nickel Complex with a Redox-Active Ligand.

    Science.gov (United States)

    Wang, Dong; Bruner, Charlie O

    2017-11-20

    The oxidation of water (H 2 O) to dioxygen (O 2 ) is important in natural photosynthesis. One of nature's strategies for managing such multi-electron transfer reactions is to employ redox-active metal-organic cofactor arrays. One prototype example is the copper tyrosinate active site found in galactose oxidase. In this work, we have implemented such a strategy to develop a bio-inspired nickel phenolate complex capable of catalyzing the oxidation of H 2 O to O 2 electrochemically at neutral pH with a modest overpotential. Employment of the redox-active ligand turned out to be a useful strategy to avoid the formation of high-valent nickel intermediates while a reasonable turnover rate (0.15 s -1 ) is retained.

  10. Photochemical oxidant transport - Mesoscale lake breeze and synoptic-scale aspects

    Science.gov (United States)

    Lyons, W. A.; Cole, H. S.

    1976-01-01

    Data from routine ozone monitoring in southeastern Wisconsin and limited monitoring of the Milwaukee area by the Environmental Protection Agency are examined. Hourly averages as high as 30 pphm have been recorded in southeastern Wisconsin, and high readings have been reported in rural regions throughout the state. The observations indicate that photochemical oxidants and their nitrogen oxide and reactive hydrocarbon precursers advect from Chicago and northern Indiana into southeastern Wisconsin. There is evidence that synoptic-scale transport of photochemical oxidants occurs, allowing the pollution of entire anticyclones. These results cast doubt on the validity of the Air Quality Control Regions established by amendment to the Clean Air Act of 1970.

  11. Novel hybrid materials based on the vanadium oxide nanobelts

    Energy Technology Data Exchange (ETDEWEB)

    Zabrodina, G.S., E-mail: kudgs@mail.ru [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Makarov, S.G.; Kremlev, K.V. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Yunin, P.A.; Gusev, S.A. [Institute for Physics of Microstructures Russian Academy of Sciences, Nizhny Novgorod 603087 (Russian Federation); Kaverin, B.S.; Kaverina, L.B. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Ketkov, S.Yu. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation)

    2016-04-15

    Graphical abstract: - Highlights: • Flat and curved vanadium oxide nanobelts have been synthesized. • Hybrid material was prepared via decoration of flexible nanobelts with zinc phthalocyanine. • Investigations of the thermal stability, morphologies and structures were carried out. - Abstract: Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V{sub 2}O{sub 5}·nH{sub 2}O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB – cetyltrimethylammonium bromide, TBAB – tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA){sub 0.33}V{sub 2}O{sub 5} flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA){sub 0.33}V{sub 2}O{sub 5}, (TBA){sub 0.16}V{sub 2}O{sub 5} nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

  12. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Science.gov (United States)

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  13. Pore-scale investigation of mass transport and electrochemistry in a solid oxide fuel cell anode

    Energy Technology Data Exchange (ETDEWEB)

    Grew, Kyle N.; Joshi, Abhijit S.; Peracchio, Aldo A.; Chiu, Wilson K.S. [Department of Mechanical Engineering, University of Connecticut, 191 Auditorium Road, Storrs, CT 06269-3139 (United States)

    2010-04-15

    The development and validation of a model for the study of pore-scale transport phenomena and electrochemistry in a Solid Oxide Fuel Cell (SOFC) anode are presented in this work. This model couples mass transport processes with a detailed reaction mechanism, which is used to model the electrochemical oxidation kinetics. Detailed electrochemical oxidation reaction kinetics, which is known to occur in the vicinity of the three-phase boundary (TPB) interfaces, is discretely considered in this work. The TPB regions connect percolating regions of electronic and ionic conducting phases of the anode, nickel (Ni) and yttria-stabilized zirconia (YSZ), respectively; with porous regions supporting mass transport of the fuel and product. A two-dimensional (2D), multi-species lattice Boltzmann method (LBM) is used to describe the diffusion process in complex pore structures that are representative of the SOFC anode. This diffusion model is discretely coupled to a kinetic electrochemical oxidation mechanism using localized flux boundary conditions. The details of the oxidation kinetics are prescribed as a function of applied activation overpotential and the localized hydrogen and water mole fractions. This development effort is aimed at understanding the effects of the anode microstructure within TPB regions. This work describes the methods used so that future studies can consider the details of SOFC anode microstructure. (author)

  14. Macrophage mitochondrial damage from StAR transport of 7-hydroperoxycholesterol: implications for oxidative stress-impaired reverse cholesterol transport.

    Science.gov (United States)

    Korytowski, Witold; Wawak, Katarzyna; Pabisz, Pawel; Schmitt, Jared C; Girotti, Albert W

    2014-01-03

    StAR family proteins in vascular macrophages participate in reverse cholesterol transport (RCT). We hypothesize that under pathophysiological oxidative stress, StARs will transport not only cholesterol to macrophage mitochondria, but also pro-oxidant cholesterol hydroperoxides (7-OOHs), thereby impairing early-stage RCT. Upon stimulation with dibutyryl-cAMP, RAW264.7 macrophages exhibited a strong time-dependent induction of mitochondrial StarD1 and plasma membrane ABCA1, which exports cholesterol. 7α-OOH uptake by stimulated RAW cell mitochondria (like cholesterol uptake) was strongly reduced by StarD1 knockdown, consistent with StarD1 involvement. Upon uptake by mitochondria, 7α-OOH (but not redox-inactive 7α-OH) triggered lipid peroxidation and membrane depolarization while reducing ABCA1 upregulation. These findings provide strong initial support for our hypothesis. Copyright © 2013. Published by Elsevier B.V.

  15. Gold nanoparticles in oxidation catalysis [Les nanoparticules d'or en catalyse d'oxydation

    KAUST Repository

    Caps, Valerie

    2010-10-25

    When gold dimensions are reduced to a few nanometers, gold exhibits unique properties in oxidation catalysis. By performing selective oxidations of hydrocarbons at low temperature (typically below 100°C), gold nanoparticles achieve high selectivities at levels of conversion usually obtained at higher temperature. This is attributed to the activation modes of molecular oxygen on gold. Indeed, unlike platinum, gold does not chemisorb oxygen at its operating temperature. On the other hand, it seems to catalyze the formation of reduced and active dioxygen species in the presence of a reductant (hydrogen or hydrocarbon) and the decomposition of organic hydroperoxides. It thus allows using an alkane as a promoter of the epoxidation of an alkene. In the liquid phase, this translates into an ultra-selective radical mechanism, initiated and controlled by gold particles, which uses oxygen from the air at atmospheric pressure as oxidant and which can be generalized to other types of oxidations. This unique activity at low temperature, which can be optimized upon a thorough control of the surface chemistry of the material, makes gold a catalyst of choice to reconsider the oxidative transformations of petrochemicals in an eco-efficient way.

  16. Towards printed perovskite solar cells with cuprous oxide hole transporting layers

    DEFF Research Database (Denmark)

    Wang, Yan; Xia, Zhonggao; Liang, Jun

    2015-01-01

    Solution-processed p-type metal oxide materials have shown great promise in improving the stability of perovskite-based solar cells and offering the feasibility for a low cost printing fabrication process. Herein, we performed a device modeling study on planar perovskite solar cells with cuprous...... oxide (Cu2O) hole transporting layers (HTLs) by using a solar cell simulation program, wxAMPS. The performance of a Cu2O/perovskite solar cell was correlated to the material properties of the Cu2O HTL, such as thickness, carrier mobility, mid-gap defect, and doping...

  17. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-10-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

  18. Solid oxide fuel cells for transportation: A clean, efficient alternative for propulsion

    International Nuclear Information System (INIS)

    Kumar, R.; Krumpelt, M.; Myles, K.M.

    1993-01-01

    Fuel cells show great promise for providing clean and efficient transportation power. Of the fuel cell propulsion systems under investigation, the solid oxide fuel cell (SOFC) is particularly attractive for heavy duty transportation applications that have a relatively long duty cycle, such as locomotives, trucks, and barges. Advantages of the SOFC include a simple, compact system configuration; inherent fuel flexibility for hydrocarbon and alternative fuels; and minimal water management. The specific advantages of the SOFC for powering a railroad locomotive are examined. Feasibility, practicality, and safety concerns regarding SOFCs in transportation applications are discussed, as am the major R ampersand D issues

  19. Ab Initio Calculations of Transport Properties of Vanadium Oxides

    Science.gov (United States)

    Lamsal, Chiranjivi; Ravindra, N. M.

    2018-04-01

    The temperature-dependent transport properties of vanadium oxides have been studied near the Fermi energy using the Kohn-Sham band structure approach combined with Boltzmann transport equations. V2O5 exhibits significant thermoelectric properties, which can be attributed to its layered structure and stability. Highly anisotropic electrical conduction in V2O5 is clearly manifested in the calculations. Due to specific details of the band structure and anisotropic electron-phonon interactions, maxima and crossovers are also seen in the temperature-dependent Seebeck coefficient of V2O5. During the phase transition of VO2, the Seebeck coefficient changes by 18.9 µV/K, which is close to (within 10% of) the observed discontinuity of 17.3 µV/K.

  20. Intestinal glutathione: determinant of mucosal peroxide transport, metabolism, and oxidative susceptibility

    International Nuclear Information System (INIS)

    Aw, Tak Yee

    2005-01-01

    The intestine is a primary site of nutrient absorption and a critical defense barrier against dietary-derived mutagens, carcinogens, and oxidants. Accumulation of oxidants like peroxidized lipids in the gut lumen can contribute to impairment of mucosal metabolic pathways, enterocyte dysfunction independent of cell injury, and development of gut pathologies, such as inflammation and cancer. Despite this recognition, we know little of the pathways of intestinal transport, metabolism, and luminal disposition of dietary peroxides in vivo or of the underlying mechanisms of lipid peroxide-induced genesis of intestinal disease processes. This chapter summarizes our current understanding of the determinants of intestinal absorption and metabolism of peroxidized lipids. I will review experimental evidence from our laboratory and others (Table 1) supporting the pivotal role that glutathione (GSH) and reduced nicotinamide adenine dinucleotide phosphate (NADPH) play in mucosal transport and metabolism of lipid hydroperoxides and how reductant availability can be compromised under chronic stress such as hypoxia, and the influence of GSH on oxidative susceptibility, and redox contribution to genesis of gut disorders. The discussion is pertinent to understanding dietary lipid peroxides and GSH redox balance in intestinal physiology and pathophysiology and the significance of luminal GSH in preserving the integrity of the intestinal epithelium

  1. Simulation of uranium transport with variable temperature and oxidation potential: The computer program THCC [Thermo-Hydro-Chemical Coupling

    International Nuclear Information System (INIS)

    Carnahan, C.L.

    1986-12-01

    A simulator of reactive chemical transport has been constructed with the capabilities of treating variable temperatures and variable oxidation potentials within a single simulation. Homogeneous and heterogeneous chemical reactions are simulated at temperature-dependent equilibrium, and changes of oxidation states of multivalent elements can be simulated during transport. Chemical mass action relations for formation of complexes in the fluid phase are included explicitly within the partial differential equations of transport, and a special algorithm greatly simplifies treatment of reversible precipitation of solid phases. This approach allows direct solution of the complete set of governing equations for concentrations of all aqueous species and solids affected simultaneously by chemical and physical processes. Results of example simulations of transport, along a temperature gradient, of uranium solution species under conditions of varying pH and oxidation potential and with reversible precipitation of uraninite and coffinite are presented. The examples illustrate how inclusion of variable temperature and oxidation potential in numerical simulators can enhance understanding of the chemical mechanisms affecting migration of multivalent waste elements

  2. Intercontinental transport of aerosols and photochemical oxidants from Asia and its consequences

    International Nuclear Information System (INIS)

    Wuebbles, Donald J.; Lei, Hang; Lin, Jintai

    2007-01-01

    The intercontinental transport of aerosols and photochemical oxidants from Asia is a crucial issue for air quality concerns in countries downwind of the significant emissions and concentrations of pollutants occurring in this important region of the world. Since the lifetimes of some important pollutants are long enough to be transported over long distance in the troposphere, regional control strategies for air pollution in downwind countries might be ineffective without considering the effects of long-range transport of pollutants from Asia. Field campaigns provide strong evidence for the intercontinental transport of Asian pollutants. They, together with ground-based observations and model simulations, show that the air quality over parts of North America is being affected by the pollutants transported from Asia. This paper examines the current understanding of the intercontinental transport of gases and aerosols from Asia and resulting effects on air quality, and on the regional and global climate system. - Air quality over parts of North America is being affected by pollutants transported from Asia

  3. First Combined in Vivo X-Ray Tomography and High-Resolution Molecular Electron Paramagnetic Resonance (EPR) Imaging of the Mouse Knee Joint Taking into Account the Disappearance Kinetics of the EPR Probe

    OpenAIRE

    Nicolas Bézière; Christophe Decroos; Karen Mkhitaryan; Elizabeth Kish; Frédéric Richard; Stéphanie Bigot-Marchand; Sylvain Durand; Florence Cloppet; Caroline Chauvet; Marie-Thérèse Corvol; François Rannou; Yun Xu-Li; Daniel Mansuy; Fabienne Peyrot; Yves-Michel Frapart

    2012-01-01

    Although laboratory data clearly suggest a role for oxidants (dioxygen and free radicals derived from dioxygen) in the pathogenesis of many age-related and degenerative diseases (such as arthrosis and arthritis), methods to image such species in vivo are still very limited. This methodological problem limits physiopathologic studies about the role of those species in vivo, the effects of their regulation using various drugs, and the evaluation of their levels for diagnosis of degenerative dis...

  4. Design and operational parameters of transportable supercritical water oxidation waste destruction unit

    International Nuclear Information System (INIS)

    McFarland, R.D.; Brewer, G.R.; Rofer, C.K.

    1991-12-01

    Supercritical water oxidation (SCWO) is the destruction of hazardous waste by oxidation in the presence of water at temperatures and pressures above its critical point. A 1 gal/h SCWO waste destruction unit (WDU) has been designed, built, and operated at Los Alamos National Laboratory. This unit is transportable and is intended to demonstrate the SCWO technology on wastes at Department of Energy sites. This report describes the design of the WDU and the preliminary testing phase leading to demonstration

  5. Carnitine transport and fatty acid oxidation.

    Science.gov (United States)

    Longo, Nicola; Frigeni, Marta; Pasquali, Marzia

    2016-10-01

    Carnitine is essential for the transfer of long-chain fatty acids across the inner mitochondrial membrane for subsequent β-oxidation. It can be synthesized by the body or assumed with the diet from meat and dairy products. Defects in carnitine biosynthesis do not routinely result in low plasma carnitine levels. Carnitine is accumulated by the cells and retained by kidneys using OCTN2, a high affinity organic cation transporter specific for carnitine. Defects in the OCTN2 carnitine transporter results in autosomal recessive primary carnitine deficiency characterized by decreased intracellular carnitine accumulation, increased losses of carnitine in the urine, and low serum carnitine levels. Patients can present early in life with hypoketotic hypoglycemia and hepatic encephalopathy, or later in life with skeletal and cardiac myopathy or sudden death from cardiac arrhythmia, usually triggered by fasting or catabolic state. This disease responds to oral carnitine that, in pharmacological doses, enters cells using the amino acid transporter B(0,+). Primary carnitine deficiency can be suspected from the clinical presentation or identified by low levels of free carnitine (C0) in the newborn screening. Some adult patients have been diagnosed following the birth of an unaffected child with very low carnitine levels in the newborn screening. The diagnosis is confirmed by measuring low carnitine uptake in the patients' fibroblasts or by DNA sequencing of the SLC22A5 gene encoding the OCTN2 carnitine transporter. Some mutations are specific for certain ethnic backgrounds, but the majority are private and identified only in individual families. Although the genotype usually does not correlate with metabolic or cardiac involvement in primary carnitine deficiency, patients presenting as adults tend to have at least one missense mutation retaining residual activity. This article is part of a Special Issue entitled: Mitochondrial Channels edited by Pierre Sonveaux, Pierre Maechler

  6. Influence Of pH On The Transport Of Nanoscale Zinc Oxide In Saturated Porous Media

    Science.gov (United States)

    Widespread use of nanoscale zinc oxide (nZnO) in various fields causes subsurface environment contamination. Even though the transport of dissolved zinc ions in subsurface environments such as soils and sediments has been widely studied, the transport mechanism of nZnO in such e...

  7. Periodate as an Oxidant for Catalytic Water Oxidation: Oxidation via Electron Transfer or O-Atom Transfer?

    NARCIS (Netherlands)

    Hetterscheid, D.G.H.; Reek, J.N.H.

    2014-01-01

    Treatment of Ir(OH)(2) with sodium periodate in aqueous solution results in formation of dioxygen following the rate law v = k(obs)[Ir](0.65)[IO4](0.5), with k(obs) = 1.5 x 10(-3) {Ir(OH)(2) = [IrCp*(Me2NHC)(OH)(2)], where Me2NHC = N-dimethylimid-azolin- 2-ylidene and Cp* = cyclopentadienyl}. In

  8. Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

    Science.gov (United States)

    Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

    2017-01-18

    As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

  9. Oxidative Metabolites of Curcumin Poison Human Type II Topoisomerases†

    Science.gov (United States)

    Ketron, Adam C.; Gordon, Odaine N.; Schneider, Claus; Osheroff, Neil

    2013-01-01

    The polyphenol curcumin is the principal flavor and color component of the spice turmeric. Beyond its culinary uses, curcumin is believed to positively impact human health and displays antioxidant, anti-inflammatory, antibacterial, and chemopreventive properties. It also is in clinical trials as an anticancer agent. In aqueous solution at physiological pH, curcumin undergoes spontaneous autoxidation that is enhanced by oxidizing agents. The reaction proceeds through a series of quinone methide and other reactive intermediates to form a final dioxygenated bicyclopentadione product. Several naturally occurring polyphenols that can form quinones have been shown to act as topoisomerase II poisons (i.e., increase levels of topoisomerase II-mediated DNA cleavage). Because several of these compounds have chemopreventive properties, we determined the effects of curcumin, its oxidative metabolites, and structurally related degradation products (vanillin, ferulic acid, and feruloylmethane), on the DNA cleavage activities of human topoisomerase IIα and IIβ. Intermediates in the curcumin oxidation pathway increased DNA scission mediated by both enzymes ~4-5–fold. In contrast, curcumin and the bicyclopentadione, as well as vanillin, ferulic acid, and feruloylmethane, had no effect on DNA cleavage. As found for other quinone-based compounds, curcumin oxidation intermediates acted as redox-dependent (as opposed to interfacial) topoisomerase II poisons. Finally, under conditions that promote oxidation, the dietary spice turmeric enhanced topoisomerase II-mediated DNA cleavage. Thus, even within the more complex spice formulation, oxidized curcumin intermediates appear to function as topoisomerase II poisons. PMID:23253398

  10. Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

    DEFF Research Database (Denmark)

    Hansen, Thomas S.; Sádaba, Irantzu; Garcia, Eduardo

    2013-01-01

    containing promoters (NCPs) to obtain excellent yields. In acetonitrile a 95% DFF yield was obtained after 24h with ambient pressure of dioxygen at room temperature in the presence of different NCPs, which – to our knowledge – is the best result reported thus far for this reaction. The use of NCPs made...... it further possible to apply various traditional solvents, e.g. acetone, methanol and methyl isobutyl ketone for the reaction. The latter can be used as extraction solvent for HMF synthesis in aqueous media and thus integrate the two processes. Additionally, HMF was oxidized to 2,5-furandicarboxylic acid...

  11. Charge carrier transport mechanisms in nanocrystalline indium oxide

    International Nuclear Information System (INIS)

    Forsh, E.A.; Marikutsa, A.V.; Martyshov, M.N.; Forsh, P.A.; Rumyantseva, M.N.; Gaskov, A.M.; Kashkarov, P.K.

    2014-01-01

    The charge transport properties of nanocrystalline indium oxide (In 2 O 3 ) are studied. A number of nanostructured In 2 O 3 samples with various nanocrystal sizes are prepared by sol–gel method and characterized using various techniques. The mean nanocrystals size varies from 7–8 nm to 18–20 nm depending on the conditions of their preparation. Structural characterizations of the In 2 O 3 samples are performed by means of transmission electron microscopy and X-ray diffraction. The analysis of dc and ac conductivity in a wide temperature range (T = 50–300 K) shows that at high temperatures charge carrier transport takes place over conduction band and at low temperatures a variable range hopping transport mechanism can be observed. We find out that the temperature of transition from one mechanism to another depends on nanocrystal size: the transition temperature rises when nanocrystals are bigger in size. The average hopping distance between two sites and the activation energy are calculated basing on the analysis of dc conductivity at low temperature. Using random barrier model we show a uniform hopping mechanism taking place in our samples and conclude that nanocrystalline In 2 O 3 can be regarded as a disordered system. - Highlights: • In 2 O 3 samples with various nanocrystal sizes are prepared by sol–gel method. • The mean nanocrystal size varies from 7–8 nm to 18–20 nm. • At high temperatures charge carrier transport takes place over conduction band. • At low temperatures a variable range hopping transport mechanism can be observed. • We show a uniform hopping mechanism taking place in our samples

  12. Reduced coupling of oxidative phosphorylation in vivo precedes electron transport chain defects due to mild oxidative stress in mice.

    Directory of Open Access Journals (Sweden)

    Michael P Siegel

    Full Text Available Oxidative stress and mitochondrial function are at the core of many degenerative conditions. However, the interaction between oxidative stress and in vivo mitochondrial function is unclear. We used both pharmacological (2 week paraquat (PQ treatment of wild type mice and transgenic (mice lacking Cu, Zn-superoxide dismutase (SOD1(-/- models to test the effect of oxidative stress on in vivo mitochondrial function in skeletal muscle. Magnetic resonance and optical spectroscopy were used to measure mitochondrial ATP and oxygen fluxes and cell energetic state. In both models of oxidative stress, coupling of oxidative phosphorylation was significantly lower (lower P/O at rest in vivo in skeletal muscle and was dose-dependent in the PQ model. Despite this reduction in efficiency, in vivo mitochondrial phosphorylation capacity (ATPmax was maintained in both models, and ex vivo mitochondrial respiration in permeabilized muscle fibers was unchanged following PQ treatment. In association with the reduced P/O, PQ treatment led to a dose-dependent reduction in PCr/ATP ratio and increased phosphorylation of AMPK. These results indicate that oxidative stress uncouples oxidative phosphorylation in vivo and results in energetic stress in the absence of defects in the mitochondrial electron transport chain.

  13. Correlation of nanostructure and charge transport properties of oxidized a -SiC:H films

    Energy Technology Data Exchange (ETDEWEB)

    Gordienko, S.O.; Nazarov, A.N.; Vasin, A.V.; Rusavsky, A.V.; Lysenko, V.S. [Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, Prospekt Nauki 41, 03028 Kyiv (Ukraine)

    2012-06-15

    This paper considers the influence of low temperature oxidation on structural and electrical properties of amorphous carbon-rich a -Si{sub 1-x}C{sub x}:H thin films fabricated by reactive RF magnetron sputtering. It is shown that oxidation leads to formation of SiO{sub x} matrix with graphite-like carbon inclusions. Such conductive precipitates has a strong effect on charge transport in oxidized a -Si{sub 1-x}C{sub x}:H films (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  14. Stability and transport of graphene oxide nanoparticles in groundwater and surface water

    Science.gov (United States)

    A transport study investigating the effects of natural organic matter (NOM) in the presence of monovalent (KCl) and divalent (CaCl2) salts was performed in a packed bed column. The electrophoretic mobility (EPM) and effective diameter of the graphene oxide nanoparticles (GONPs) were measured as a fu...

  15. Electrical transport through single-wall carbon nanotube-anodic aluminum oxide-aluminum heterostructures

    International Nuclear Information System (INIS)

    Kukkola, Jarmo; Rautio, Aatto; Sala, Giovanni; Pino, Flavio; Toth, Geza; Leino, Anne-Riikka; Maeklin, Jani; Jantunen, Heli; Uusimaeki, Antti; Kordas, Krisztian; Gracia, Eduardo; Terrones, Mauricio; Shchukarev, Andrey; Mikkola, Jyri-Pekka

    2010-01-01

    Aluminum foils were anodized in sulfuric acid solution to form thick porous anodic aluminum oxide (AAO) films of thickness ∼6 μm. Electrodes of carboxyl-functionalized single-wall carbon nanotube (SWCNT) thin films were inkjet printed on the anodic oxide layer and the electrical characteristics of the as-obtained SWCNT-AAO-Al structures were studied. Nonlinear current-voltage transport and strong temperature dependence of conduction through the structure was measured. The microstructure and chemical composition of the anodic oxide layer was analyzed using transmission and scanning electron microscopy as well as x-ray photoelectron spectroscopy. Schottky emission at the SWCNT-AAO and AAO-Al interfaces allowed by impurity states in the anodic aluminum oxide film together with ionic surface conduction on the pore walls of AAO gives a reasonable explanation for the measured electrical conduction. Calcined AAO is proposed as a dielectric material for SWCNT-field effect transistors.

  16. Regulation of taurine transport at the blood-placental barrier by calcium ion, PKC activator and oxidative stress conditions

    Directory of Open Access Journals (Sweden)

    Lee Na-Young

    2010-08-01

    Full Text Available Abstract Background In the present study, we investigated the changes of uptake and efflux transport of taurine under various stress conditions using rat conditionally immortalized syncytiotrophoblast cell line (TR-TBT cells, as in vitro blood-placental barrier (BPB model. Methods The transport of taurine in TR-TBT cells were characterized by cellular uptake study using radiolabeled taurine. The efflux of taurine was measured from the amount of radiolabeled taurine remaining in the cells after the uptake of radiolabeled taurine for 60 min. Results Taurine uptake was significantly decreased by phosphorylation of protein kinase C (PKC activator in TR-TBT cells. Also, calcium ion (Ca2+ was involved in taurine transport in TR-TBT cells. Taurine uptake was inhibited and efflux was enhanced under calcium free conditions in the cells. In addition, oxidative stress induced the change of taurine transport in TR-TBT cells, but the changes were different depending on the types of oxidative stress inducing agents. Tumor necrosis factor-α (TNF-α, lipopolysaccharide (LPS and diethyl maleate (DEM significantly increased taurine uptake, but H2O2 and nitric oxide (NO donor decreased taurine uptake in the cells. Taurine efflux was down-regulated by TNF-α in TR-TBT cells. Conclusion Taurine transport in TR-TBT cells were regulated diversely at extracellular Ca2+ level, PKC activator and oxidative stress conditions. It suggested that variable stresses affected the taurine supplies from maternal blood to fetus and taurine level of fetus.

  17. The water-water cycle as alternative photon and electron sinks.

    OpenAIRE

    Asada, K

    2000-01-01

    The water-water cycle in chloroplasts is the photoreduction of dioxygen to water in photosystem I (PS I) by the electrons generated in photosystem II (PS II) from water. In the water-water cycle, the rate of photoreduction of dioxygen in PS I is several orders of magnitude lower than those of the disproportionation of superoxide catalysed by superoxide dismutase, the reduction of hydrogen peroxide to water catalysed by ascorbate peroxidase, and the reduction of the resulting oxidized forms of...

  18. Kinetic studies on the oxidation of oxyhemoglobin by biologically active iron thiosemicarbazone complexes: relevance to iron-chelator-induced methemoglobinemia.

    Science.gov (United States)

    Basha, Maram T; Rodríguez, Carlos; Richardson, Des R; Martínez, Manuel; Bernhardt, Paul V

    2014-03-01

    The oxidation of oxyhemoglobin to methemoglobin has been found to be facilitated by low molecular weight iron(III) thiosemicarbazone complexes. This deleterious reaction, which produces hemoglobin protein units unable to bind dioxygen and occurs during the administration of iron chelators such as the well-known 3-aminopyridine-2-pyridinecarbaldehyde thiosemicarbazone (3-AP; Triapine), has been observed in the reaction with Fe(III) complexes of some members of the 3-AP structurally-related thiosemicarbazone ligands derived from di-2-pyridyl ketone (HDpxxT series). We have studied the kinetics of this oxidation reaction in vitro using human hemoglobin and found that the reaction proceeds with two distinct time-resolved steps. These have been associated with sequential oxidation of the two different oxyheme cofactors in the α and β protein chains. Unexpected steric and hydrogen-bonding effects on the Fe(III) complexes appear to be the responsible for the observed differences in the reaction rate across the series of HDpxxT ligand complexes used in this study.

  19. Diels-Alder reactions using 4,7-dioxygenated indanones as dienophiles for regioselective construction of oxygenated 2,3-dihydrobenz[f]indenone skeleton

    Directory of Open Access Journals (Sweden)

    2008-05-01

    Full Text Available Regioselective construction of 4,8,9-trioxygenated 2,3-dihydrobenz[f]indenones, key intermediates for the synthesis of kinamycin antibiotics, was achieved via Diels-Alder reactions (DAR using 4,7-dioxygenated indanone-type compounds as dienophiles. Reaction of indanetrione with 1-methoxybutadiene gave a 1 : 1 mixture of undesired 4,5,9-trioxygenated 2,3-dihydrobenz[f]indenone and [4.4.3]propellane. The addition of Lewis acid did not affect the product ratio, whereas the use of the 6-bromoindanetrione exclusively afforded the latter propellane. On the other hand, DAR of benzyne derived from bromoindan and furan gave 5,8-epoxy-2,3-dihydrobenz[f]indene, which was subjected to acid-induced ring opening to give 2,3-dihydrobenz[f]indenone with undesired 4,5,9-trioxy functions.

  20. Immunological, clinical, haematological and oxidative responses to long distance transportation in horses.

    Science.gov (United States)

    Padalino, Barbara; Raidal, Sharanne Lee; Carter, Nicole; Celi, Pietro; Muscatello, Gary; Jeffcott, Leo; de Silva, Kumudika

    2017-12-01

    Horses are transported frequently and often over long distances. Transportation may represent a physiological stressor with consequential health and welfare implications. This study reports the effects of a long distance journey on immunological, clinical, haematological, inflammatory and oxidative parameters in an Experimental Group (EG) of ten horses, comparing them with six horses of similar age and breed used as a non-transported Control Group (CG). Clinical examination and blood sampling were performed twice on all horses: immediately after unloading for the EG, and at rest on the same day for the CG (day 1); at rest on the same day one week later for both groups (day 7). On day 1 EG horses showed increased heart and respiratory rates (Ptransportation induced an acute phase response impairing the cell-mediated immune response. Clinical examinations, including assessing CRT and body weight loss, and the monitoring of redox balance may be useful in evaluating the impact of extensive transport events on horses. A better understanding of the link between transportation stress, the immune system and the acute phase response is likely to inform strategies for enhancing the welfare of transported horses. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

    Science.gov (United States)

    Surasani, V.; Li, L.

    2011-12-01

    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  2. Laccases as palladium oxidases.

    Science.gov (United States)

    Mekmouche, Yasmina; Schneider, Ludovic; Rousselot-Pailley, Pierre; Faure, Bruno; Simaan, A Jalila; Bochot, Constance; Réglier, Marius; Tron, Thierry

    2015-02-01

    The first example of a coupled catalytic system involving an enzyme and a palladium(ii) catalyst competent for the aerobic oxidation of alcohol in mild conditions is described. In the absence of dioxygen, the fungal laccase LAC3 is reduced by a palladium(0) species as evidenced by the UV/VIS and ESR spectra of the enzyme. During the oxidation of veratryl alcohol performed in water, at room temperature and atmospheric pressure, LAC3 regenerates the palladium catalyst, is reduced and catalyzes the four-electron reduction of dioxygen into water with no loss of enzyme activity. The association of a laccase with a water-soluble palladium complex results in a 7-fold increase in the catalytic efficiency of the complex. This is the first step in the design of a family of renewable palladium catalysts for aerobic oxidation.

  3. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Science.gov (United States)

    Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

    2016-01-12

    Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  4. A novel dioxygenation product of arachidonic acid possesses potent chemotactic activity for human polymorphonuclear leukocytes.

    Science.gov (United States)

    Shak, S; Perez, H D; Goldstein, I M

    1983-12-25

    We have found that a novel dioxygenation product of arachidonic acid, 8(S),15(S)-dihydroxy-5,11-cis-9,13-trans-eicosatetraenoic acid (8,15-diHETE), possesses chemotactic activity for human polymorphonuclear leukocytes comparable to that of leukotriene B4. Authentic 8,15-diHETE, identified by gas chromatography-mass spectrometry, was prepared by treating arachidonic acid with soybean lipoxygenase and was purified by reverse-phase high performance liquid chromatography. Using a "leading front" assay, 8,15-diHETE exhibited significant chemotactic activity at a concentration of 5.0 ng/ml. Maximum chemotactic activity was observed at a concentration of 30 ng/ml. The 8,15-diHETE generated by mixed human leukocytes after stimulation with arachidonic acid and the calcium ionophore, A23187, exhibited quantitatively similar chemotactic activity. Two synthetic all-trans conjugated isomers of 8,15-diHETE, however, were not chemotactic at concentrations up to 500 ng/ml. In contrast to its potent chemotactic activity, 8,15-diHETE (at concentrations up to 10 micrograms/ml) was relatively inactive with respect to its ability to provoke either degranulation or generation of superoxide anion radicals by cytochalasin B-treated leukocytes. Both leukotriene B4 and 8,15-diHETE may be important mediators of inflammation.

  5. Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies.

    Science.gov (United States)

    Shevela, Dmitriy; Koroidov, Sergey; Najafpour, M Mahdi; Messinger, Johannes; Kurz, Philipp

    2011-05-02

    Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. An investigation on high-temperature electrical transport properties of graphene-oxide nano-thinfilms

    International Nuclear Information System (INIS)

    Venugopal, Gunasekaran; Krishnamoorthy, Karthikeyan; Kim, Sang-Jae

    2013-01-01

    High-temperature electrical transport properties are investigated for graphene-oxide nano thinfilms. The graphene-oxide nanoparticles are synthesized by modified Hummers method and characterized by UV–vis, Raman and X-ray diffraction techniques. The surface morphology of graphene-oxide film is analyzed using scanning electron and atomic force microscopy. The experimental results on high-temperature electrical studies of thinfilms exhibit metallic behavior followed by three-dimensional variable range hopping mechanism. The current–voltage characteristics at various temperatures (from 293 K to 573 K) were investigated. The effect of high-temperature on the functional groups of graphene-oxide film is evidently examined using X-ray photoelectron, thermal gravimetric analysis and Fourier transform infra-red spectroscopy. Transistor characteristics were performed after heat treatment resulting ambipolar behavior with holes and electron mobility of 127 and 66.9 cm 2 V −1 s −1 respectively. Our results are comparable to reduced graphene-oxide, indicating the advantage of our approach requires no further reduction to develop graphene-based transparent and conductive electrodes for dye-sensitized solar cells and ultra-capacitor applications.

  7. Calcium-manganese oxides as structural and functional models for active site in oxygen evolving complex in photosystem II: lessons from simple models.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi

    2011-01-01

    The oxygen evolving complex in photosystem II which induces the oxidation of water to dioxygen in plants, algae and certain bacteria contains a cluster of one calcium and four manganese ions. It serves as a model to split water by sunlight. Reports on the mechanism and structure of photosystem II provide a more detailed architecture of the oxygen evolving complex and the surrounding amino acids. One challenge in this field is the development of artificial model compounds to study oxygen evolution reaction outside the complicated environment of the enzyme. Calcium-manganese oxides as structural and functional models for the active site of photosystem II are explained and reviewed in this paper. Because of related structures of these calcium-manganese oxides and the catalytic centers of active site of the oxygen evolving complex of photosystem II, the study may help to understand more about mechanism of oxygen evolution by the oxygen evolving complex of photosystem II. Copyright © 2010 Elsevier B.V. All rights reserved.

  8. Charge transport along luminescent oxide layers containing Si and SiC nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Jambois, O. [EME, Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain)]. E-mail: ojambois@el.ub.es; Vila, A. [EME, Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Pellegrino, P. [EME, Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Carreras, J. [EME, Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Perez-Rodriguez, A. [EME, Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Garrido, B. [EME, Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Bonafos, C. [Nanomaterials Group, CEMES-CNRS, 29 rue J. Marvig 31055, Toulouse (France); BenAssayag, G. [Nanomaterials Group, CEMES-CNRS, 29 rue J. Marvig 31055, Toulouse (France)

    2006-12-15

    The electrical conductivity of silicon oxides containing silicon and silicon-carbon nanoparticles has been investigated. By use of sequential Si{sup +} and C{sup +} ion implantations in silicon oxide followed by an annealing at 1100 deg. C, luminescent Si nanocrystals and SiC nanoparticles were precipitated. The characterization of the electrical transport has been carried out on two kinds of structures, allowing parallel or perpendicular transport, with respect to the substrate. The first type of samples were elaborated by means of a focus-ion-beam technique: electrical contacts to embedded nanoparticles were made by milling two nanotrenches on the sample surface until reaching the buried layer, then filling them with tungsten. The distance between the electrodes is about 100 nm. The second type of samples correspond to 40 nm thick typical MOS capacitors. The electron transport along the buried layer has shown a dramatic lowering of the electrical current, up to five orders of magnitude, when applying a sequence of voltages. It has been related to a progressive charge retention inside the nanoparticles, which, on its turn, suppresses the electrical conduction along the layer. On the other hand, the MOS capacitors show a reversible carrier charge and discharge effect that limits the current at low voltage, mostly due to the presence of C in the layers. A typical Fowler-Nordheim injection takes place at higher applied voltages, with a threshold voltage equal to 23 V.

  9. Thermal radiative near field transport between vanadium dioxide and silicon oxide across the metal insulator transition

    Energy Technology Data Exchange (ETDEWEB)

    Menges, F.; Spieser, M.; Riel, H.; Gotsmann, B., E-mail: bgo@zurich.ibm.com [IBM Research-Zurich, Säumerstrasse 4, CH-8803 Rüschlikon (Switzerland); Dittberner, M. [IBM Research-Zurich, Säumerstrasse 4, CH-8803 Rüschlikon (Switzerland); Photonics Laboratory, ETH Zurich, 8093 Zurich (Switzerland); Novotny, L. [Photonics Laboratory, ETH Zurich, 8093 Zurich (Switzerland); Passarello, D.; Parkin, S. S. P. [IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120 (United States)

    2016-04-25

    The thermal radiative near field transport between vanadium dioxide and silicon oxide at submicron distances is expected to exhibit a strong dependence on the state of vanadium dioxide which undergoes a metal-insulator transition near room temperature. We report the measurement of near field thermal transport between a heated silicon oxide micro-sphere and a vanadium dioxide thin film on a titanium oxide (rutile) substrate. The temperatures of the 15 nm vanadium dioxide thin film varied to be below and above the metal-insulator-transition, and the sphere temperatures were varied in a range between 100 and 200 °C. The measurements were performed using a vacuum-based scanning thermal microscope with a cantilevered resistive thermal sensor. We observe a thermal conductivity per unit area between the sphere and the film with a distance dependence following a power law trend and a conductance contrast larger than 2 for the two different phase states of the film.

  10. Exploring the mechanism of tryptophan 2,3-dioxygenase

    Science.gov (United States)

    Thackray, Sarah J.; Mowat, Christopher G.; Chapman, Stephen K.

    2008-01-01

    The haem proteins TDO (tryptophan 2,3-dioxygenase) and IDO (indoleamine 2,3-dioxygenase) are specific and powerful oxidation catalysts that insert one molecule of dioxygen into L-tryptophan in the first and rate-limiting step in the kynurenine pathway. Recent crystallographic and biochemical analyses of TDO and IDO have greatly aided our understanding of the mechanisms employed by these enzymes in the binding and activation of dioxygen and tryptophan. In the present paper, we briefly discuss the function, structure and possible catalytic mechanism of these enzymes. PMID:19021508

  11. Local charge transport properties of hydrazine reduced monolayer graphene oxide sheets prepared under pressure condition

    DEFF Research Database (Denmark)

    Ryuzaki, Sou; Meyer, Jakob Abild Stengaard; Petersen, Søren Vermehren

    2014-01-01

    Charge transport properties of chemically reduced graphene oxide (RGO) sheets prepared by treatment with hydrazine were examined using conductive atomic force microscopy. The current-voltage (I-V) characteristics of monolayer RGO sheets prepared under atmospheric pressure followed an exponentially...

  12. Functionalized derivatives of 1,4-dimethylnaphthalene as precursors for biomedical applications: synthesis, structures, spectroscopy and photochemical activation in the presence of dioxygen.

    Science.gov (United States)

    Posavec, Damir; Zabel, Manfred; Bogner, Udo; Bernhardt, Günther; Knör, Günther

    2012-09-21

    Decomposition of endoperoxide containing molecules is an attractive approach for the delayed release of singlet oxygen under mild reaction conditions. Here we describe a new method for the adaptation of the corresponding decay times by controlling the supramolecular functional structure of the surrounding matrix in the immediate vicinity of embedded singlet oxygen precursors. Thus, a significant prolongation of the lifetime of the endoperoxide species is possible by raising the energy barrier of the thermal (1)O(2)-releasing step via a restriction of the free volume of the applied carrier material. Enabling such a prolonged decomposition period is crucial for potential biomedical applications of endoperoxide containing molecules, since sufficient time for appropriate cell uptake and transport to the desired target region must be available under physiological conditions before the tissue damaging-power of the reactive oxygen species formed is completely exhausted. Two novel polyaromatic systems for the intermediate storage and transport of endoperoxides and the controlled release of singlet oxygen in the context of anticancer and antibiotic activity have been prepared and characterized. These compounds are based on functionalized derivatives of the 1,4-dimethylnaphthalene family which are readily forming metastable endoperoxide species in the presence of dioxygen, a photosensitizer molecule such as methylene blue and visible light. In contrast to previously known systems of similar photoreactivity, the endoperoxide carrying molecules have been designed with optimized molecular properties in terms of potential chemotherapeutic applications. These include modifications of polarity to improve their incorporation into various biocompatible carrier materials, the introduction of hydrogen bonding motifs to additionally influence the endoperoxide decay kinetics, and the synthesis of bifunctional derivatives to enable synergistic effects of multiple singlet oxygen binding

  13. Carbazole angular dioxygenation and mineralization by bacteria isolated from hydrocarbon-contaminated tropical African soil.

    Science.gov (United States)

    Salam, L B; Ilori, M O; Amund, O O; Numata, M; Horisaki, T; Nojiri, H

    2014-01-01

    Four bacterial strains isolated from hydrocarbon-contaminated soils in Lagos, Nigeria, displayed extensive degradation abilities on carbazole, an N-heterocyclic aromatic hydrocarbon. Physicochemical analyses of the sampling sites (ACPP, MWO, NESU) indicate gross pollution of the soils with a high hydrocarbon content (157,067.9 mg/kg) and presence of heavy metals. Phylogenetic analysis of the four strains indicated that they were identified as Achromobacter sp. strain SL1, Pseudomonas sp. strain SL4, Microbacterium esteraromaticum strain SL6, and Stenotrophomonas maltophilia strain BA. The rates of degradation of carbazole by the four isolates during 30 days of incubation were 0.057, 0.062, 0.036, and 0.050 mg L(-1) h(-1) for strains SL1, SL4, SL6, and BA. Gas chromatographic (GC) analyses of residual carbazole after 30 days of incubation revealed that 81.3, 85, 64.4, and 76 % of 50 mg l(-1) carbazole were degraded by strains SL1, SL4, SL6, and BA, respectively. GC-mass spectrometry and high-performance liquid chromatographic analyses of the extracts from the growing and resting cells of strains SL1, SL4, and SL6 cultured on carbazole showed detection of anthranilic acid and catechol while these metabolites were not detected in strain BA under the same conditions. This study has established for the first time carbazole angular dioxygenation and mineralization by isolates from African environment.

  14. ZnO Nanowires Synthesized by Vapor Phase Transport Deposition on Transparent Oxide Substrates

    Directory of Open Access Journals (Sweden)

    Taylor Curtis

    2010-01-01

    Full Text Available Abstract Zinc oxide nanowires have been synthesized without using metal catalyst seed layers on fluorine-doped tin oxide (FTO substrates by a modified vapor phase transport deposition process using a double-tube reactor. The unique reactor configuration creates a Zn-rich vapor environment that facilitates formation and growth of zinc oxide nanoparticles and wires (20–80 nm in diameter, up to 6 μm in length, density <40 nm apart at substrate temperatures down to 300°C. Electron microscopy and other characterization techniques show nanowires with distinct morphologies when grown under different conditions. The effect of reaction parameters including reaction time, temperature, and carrier gas flow rate on the size, morphology, crystalline structure, and density of ZnO nanowires has been investigated. The nanowires grown by this method have a diameter, length, and density appropriate for use in fabricating hybrid polymer/metal oxide nanostructure solar cells. For example, it is preferable to have nanowires no more than 40 nm apart to minimize exciton recombination in polymer solar cells.

  15. Light-emitting diodes based on solution-processed nontoxic quantum dots: oxides as carrier-transport layers and introducing molybdenum oxide nanoparticles as a hole-inject layer.

    Science.gov (United States)

    Bhaumik, Saikat; Pal, Amlan J

    2014-07-23

    We report fabrication and characterization of solution-processed quantum dot light-emitting diodes (QDLEDs) based on a layer of nontoxic and Earth-abundant zinc-diffused silver indium disulfide (AIZS) nanoparticles as an emitting material. In the QDLEDs fabricated on indium tin oxide (ITO)-coated glass substrates, we use layers of oxides, such as graphene oxide (GO) and zinc oxide (ZnO) nanoparticles as a hole- and electron-transport layer, respectively. In addition, we introduce a layer of MoO3 nanoparticles as a hole-inject one. We report a comparison of the characteristics of different device architectures. We show that an inverted device architecture, ITO/ZnO/AIZS/GO/MoO3/Al, yields a higher electroluminescence (EL) emission, compared to direct ones, for three reasons: (1) the GO/MoO3 layers introduce barriers for electrons to reach the Al electrode, and, similarly, the ZnO layers acts as a barrier for holes to travel to the ITO electrode; (2) the introduction of a layer of MoO3 nanoparticles as a hole-inject layer reduces the barrier height for holes and thereby balances charge injection in the inverted structure; and (3) the wide-bandgap zinc oxide next to the ITO electrode does not absorb the EL emission during its exit from the device. In the QDLEDs with oxides as carrier inject and transport layers, the EL spectrum resembles the photoluminescence emission of the emitting material (AIZS), implying that excitons are formed in the quaternary nanocrystals and decay radiatively.

  16. Ru-bis(pyridine)pyrazolate (bpp)-Based Water-Oxidation Catalysts Anchored on TiO2: The Importance of the Nature and Position of the Anchoring Group.

    Science.gov (United States)

    Francàs, Laia; Richmond, Craig; Garrido-Barros, Pablo; Planas, Nora; Roeser, Stephan; Benet-Buchholz, Jordi; Escriche, Lluís; Sala, Xavier; Llobet, Antoni

    2016-04-04

    Three distinct functionalisation strategies have been applied to the in,in-[{Ru(II)(trpy)}2(μ-bpp)(H2O)2](3+) (trpy=2,2':6',2''-terpyridine, bpp=bis(pyridine)pyrazolate) water-oxidation catalyst framework to form new derivatives that can adsorb onto titania substrates. Modifications included the addition of sulfonate, carboxylate, and phosphonate anchoring groups to the terpyridine and bis(pyridyl)pyrazolate ligands. The complexes were characterised in solution by using 1D NMR, 2D NMR, and UV/Vis spectroscopic analysis and electrochemical techniques. The complexes were then anchored on TiO2-coated fluorinated tin oxide (FTO) films, and the reactivity of these new materials as water-oxidation catalysts was tested electrochemically through controlled-potential electrolysis (CPE) with oxygen evolution detected by headspace analysis with a Clark electrode. The results obtained highlight the importance of the catalyst orientation with respect to the titania surface in regard to its capacity to catalytically oxidize water to dioxygen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Tuning the Relative Stability and Reactivity of Manganese Dioxygen and Peroxo Intermediates via Systematic Ligand Modification.

    Science.gov (United States)

    Kovacs, Julie A

    2015-10-20

    Many fundamental processes of life depend on the chemical energy stored in the O–O bond of dioxygen (O2), the majority of which is derived from photosynthetic H2O oxidation. Key steps in these processes involve Mn-, Fe-, or Cu-promoted formation or cleavage of O–O and O–H bonds, the mechanisms of which are not fully understood, especially with Mn. Metal–peroxo and high-valent metal–oxo species are proposed to be involved as intermediates. The metal ion properties that favor O–O and O–H bond formation versus cleavage have yet to be systematically explored. Herein we examine the O2 reactivity of a series of structurally related Mn(II) complexes and show that several metastable intermediates are observed, the relative stabilities of which depend on subtle differences in ligand architecture. We show that in contrast to Fe and Cu complexes, O2 binds irreversibly to Mn(II). By crystallizing an entire series of the first reported examples of Mn(III)–OOR peroxos as well as an O2-derived binuclear trans-μ-1,2-bridged Mn(III)–peroxo with varying degrees of O–O bond activation, we demonstrate that there are distinct correlations between spectroscopic, structural, and reactivity properties. Rate-limiting O–O bond cleavage is shown to afford a reactive species capable of abstracting H atoms from 2,4-tBu2-PhOH or 1,4-cyclohexadiene, depending on the ligand substituents. The weakly coordinated N-heterocycle Mn···Npy,quino distance is shown to correlate with the peroxo O–O bond length and modulate the π overlap between the filled πv*(O–O) and Mn dxz orbitals. We also show that there is a strong correlation between the peroxo → Mn charge transfer (CT) band and the peroxo O–O bond length. The energy difference between the CT bands associated with the peroxos possessing the shortest and longest O–O bonds shows that these distances are spectroscopically distinguishable. We show that we can use this spectroscopic parameter to estimate the O

  18. Transport, retention, and size perturbation of graphene oxide in saturated porous media: Effects of input concentration and grain size

    Science.gov (United States)

    Accurately predicting the fate and transport of graphene oxide (GO) in porous media is critical to assess its environmental impact. In this work, sand column experiments were conducted to determine the effect of input concentration and grain size on transport, retention, and size perturbation of GO ...

  19. Charge transport in dye-sensibilized porous zinc oxide films; Ladungstransport in farbstoffsensibilisierten poroesen Zinkoxidfilmen

    Energy Technology Data Exchange (ETDEWEB)

    Reemts, J.

    2006-05-18

    During the last decades, zinc oxide has attracted a lot of attention as an important material in various electrical, chemical, and optical applications. In the present work results are discussed gained from investigations of highly porous electrochemically deposited zinc oxide, which is a promising electrode material both in the area of solar energy conversion and sensor technology. The films were prepared by adding detergents during the electrodeposition process. The detergents have a structure-directing influence during the film deposition and, therefore, on the morphology of the films. The obtained electrodes can easily be sensitized for light or different chemicals by a simple adsorption of different molecules. In the present work I discuss the fundamental charge transport properties of electrochemically deposited zinc oxide films. Temperature-dependent measurements of the current-voltage characteristics are carried out and the spectral response of the photoconductivity is investigated. In order to understand the charge transport properties of this highly porous material, it is necessary to get a deeper insight in the electrode morphology. Therefore, different optical and scanning probe microscopy methods are used to characterize the inner structure of the electrodes. The electrical conductivity of the zinc oxide films can be seen as a thermally activated process, which can be explained by electronic transitions from the valence band of the zinc oxide to two shallow impurity levels. The current-voltage characteristic unveils a nonlinear behavior which can be explained by a space-charge-limited current model with traps distributed in energy. Upon excitation with different wavelengths, the conductivity of the zinc oxide increases already under sub-band gap illumination due to widely distributed trap states within the band gap. The transients of the photoconductivity follow a stretched exponential law with time scales in the range of several hours, either if the

  20. A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

    Science.gov (United States)

    Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

    2009-11-01

    Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

  1. Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

    KAUST Repository

    Anneser, Markus R.; Haslinger, Stefan; Pö thig, Alexander; Cokoja, Mirza; D'Elia, Valerio; Hö gerl, Manuel P.; Basset, Jean-Marie; Kü hn, Fritz E.

    2016-01-01

    The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure

  2. Moving protons with pendant amines: proton mobility in a nickel catalyst for oxidation of hydrogen.

    Science.gov (United States)

    O'Hagan, Molly; Shaw, Wendy J; Raugei, Simone; Chen, Shentan; Yang, Jenny Y; Kilgore, Uriah J; DuBois, Daniel L; Bullock, R Morris

    2011-09-14

    Proton transport is ubiquitous in chemical and biological processes, including the reduction of dioxygen to water, the reduction of CO(2) to formate, and the production/oxidation of hydrogen. In this work we describe intramolecular proton transfer between Ni and positioned pendant amines for the hydrogen oxidation electrocatalyst [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+) (P(Cy)(2)N(Bn)(2) = 1,5-dibenzyl-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane). Rate constants are determined by variable-temperature one-dimensional NMR techniques and two-dimensional EXSY experiments. Computational studies provide insight into the details of the proton movement and energetics of these complexes. Intramolecular proton exchange processes are observed for two of the three experimentally observable isomers of the doubly protonated Ni(0) complex, [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+), which have N-H bonds but no Ni-H bonds. For these two isomers, with pendant amines positioned endo to the Ni, the rate constants for proton exchange range from 10(4) to 10(5) s(-1) at 25 °C, depending on isomer and solvent. No exchange is observed for protons on pendant amines positioned exo to the Ni. Analysis of the exchange as a function of temperature provides a barrier for proton exchange of ΔG(‡) = 11-12 kcal/mol for both isomers, with little dependence on solvent. Density functional theory calculations and molecular dynamics simulations support the experimental observations, suggesting metal-mediated intramolecular proton transfers between nitrogen atoms, with chair-to-boat isomerizations as the rate-limiting steps. Because of the fast rate of proton movement, this catalyst may be considered a metal center surrounded by a cloud of exchanging protons. The high intramolecular proton mobility provides information directly pertinent to the ability of pendant amines to accelerate proton transfers during catalysis of hydrogen oxidation. These results may also have broader implications for proton movement in

  3. Tracking Oxidation During Transport of Trace Gases in Air from the Northern to Southern Hemisphere

    Science.gov (United States)

    Montzka, S. A.; Moore, F. L.; Atlas, E. L.; Parrish, D. D.; Miller, B. R.; Sweeney, C.; McKain, K.; Hall, B. D.; Siso, C.; Crotwell, M.; Hintsa, E. J.; Elkins, J. W.; Blake, D. R.; Barletta, B.; Meinardi, S.; Claxton, T.; Hossaini, R.

    2017-12-01

    Trace gas mole fractions contain the imprint of recent influences on an air mass such as sources, transport, and oxidation. Covariations among the many gases measured from flasks during ATom and HIPPO, and from the ongoing NOAA cooperative air sampling program enable recent influences to be identified from a wide range of sources including industrial activity, biomass burning, emissions from wetlands, and uptake by terrestrial ecosystems. In this work we explore the evolution of trace gas concentrations owing to atmospheric oxidation as air masses pass through the tropics, the atmospheric region with the highest concentrations of the hydroxyl radical. Variations in C2-C5 hydrocarbon concentrations downwind of source regions provide a measure of photochemical ageing in an air mass since emission, but they become less useful when tracking photochemical ageing as air is transported from the NH into the SH owing to their low mixing ratios, lifetimes that are very short relative to transport times, non-industrial sources in the tropics (e.g., biomass burning), and southern hemispheric sources. Instead, we consider a range of trace gases and trace gas pairs that provide a measure of photochemical processing as air transits the tropics. To be useful in this analysis, these trace gases would have lifetimes comparable to interhemispheric transport times, emissions arising from only the NH at constant relative magnitudes, and concentrations sufficient to allow precise and accurate measurements in both hemispheres. Some anthropogenically-emitted chlorinated hydrocarbons meet these requirements and have been measured during ATom, HIPPO, and from NOAA's ongoing surface sampling efforts. Consideration of these results and their implications for tracking photochemical processing in air as it is transported across the tropics will be presented.

  4. Visible light-driven O2 reduction by a porphyrin-laccase system.

    Science.gov (United States)

    Lazarides, Theodore; Sazanovich, Igor V; Simaan, A Jalila; Kafentzi, Maria Chrisanthi; Delor, Milan; Mekmouche, Yasmina; Faure, Bruno; Réglier, Marius; Weinstein, Julia A; Coutsolelos, Athanassios G; Tron, Thierry

    2013-02-27

    Several recent studies have shown that the combination of photosensitizers with metalloenzymes can support a light-driven multielectron reduction of molecules such as CO(2) or HCN. Here we show that the association of the zinc tetramethylpyridinium porphyrin (ZnTMPyP(4+)) photosensitizer with the multicopper oxidase (MCO) laccase allows to link the oxidation of an organic molecule to the four electrons reduction of dioxygen into water. The enzyme is photoreduced within minutes with porphyrin/enzyme ratio as low as 1:40. With a 1:1 ratio, the dioxygen consumption rate is 1.7 μmol L(-1) s(-1). Flash photolysis experiments support the formation of the triplet excited state of ZnTMPyP(4+) which reduces the enzyme to form a radical cation of the porphyrin with a k(ET) ≈ 10(7) s(-1) M(-1). The long-lived triplet excited state of the ZnTMPyP(4+) (τ(0) = 0.72 ms) accounts for a substantial electron-transfer quantum yield, φ(ET) = 0.35. Consequently, the enzyme-dependent photo-oxidation of the electron donor occurs with a turnover of 8 min(-1) for the one-electron oxidation process, thereby supporting the suitability of such enzyme/sensitizer hybrid systems for aerobic photodriven transformations on substrates. This study is the first example of a phorphyrin-sensitized four-electron reduction of an enzyme of the MCO family, leading to photoreduction of dioxygen into water.

  5. Relationships between nitric oxide, nitroxyl ion, nitrosonium cation and peroxynitrite.

    Science.gov (United States)

    Hughes, M N

    1999-05-05

    This review is concerned mainly with the three redox-related, but chemically distinct, species NO-, NO. and NO+, with greatest emphasis being placed on the chemistry and biology of the nitroxyl ion. Biochemical routes for the formation of nitroxyl ion and methods for showing the intermediacy of this species are discussed, together with chemical methods for generating nitroxyl ion in solution. Reactions of nitroxyl ion with NO., thiols, iron centres in haem and with dioxygen are reviewed The significance of the reaction between NO- and dioxygen as a source of peroxynitrite is assessed, and attention drawn to the possible significance of the spin state of the nitroxyl ion in this context. The biological significance of nitrosation and the importance of S-nitrosothiols and certain metal nitrosyl complexes as carriers of NO+ at physiological pH is stressed. Some features in the chemistry of peroxynitrite are noted.

  6. Advective and diffusive contributions to reactive gas transport during pyrite oxidation in the unsaturated zone

    NARCIS (Netherlands)

    Binning, P. J.; POSTMA, D; Russell, T. F.; Wesselingh, J. A.; Boulin, P. F.

    2007-01-01

    [1] Pyrite oxidation in unsaturated mine waste rock dumps and soils is limited by the supply of oxygen from the atmosphere. In models, oxygen transport through the subsurface is often assumed to be driven by diffusion. However, oxygen comprises 23.2% by mass of dry air, and when oxygen is consumed

  7. Impacts of nitric oxide and superoxide on renal medullary oxygen transport and urine concentration

    Science.gov (United States)

    Edwards, Aurélie; Layton, Anita T.

    2015-01-01

    The goal of this study was to investigate the reciprocal interactions among oxygen (O2), nitric oxide (NO), and superoxide (O2−) and their effects on medullary oxygenation and urinary output. To accomplish that goal, we developed a detailed mathematical model of solute transport in the renal medulla of the rat kidney. The model represents the radial organization of the renal tubules and vessels, which centers around the vascular bundles in the outer medulla and around clusters of collecting ducts in the inner medulla. Model simulations yield significant radial gradients in interstitial fluid oxygen tension (Po2) and NO and O2− concentration in the OM and upper IM. In the deep inner medulla, interstitial fluid concentrations become much more homogeneous, as the radial organization of tubules and vessels is not distinguishable. The model further predicts that due to the nonlinear interactions among O2, NO, and O2−, the effects of NO and O2− on sodium transport, osmolality, and medullary oxygenation cannot be gleaned by considering each solute's effect in isolation. An additional simulation suggests that a sufficiently large reduction in tubular transport efficiency may be the key contributing factor, more so than oxidative stress alone, to hypertension-induced medullary hypoxia. Moreover, model predictions suggest that urine Po2 could serve as a biomarker for medullary hypoxia and a predictor of the risk for hospital-acquired acute kidney injury. PMID:25651567

  8. In Situ Insight into Reversible O2 Gas-Solid Reactions

    DEFF Research Database (Denmark)

    Wegeberg, Christina

    2016-01-01

    Non-porous crystalline solids containing a series of cationic tetracobalt complexes reversibly, selectively and stoichiometrically chemisorb dioxygen in temperature/O2 partial pressure induced processes involving the oxidation of cobalt with concurrent reduction of two equivalents of sorbed O2 to...

  9. IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

    Science.gov (United States)

    Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

    2013-01-01

    Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

  10. Impact of energy efficiency and replacement of diesel fuel with natural gas in public transport on reducing emissions of nitrogen oxides

    Energy Technology Data Exchange (ETDEWEB)

    Dimitrovski, Dame; Jovanovski, Antonio [Faculty of Mechanical Engineering, ' Ss. Cyril and Methodius' University, Skopje (Macedonia, The Former Yugoslav Republic of)

    2014-07-01

    This paper analyzes the direct emissions of nitrogen oxides from the public transport (bus) in urban areas in the Republic of Macedonia. As influential factors on which to compare the quantity of these emissions are taken: Penetration of new (energy efficient) technologies in bus transport, the intensity of the bus fleet renewal for public transport and replacement of diesel with natural gas. (Author)

  11. Dinitrosyl iron complexes and S-nitrosothiols are two possible forms for stabilization and transport of nitric oxide in biological systems.

    Science.gov (United States)

    Vanin, A F

    1998-07-01

    The physicochemical properties, mechanisms of synthesis and decomposition of dinitrosyl iron complexes (DNICs) with thiol-containing ligands and of S-nitrosothiols (RS-NO), and the potential role of these compounds in storage and transport of NO in biological systems are reviewed. Special attention is given to the phenomenon of mutual transformation of DNIC and RS-NO catalyzed by Fe2+. Each Fe2+ binds two neutral NO molecules in the DNICs, catalyzes their mutual oxidation--reduction with formation of nitrous oxide and nitrosonium ions appearing in the DNICs. These ions S-nitrosate thiol-compounds with RS-NO formation. Fe2+ binds two RS-NO molecules and catalyzes their mutual oxidation--reduction followed by decomposition of the resulting molecules. Mutual conversion of DNICs and RS-NO regulated by iron, thiol, and NO levels is suggested to provide NO transport in cells and tissues.

  12. Operation of staged membrane oxidation reactor systems

    Science.gov (United States)

    Repasky, John Michael

    2012-10-16

    A method of operating a multi-stage ion transport membrane oxidation system. The method comprises providing a multi-stage ion transport membrane oxidation system with at least a first membrane oxidation stage and a second membrane oxidation stage, operating the ion transport membrane oxidation system at operating conditions including a characteristic temperature of the first membrane oxidation stage and a characteristic temperature of the second membrane oxidation stage; and controlling the production capacity and/or the product quality by changing the characteristic temperature of the first membrane oxidation stage and/or changing the characteristic temperature of the second membrane oxidation stage.

  13. Native oxide transport and removal during the atomic layer deposition of Ta{sub 2}O{sub 5} on InAs(100) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Henegar, Alex J.; Gougousi, Theodosia, E-mail: gougousi@umbc.edu [Department of Physics, UMBC, Baltimore, Maryland 21250 (United States)

    2016-05-15

    Atomic layer deposition (ALD) was used to deposit Ta{sub 2}O{sub 5} on etched and native oxide-covered InAs(100) using pentakis dimethyl amino tantalum and H{sub 2}O at 200–300 °C. The transport and removal of the native oxides during the ALD process was investigated using x-ray photoelectron spectroscopy (XPS). Depositions above 200 °C on etched surfaces protected the interface from reoxidation. On native oxide-covered surfaces, depositions resulted in enhanced native oxide removal at higher temperatures. The arsenic oxides were completely removed above 250 °C after 3 nm of film growth, but some of the As{sub 2}O{sub 3} remained in the film at lower temperatures. Angle-resolved and sputter depth profiling XPS confirmed indium and arsenic oxide migration into the Ta{sub 2}O{sub 5} film at deposition temperatures as low as 200 °C. Continuous removal of both arsenic and indium oxides was confirmed even after the deposition of several monolayers of a coalesced Ta{sub 2}O{sub 5} film, and it was demonstrated that native oxide transport is a prevalent component of the interface “clean-up” mechanism.

  14. Modeling the transport properties of epitaxially grown thermoelectric oxide thin films using spectroscopic ellipsometry

    KAUST Repository

    Sarath Kumar, S. R.

    2012-02-01

    The influence of oxygen vacancies on the transport properties of epitaxial thermoelectric (Sr,La)TiO3 thin films is determined using electrical and spectroscopic ellipsometry (SE) measurements. Oxygen vacancy concentration was varied by ex-situ annealing in Ar and Ar/H2. All films exhibited degenerate semiconducting behavior, and electrical conductivity decreased (258–133 S cm−1) with increasing oxygen content. Similar decrease in the Seebeck coefficient is observed and attributed to a decrease in effective mass (7.8–3.2 me ), as determined by SE. Excellent agreement between transport properties deduced from SE and direct electrical measurements suggests that SE is an effective tool for studying oxide thin film thermoelectrics.

  15. Modeling the transport properties of epitaxially grown thermoelectric oxide thin films using spectroscopic ellipsometry

    KAUST Repository

    Sarath Kumar, S. R.; Abutaha, Anas I.; Hedhili, Mohamed N.; Alshareef, Husam N.

    2012-01-01

    The influence of oxygen vacancies on the transport properties of epitaxial thermoelectric (Sr,La)TiO3 thin films is determined using electrical and spectroscopic ellipsometry (SE) measurements. Oxygen vacancy concentration was varied by ex-situ annealing in Ar and Ar/H2. All films exhibited degenerate semiconducting behavior, and electrical conductivity decreased (258–133 S cm−1) with increasing oxygen content. Similar decrease in the Seebeck coefficient is observed and attributed to a decrease in effective mass (7.8–3.2 me ), as determined by SE. Excellent agreement between transport properties deduced from SE and direct electrical measurements suggests that SE is an effective tool for studying oxide thin film thermoelectrics.

  16. Nitric oxide transport in blood: a third gas in the respiratory cycle.

    Science.gov (United States)

    Doctor, Allan; Stamler, Jonathan S

    2011-01-01

    The trapping, processing, and delivery of nitric oxide (NO) bioactivity by red blood cells (RBCs) have emerged as a conserved mechanism through which regional blood flow is linked to biochemical cues of perfusion sufficiency. We present here an expanded paradigm for the human respiratory cycle based on the coordinated transport of three gases: NO, O₂, and CO₂. By linking O₂ and NO flux, RBCs couple vessel caliber (and thus blood flow) to O₂ availability in the lung and to O₂ need in the periphery. The elements required for regulated O₂-based signal transduction via controlled NO processing within RBCs are presented herein, including S-nitrosothiol (SNO) synthesis by hemoglobin and O₂-regulated delivery of NO bioactivity (capture, activation, and delivery of NO groups at sites remote from NO synthesis by NO synthase). The role of NO transport in the respiratory cycle at molecular, microcirculatory, and system levels is reviewed. We elucidate the mechanism through which regulated NO transport in blood supports O₂ homeostasis, not only through adaptive regulation of regional systemic blood flow but also by optimizing ventilation-perfusion matching in the lung. Furthermore, we discuss the role of NO transport in the central control of breathing and in baroreceptor control of blood pressure, which subserve O₂ supply to tissue. Additionally, malfunctions of this transport and signaling system that are implicated in a wide array of human pathophysiologies are described. Understanding the (dys)function of NO processing in blood is a prerequisite for the development of novel therapies that target the vasoactive capacities of RBCs. © 2011 American Physiological Society.

  17. High Performance Nano-Crystalline Oxide Fuel Cell Materials. Defects, Structures, Interfaces, Transport, and Electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, Scott [Northwestern Univ., Evanston, IL (United States); Poeppelmeier, Ken [Northwestern Univ., Evanston, IL (United States); Mason, Tom [Northwestern Univ., Evanston, IL (United States); Marks, Lawrence [Northwestern Univ., Evanston, IL (United States); Voorhees, Peter [Northwestern Univ., Evanston, IL (United States)

    2016-09-07

    This project addresses fundamental materials challenges in solid oxide electrochemical cells, devices that have a broad range of important energy applications. Although nano-scale mixed ionically and electronically conducting (MIEC) materials provide an important opportunity to improve performance and reduce device operating temperature, durability issues threaten to limit their utility and have remained largely unexplored. Our work has focused on both (1) understanding the fundamental processes related to oxygen transport and surface-vapor reactions in nano-scale MIEC materials, and (2) determining and understanding the key factors that control their long-term stability. Furthermore, materials stability has been explored under the “extreme” conditions encountered in many solid oxide cell applications, i.e, very high or very low effective oxygen pressures, and high current density.

  18. Plutonium transport for the oxide form. Air and road accidentology

    International Nuclear Information System (INIS)

    Degrange, J.P.; Hubert, P.; Pages, P.

    1989-07-01

    The aim of the study is to define the probability of accident that can be applied to a packaging for plutonium oxide transport. The analysis is designed essentially for packagings of few tons with impact resistance corresponding to a speed of 10 m/s but can be used for packagings with a resistance corresponding to IAEA tests. This work is based on analysis and processing of 2 accident files: one on road accidents, the other on air accidents. Computer codes are developed, from one hand, to obtain stress indicator distribution by Monte Carlo methods and on the other hand to link these distributions to itinerary parameters. Previous similar studies are examined and compared to figures obtained here and explained as far as possible [fr

  19. Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

    Science.gov (United States)

    Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

    2017-01-17

    Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

  20. Graphene oxide-facilitated transport of levofloxacin and ciprofloxacin in saturated and unsaturated porous media.

    Science.gov (United States)

    Sun, Kaixuan; Dong, Shunan; Sun, Yuanyuan; Gao, Bin; Du, Wenchao; Xu, Hongxia; Wu, Jichun

    2018-04-15

    In this work, effects of graphene oxide (GO) on the co-transport of the two typical Fluoroquinolones (FQs) - levofloxacin (LEV) and ciprofloxacin (CIP) in saturated and unsaturated quartz sand media were studied. The adsorption isotherms showed that GO had much larger sorption capacities to LEV and CIP than sand with the largest Langmuir adsorption capacity of 409 mg g -1 (CIP-GO); while the sorption affinity of the two FQs onto the two adsorbents might follow the order of CIP-sand > LEV-sand > LEV-GO > CIP-GO. GO promoted the mobility of the two FQs in both saturated and unsaturated porous media due to its strong mobility and sorption capacity. The GO-bound LEV/CIP was responsible for the LEV/CIP transport in the porous media, and transport of GO-bound FQs increased with the increasing of initial GO concentration. Under unsaturated conditions, moisture showed little effect on the transport of GO-bound CIP; however, the mobility of GO-bound LEV reduced with the decreasing of moisture content, suggesting the transport of adsorbed LEV from GO to air-water interface. GO sorption reduced the antibacterial ability of the two FQs, but they were still effective in inhibiting E. coli growth. Copyright © 2018 Elsevier B.V. All rights reserved.

  1. Transport stress induces heart damage in newly hatched chicks via blocking the cytoprotective heat shock response and augmenting nitric oxide production.

    Science.gov (United States)

    Sun, F; Zuo, Y-Z; Ge, J; Xia, J; Li, X-N; Lin, J; Zhang, C; Xu, H-L; Li, J-L

    2018-04-20

    Transport stress affects the animal's metabolism and psychological state. As a pro-survival pathway, the heat shock response (HSR) protects healthy cells from stressors. However, it is unclear whether the HSR plays a role in transport stress-induced heart damage. To evaluate the effects of transport stress on heart damage and HSR protection, newly hatched chicks were treated with transport stress for 2 h, 4 h and 8 h. Transport stress caused decreases in body weight and increases in serum creatine kinase (CK) activity, nitric oxide (NO) content in heart tissue, cardiac nitric oxide syntheses (NOS) activity and NOS isoforms transcription. The mRNA expression of heat shock factors (HSFs, including HSF1-3) and heat shock proteins (HSPs, including HSP25, HSP40, HSP47, HSP60, HSP70, HSP90 and HSP110) in the heart of 2 h transport-treated chicks was upregulated. After 8 h of transport stress in chicks, the transcription levels of the same HSPs and HSF2 were reduced in the heart. It was also found that the changes in the HSP60, HSP70 and HSP90 protein levels had similar tendencies. These results suggested that transport stress augmented NO generation through enhancing the activity of NOS and the transcription of NOS isoforms. Therefore, this study provides new evidence that transport stress induces heart damage in the newly hatched chicks by blocking the cytoprotective HSR and augmenting NO production.

  2. Synthesis of a '4+1' Re(V) complex from Re(III), and its ...

    African Journals Online (AJOL)

    bis(2-hydroxybenzyl)-2-(2-aminoethyl)dimethylamine) was prepared from the oxidation of [ReCl3(MeCN)(PPh3)2] by dioxygen in the presence of H2had in ethanol. This reaction was done under reflux conditions for a relatively short reaction ...

  3. Graphene Oxide-TiO2 Nanocomposite Films for Electron Transport Applications

    Science.gov (United States)

    Saleem, Abida; Ullah, Naveed; Khursheed, Kamran; Iqbal, Tahir; Shah, Saqlain A.; Asjad, Muhammad; Sarwar, Nazim; Saleem, Murtaza; Arshad, Muhammad

    2018-03-01

    Graphene oxide-titanium dioxide (GO-TiO2) nanocomposite thin films were prepared for application as the window layer of perovskite solar cells. Graphene oxide (GO) was prepared by a modified Hummer's method, and titanium dioxide (TiO2) nanoparticles were synthesized by hydrothermal solution method. Thin films of GO-TiO2 nanocomposite were prepared with different wt.% of GO by spin coating on indium tin oxide (ITO) substrate followed by annealing at 150°C. X-ray diffraction analysis revealed rutile phase of TiO2 nanostructures. The bandgap of the pure TiO2 thin film was found to be 3.5 eV, reducing to 2.9 eV for the GO-TiO2 nanocomposites with a red-shift towards higher wavelength. Furthermore, thermal postannealing at 400°C improved the transparency in the visible region and decreased the sheet resistance. Morphological and elemental analysis was performed by scanning electron microscopy and energy-dispersive x-ray spectroscopy, respectively. The current-voltage characteristic of the GO-TiO2 nanocomposites indicated Ohmic contact with the ITO substrate. The chemical composition of the as-synthesized GO-TiO2 nanocomposites was investigated by x-ray photoelectron spectroscopy (XPS). The results presented herein demonstrate a new, low-temperature solution-processing approach to obtain rGO-TiO2 composite material for use as the electron transport layer of perovskite solar cells.

  4. Enhanced permanganate in situ chemical oxidation through MnO2 particle stabilization: evaluation in 1-D transport systems.

    Science.gov (United States)

    Crimi, Michelle; Quickel, Mark; Ko, Saebom

    2009-02-27

    In situ chemical oxidation using permanganate is an increasingly employed approach to organic contaminant remediation at hazardous waste sites. Manganese dioxide (MnO2) particles form as a by-product of the reaction of permanganate with contaminants and naturally-reduced subsurface materials. These particles are of interest because they have the potential to deposit in the subsurface and impact the flow regime in/around permanganate injection, including the well screen, filter pack, and the surrounding subsurface formation. Control of these particles can allow for improved oxidant injection and transport, and contact between the oxidant and contaminants of concern. Sodium hexametaphosphate (HMP) has previously been identified as a promising aid to stabilize MnO2 in solution when included in the oxidizing solution, increasing the potential to inhibit particle deposition and impact subsurface flow. The goal of the experimental studies described herein was to investigate the ability of HMP to prevent particle deposition in transport studies using four different types of porous media. Permanganate was delivered to a contaminant source zone (trichloroethylene) located within four different media types with variations in sand, clay, organic carbon, and iron oxides (as goethite) content. Deposition of MnO2 within the columns was quantified with distance from the source zone. Experiments were repeated in replicate columns with the inclusion of HMP directly with the oxidant delivery solution, and MnO2 deposition was again quantified. While total MnO2 deposition within the 60 cm columns did not change significantly with the addition of HMP, deposition within the contaminant source zone decreased by 25-85%, depending on the specific media type. The greatest differences in deposition were observed in the goethite-containing and clay-containing columns. Columns containing these two media types experienced completely plugged flow in the oxidant-only delivery systems; however

  5. Transport of oxidants and radionuclides through a clay barrier

    International Nuclear Information System (INIS)

    Neretnieks, I.

    1978-02-01

    The masstransfer rate for oxidants to, and radionuclides from a capsule in a repository has been computed. The capsule which is 0.75 m in diameter is surrounded by Montmorillonite clay. The hole is 1.5 m in diameter. For one capsule about 1220g copper will corrode due to oxygen corrosion in 10 000 years. If the fissures in the rock nearest the hole are filled with clay, the corrosion will decrease significantly. This is valid for a case where the groundwater is in equilibrium with oxygen of 0.2 bar pressure (normal air pressure). Measurements of the oxygen content in groundwater at large depths show a more than 1 000 times smaller values. The transport rate will then be correspondingly smaller. Corrosion due to sulphate/sulphide corrosion may reach some 590 g in the same time if there is 10 mg/l of the least abundant component. The radionuclides Sr 90 , Cs 137 , Am 241 and Am 243 will decay totally in the clay barriers. Pu 240 will be seriously hindered. The total dissolution of the uranium oxide in a capsule takes at least 1.8 million years. Nuclides with high solubilities decrease in about 2 000 years to half their original concentration. The sodium in the Montmorillonite clay in the fissures is exchanged for calcium in about 20 000 years. The exchange of the sodium in the clay in the hole takes millions of years

  6. Amorphous Tin Oxide as a Low-Temperature-Processed Electron-Transport Layer for Organic and Hybrid Perovskite Solar Cells

    KAUST Repository

    Barbe, Jeremy; Tietze, Max Lutz; Neophytou, Marios; Banavoth, Murali; Alarousu, Erkki; El Labban, Abdulrahman; Abulikemu, Mutalifu; Yue, Wan; Mohammed, Omar F.; McCulloch, Iain; Amassian, Aram; Del Gobbo, Silvano

    2017-01-01

    Chemical bath deposition (CBD) of tin oxide (SnO) thin films as an electron-transport layer (ETL) in a planar-heterojunction n-i-p organohalide lead perovskite and organic bulk-heterojunction (BHJ) solar cells is reported. The amorphous SnO (a

  7. Modeling of the Nitric Oxide Transport in the Human Lungs.

    Science.gov (United States)

    Karamaoun, Cyril; Van Muylem, Alain; Haut, Benoît

    2016-01-01

    In the human lungs, nitric oxide (NO) acts as a bronchodilatator, by relaxing the bronchial smooth muscles and is closely linked to the inflammatory status of the lungs, owing to its antimicrobial activity. Furthermore, the molar fraction of NO in the exhaled air has been shown to be higher for asthmatic patients than for healthy patients. Multiple models have been developed in order to characterize the NO dynamics in the lungs, owing to their complex structure. Indeed, direct measurements in the lungs are difficult and, therefore, these models are valuable tools to interpret experimental data. In this work, a new model of the NO transport in the human lungs is proposed. It belongs to the family of the morphological models and is based on the morphometric model of Weibel (1963). When compared to models published previously, its main new features are the layered representation of the wall of the airways and the possibility to simulate the influence of bronchoconstriction (BC) and of the presence of mucus on the NO transport in lungs. The model is based on a geometrical description of the lungs, at rest and during a respiratory cycle, coupled with transport equations, written in the layers composing an airway wall and in the lumen of the airways. First, it is checked that the model is able to reproduce experimental information available in the literature. Second, the model is used to discuss some features of the NO transport in healthy and unhealthy lungs. The simulation results are analyzed, especially when BC has occurred in the lungs. For instance, it is shown that BC can have a significant influence on the NO transport in the tissues composing an airway wall. It is also shown that the relation between BC and the molar fraction of NO in the exhaled air is complex. Indeed, BC might lead to an increase or to a decrease of this molar fraction, depending on the extent of the BC and on the possible presence of mucus. This should be confirmed experimentally and might

  8. Electrical transport properties of nanoplates shaped tungsten oxide embedded poly(vinyl-alcohol) film

    Science.gov (United States)

    Das, Amit Kumar; Chatterjee, Piyali; Meikap, Ajit Kumar

    2018-04-01

    Tungsten oxide (WO3) nanoplates have been synthesized via hydrothermal method. The average crystallite size of the nanoplates is 28.9 ± 0.5 nm. The direct and indirect band gap of WO3 is observed. The AC conductivity of PVA-WO3 composite film has been observed and carrier transport mechanism follows correlated barrier hopping model. The maximum barrier height of the composite film is 0.1 eV. The electric modulus reflects the non-Debye type behaviour of relaxation time which is simulated by Kohlrausch-Willims-Watts (KWW) function.

  9. Radio-oxidation of an EPDM elastomer under weak or strong ionising radiations: measurement and modelling of dioxygen consumption

    International Nuclear Information System (INIS)

    Dely, N.

    2005-10-01

    Usually, the irradiation of polymers under ionising radiations occurs in air that is in the presence of oxygen. This leads to a radio oxidation process and to oxygen consumption. Our material is an EPDM elastomer (ethylene propylene 1,4 hexadiene) used as insulator in control-command cables in nuclear plants (Pressurised Water Reactor). A specific device has been conceived and built up during this PhD work for measuring very small oxygen consumptions with an accuracy of around 10%. Ionising radiations used are electrons at 1 MeV and carbon ions at 11 MeV per nucleon. Under both electron and ion irradiations, the influence of oxygen pressure on oxygen consumption has been studied in a very large range: between 1 and 200 mbar. In both cases, the yield of oxygen consumption is constant in-between 200 and 5 mbar. Then, at lower pressures, it decreases appreciably. On the other hand, the oxygen consumption during ion irradiation is four times smaller than during electron irradiation. This emphasizes the role of the heterogeneity of the energy deposition at a nano-metric scale. The adjustment of the experimental results obtained during electron irradiation with the general homogeneous steady-state kinetic model has allowed extracting all the values of the kinetic parameters for the chosen mechanism of radio oxidation. The knowledge of these numbers will allow us to face our results obtained during ion irradiation with a heterogeneous kinetic model under development. (author)

  10. A ketogenic diet increases transport and oxidation of ketone bodies in RG2 and 9L gliomas without affecting tumor growth.

    Science.gov (United States)

    De Feyter, Henk M; Behar, Kevin L; Rao, Jyotsna U; Madden-Hennessey, Kirby; Ip, Kevan L; Hyder, Fahmeed; Drewes, Lester R; Geschwind, Jean-François; de Graaf, Robin A; Rothman, Douglas L

    2016-08-01

    The dependence of tumor cells, particularly those originating in the brain, on glucose is the target of the ketogenic diet, which creates a plasma nutrient profile similar to fasting: increased levels of ketone bodies and reduced plasma glucose concentrations. The use of ketogenic diets has been of particular interest for therapy in brain tumors, which reportedly lack the ability to oxidize ketone bodies and therefore would be starved during ketosis. Because studies assessing the tumors' ability to oxidize ketone bodies are lacking, we investigated in vivo the extent of ketone body oxidation in 2 rodent glioma models. Ketone body oxidation was studied using (13)C MR spectroscopy in combination with infusion of a (13)C-labeled ketone body (beta-hydroxybutyrate) in RG2 and 9L glioma models. The level of ketone body oxidation was compared with nontumorous cortical brain tissue. The level of (13)C-beta-hydroxybutyrate oxidation in 2 rat glioma models was similar to that of contralateral brain. In addition, when glioma-bearing animals were fed a ketogenic diet, the ketone body monocarboxylate transporter was upregulated, facilitating uptake and oxidation of ketone bodies in the gliomas. These results demonstrate that rat gliomas can oxidize ketone bodies and indicate upregulation of ketone body transport when fed a ketogenic diet. Our findings contradict the hypothesis that brain tumors are metabolically inflexible and show the need for additional research on the use of ketogenic diets as therapy targeting brain tumor metabolism. © The Author(s) 2016. Published by Oxford University Press on behalf of the Society for Neuro-Oncology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  11. Advective and diffusive contributions to reactive gas transport during pyrite oxidation in the unsaturated zone

    DEFF Research Database (Denmark)

    Binning, Philip John; Postma, Diederik Jan; Russel, T.F.

    2007-01-01

    Pyrite oxidation in unsaturated mine waste rock dumps and soils is limited by the supply of oxygen from the atmosphere. In models, oxygen transport through the subsurface is often assumed to be driven by diffusion. However, oxygen comprises 23.2% by mass of dry air, and when oxygen is consumed at...... parameters; for example, the time to approach steady state depends exponentially on the distance between the soil surface and the subsurface reactive zone. Copyright 2007 by the American Geophysical Union....... at depth in the unsaturated zone, a pressure gradient is created between the reactive zone and the ground surface, causing a substantial advective air flow into the subsurface. To determine the balance between advective and diffusive transport, a one-dimensional multicomponent unsaturated zone gas...

  12. Improved electron transport layer

    DEFF Research Database (Denmark)

    2012-01-01

    The present invention provides: a method of preparing a coating ink for forming a zinc oxide electron transport layer, comprising mixing zinc acetate and a wetting agent in water or methanol; a coating ink comprising zinc acetate and a wetting agent in aqueous solution or methanolic solution......; a method of preparing a zinc oxide electron transporting layer, which method comprises: i) coating a substrate with the coating ink of the present invention to form a film; ii) drying the film; and iii) heating the dry film to convert the zinc acetate substantially to ZnO; a method of preparing an organic...... photovoltaic device or an organic LED having a zinc oxide electron transport layer, the method comprising, in this order: a) providing a substrate bearing a first electrode layer; b) forming an electron transport layer according to the following method: i) coating a coating ink comprising an ink according...

  13. GENERATION, TRANSPORT AND DEPOSITION OF TUNGSTEN-OXIDE AEROSOLS AT 1000 C IN FLOWING AIR-STEAM MIXTURES.

    Energy Technology Data Exchange (ETDEWEB)

    GREENE,G.A.; FINFROCK,C.C.

    2001-10-01

    Experiments were conducted to measure the rates of oxidation and vaporization of pure tungsten rods in flowing air, steam and air-steam mixtures in laminar flow. Also measured were the downstream transport of tungsten-oxide condensation aerosols and their region of deposition, including plateout in the superheated flow tube, rainout in the condenser and ambient discharge which was collected on an array of sub-micron aerosol filters. The nominal conditions of the tests, with the exception of the first two tests, were tungsten temperatures of 1000 C, gas mixture temperatures of 200 C and wall temperatures of 150 C to 200 C. It was observed that the tungsten oxidation rates were greatest in all air and least in all steam, generally decreasing non-linearly with increasing steam mole fraction. The tungsten oxidation rates in all air were more than five times greater than the tungsten oxidation rates in all steam. The tungsten vaporization rate was zero in all air and increased with increasing steam mole fraction. The vaporization rate became maximum at a steam mole fraction of 0.85 and decreased thereafter as the steam mole fraction was increased to unity. The tungsten-oxide was transported downstream as condensation aerosols, initially flowing upwards from the tungsten rod through an 18-inch long, one-inch diameter quartz tube, around a 3.5-inch radius, 90{sup o} bend and laterally through a 24-inch horizontal run. The entire length of the quartz glass flow path was heated by electrical resistance clamshell heaters whose temperatures were individually controlled and measured. The tungsten-oxide plateout in the quartz tube was collected, nearly all of which was deposited at the end of the heated zone near the entrance to the condenser which was cold. The tungsten-oxide which rained out in the condenser as the steam condensed was collected with the condensate and weighed after being dried. The aerosol smoke which escaped the condenser was collected on the sub

  14. Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

    Science.gov (United States)

    Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

    2007-01-01

    A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

  15. All-inorganic quantum-dot light-emitting-diodes with vertical nickel oxide nanosheets as hole transport layer

    Directory of Open Access Journals (Sweden)

    Jiahui Li

    2016-10-01

    Full Text Available All-inorganic quantum dot light emitting diodes (QLEDs have gained great attention as a result of their high stability under oxygen-rich, humid and high current working conditions. In this work, we have fabricated an all-inorganic QLED device (FTO/NiO/QDs/AZO/Ag with sandwich-structure, wherein the inorganic metal oxides thin films of NiO and AZO were employed as hole and electron transport layers, respectively. The porous NiO layer with vertical lamellar nanosheets interconnected microstructure have been directly synthesized on the substrate of conductive FTO glass and increased the wettability of CdSe@ZnS QDs, which result in an enhancement of current transport performance of the QLED.

  16. Some organodioxygen complexes of molybdenum(VI), tungsten(VI), zinc(II) and cadmium(II) containing some monodentate and multidentate ligands

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Leo Man Lin; Grouse, Karen A.; Mariotto, Gino

    2003-08-01

    Several novel organodioxygen complexes of the type [M(O)(O 2 ) 2 L](MMo(VI), W(VI)) and [M'(O 2 )L](M'= Cd(II) and Zn(II)) have been synthesized using monodentate, bidentate and tridentate ligands, L pyridine, picolinic acid, diethylenetriamine, 1,2-phenylenediamine, triphenylphosphine oxide. These complexes were characterized by elemental analyses, conductivity measurements, infrared, Raman spectral studies. For dioxygen complexes, the v(O=O) stretches of the superoxo moities were only Raman active, because of apparent linearity of the M-O 2 moieties, giving peaks at 1020-1030 cm -1 . The complexes were all thermodynamically stable. The dioxygen complexes containing bidentate co-ligands were found to show oxygen transfer reactions to various organic and inorganic substrates. Mechanisms have been postulated. (author)

  17. Antioxidant Deactivation on Graphenic Nanocarbon Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xinyuan [ORNL; Sen, Sujat [Brown University; Liu, Jingyu [Brown University; Kulaots, Indrek [Brown University; Geohegan, David B [ORNL; Kane, Agnes [Brown University; Puretzky, Alexander A [ORNL; Rouleau, Christopher M [ORNL; More, Karren Leslie [ORNL; Palmore, G. Tayhas R. [Brown University; Hurt, Robert H. [Brown University

    2011-01-01

    This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. It is proposed that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.

  18. Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2017-01-15

    Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

  19. Development of a pneumatic transport system for bulk transfer of metal grade uranium oxide powder

    International Nuclear Information System (INIS)

    Manna, S.; Satpati, S.K.; Roy, S.B.

    2010-01-01

    Uranium oxide powder is a commonly handled ceramic powder in nuclear industries. Design of the powder transfer system is an important aspect because of some of its typical characteristics. Pneumatic transport system has been widely used in transferring powder from one place to another. A pneumatic transport system using vacuum has been presented in the paper. This is used for bulk transfer of UO 3 powder. The system consists of a cyclone separator and filter cloth at the top of the cyclone separator. The pneumatic transfer system provides high efficiency with sustainable performance and it is a compact, robust, handy and moveable unit. No degradation of the powder quality has been observed during transfer. The system provides highly efficient, easy and safe transfer of radioactive powder, better working environment for the operator. (author)

  20. Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst

    DEFF Research Database (Denmark)

    Nielsen, Inger Staunstrup; Taarning, Esben; Egeblad, Kresten

    2007-01-01

    Methyl esters can be produced in high yield by oxidising methanolic solutions of primary alcohols with dioxygen over a heterogeneous gold catalyst. The versatility of this new methodology is demonstrated by the fact that alkylic, benzylic and allylic alcohols, as well as alcohols containing...

  1. Physical transformations of iron oxide and silver nanoparticles from an intermediate scale field transport study

    Science.gov (United States)

    Emerson, Hilary P.; Hart, Ashley E.; Baldwin, Jonathon A.; Waterhouse, Tyler C.; Kitchens, Christopher L.; Mefford, O. Thompson; Powell, Brian A.

    2014-02-01

    In recent years, there has been increasing concern regarding the fate and transport of engineered nanoparticles (NPs) in environmental systems and the potential impacts on human and environmental health due to the exponential increase in commercial and industrial use worldwide. To date, there have been relatively few field-scale studies or laboratory-based studies on environmentally relevant soils examining the chemical/physical behavior of the NPs following release into natural systems. The objective of this research is to demonstrate the behavior and transformations of iron oxide and silver NPs with different capping ligands within the unsaturated zone. Here, we show that NP transport within the vadose zone is minimal primarily due to heteroaggregation with soil surface coatings with results that >99 % of the NPs remained within 5 cm of the original source after 1 year in intermediate-scale field lysimeters. These results suggest that transport may be overestimated when compared to previous laboratory-scale studies on pristine soils and pure minerals and that future work must incorporate more environmentally relevant parameters.

  2. Development and mapping of gene-tagged SNP markers in laccases of maize (Zea mays L.)

    DEFF Research Database (Denmark)

    Andersen, J R; Asp, T; Lu, Y C

    2009-01-01

    Laccases, EC 1.10.3.2 or p-diphenol : dioxygen oxidoreductases, have been proposed to be involved in the oxidative polymerization of monolignols into lignins in plants. While 17 laccases have been identified in Arabidopsis, only five (ZmLac1-5) have so far been identified in maize. By a bioinform...

  3. Staged membrane oxidation reactor system

    Science.gov (United States)

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2012-09-11

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  4. Photoconductivity of oxidized nanostructured PbTe(In) films

    International Nuclear Information System (INIS)

    Dobrovolsky, A A; Ryabova, L I; Khokhlov, D R; Dashevsky, Z M; Kasiyan, V A

    2009-01-01

    Photoconductivity of as-grown and oxidized nanocrystalline PbTe(In) films has been studied in the dc and ac modes at temperatures 4.2–300 K. The electric transport in the films is defined by two mechanisms: conductivity through barriers at grain boundaries and transport along inversion channels at the grain surface. Modification of the transport mechanisms induced by oxidation is considered. Relatively weak oxidation results in an increase in the contribution of grain barriers to conductivity followed by an enhancement of the photoconductivity amplitude. Instead, this contribution drops in the case of deep oxidation resulting in a photoresponse reduction. It is shown that the main mechanism of charge transport in deeply oxidized films at low temperatures is hopping along inversion channels at the grain surface. It is demonstrated that the photoconductive response of nanocrystalline materials may be optimized by variation of the oxidation level, measurement frequency and temperature

  5. Electron transport within transparent assemblies of tin-doped indium oxide colloidal nanocrystals

    Science.gov (United States)

    Grisolia, J.; Decorde, N.; Gauvin, M.; Sangeetha, N. M.; Viallet, B.; Ressier, L.

    2015-08-01

    Stripe-like compact assemblies of tin-doped indium oxide (ITO) colloidal nanocrystals (NCs) are fabricated by stop-and-go convective self-assembly (CSA). Systematic evaluation of the electron transport mechanisms in these systems is carried out by varying the length of carboxylate ligands protecting the NCs: butanoate (C4), octanoate (C8) and oleate (C18). The interparticle edge-to-edge distance L0, along with a number of carbon atoms in the alkyl chain of the coating ligand, are deduced from small-angle x-ray scattering (SAXS) measurements and exhibit a linear relationship with a slope of 0.11 nm per carbon pair unit. Temperature-dependent resistance characteristics are analyzed using several electron transport models: Efros-Shklovskii variable range hopping (ES-VRH), inelastic cotunneling (IC), regular island array and percolation. The analysis indicated that the first two models (ES-VRH and IC) fail to explain the observed behavior, and that only simple activated transport takes place in these systems under the experimental conditions studied (T = 300 K to 77 K). Related transport parameters were then extracted using the regular island array and percolation models. The effective tunneling decay constant βeff of the ligands and the Coulomb charging energy EC are found to be around 5.5 nm-1 and 25 meV, respectively, irrespective of ligand lengths. The theoretical tunneling decay constant β calculated using the percolation model is in the range 9 nm-1. Electromechanical tests on the ITO nanoparticle assemblies indicate that their sensitivities are as high as ˜30 and remain the same regardless of ligand lengths, which is in agreement with the constant effective βeff extracted from regular island array and percolation models.

  6. Improvement of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-oxide-modified titania layer and soluble copper phthalocyanine as a hole transporter.

    Science.gov (United States)

    Nouri, Esmaiel; Mohammadi, Mohammad Reza; Xu, Zong-Xiang; Dracopoulos, Vassilios; Lianos, Panagiotis

    2018-01-24

    Functional perovskite solar cells can be made by using a simple, inexpensive and stable soluble tetra-n-butyl-substituted copper phthalocyanine (CuBuPc) as a hole transporter. In the present study, TiO 2 /reduced graphene oxide (T/RGO) hybrids were synthesized via an in situ solvothermal process and used as electron acceptor/transport mediators in mesoscopic perovskite solar cells based on soluble CuBuPc as a hole transporter and on graphene oxide (GO) as a buffer layer. The impact of the RGO content on the optoelectronic properties of T/RGO hybrids and on the solar cell performance was studied, suggesting improved electron transport characteristics and photovoltaic parameters. An enhanced electron lifetime and recombination resistance led to an increase in the short circuit current density, open circuit voltage and fill factor. The device based on a T/RGO mesoporous layer with an optimal RGO content of 0.2 wt% showed 22% higher photoconversion efficiency and higher stability compared with pristine TiO 2 -based devices.

  7. A microdot multilayer oxide device: let us tune the strain-ionic transport interaction.

    Science.gov (United States)

    Schweiger, Sebastian; Kubicek, Markus; Messerschmitt, Felix; Murer, Christoph; Rupp, Jennifer L M

    2014-05-27

    In this paper, we present a strategy to use interfacial strain in multilayer heterostructures to tune their resistive response and ionic transport as active component in an oxide-based multilayer microdot device on chip. For this, fabrication of strained multilayer microdot devices with sideways attached electrodes is reported with the material system Gd0.1Ce0.9O(2-δ)/Er2O3. The fast ionic conducting Gd0.1Ce0.9O(2-δ) single layers are altered in lattice strain by the electrically insulating erbia phases of a microdot. The strain activated volume of the Gd0.1Ce0.9O(2-δ) is investigated by changing the number of individual layers from 1 to 60 while keeping the microdot at a constant thickness; i.e., the proportion of strained volume was systematically varied. Electrical measurements showed that the activation energy of the devices could be altered by Δ0.31 eV by changing the compressive strain of a microdot ceria-based phase by more than 1.16%. The electrical conductivity data is analyzed and interpreted with a strain volume model and defect thermodynamics. Additionally, an equivalent circuit model is presented for sideways contacted multilayer microdots. We give a proof-of-concept for microdot contacting to capture real strain-ionic transport effects and reveal that for classic top-electrode contacting the effect is nil, highlighting the need for sideways electric contacting on a nanoscopic scale. The near order ionic transport interaction is supported by Raman spectroscopy measurements. These were conducted and analyzed together with fully relaxed single thin film samples. Strain states are described relative to the strain activated volumes of Gd0.1Ce0.9O(2-δ) in the microdot multilayer. These findings reveal that strain engineering in microfabricated devices allows altering the ionic conduction over a wide range beyond classic doping strategies for single films. The reported fabrication route and concept of strained multilayer microdots is a promising path

  8. Influence of pH on the transport of nanoscale zinc oxide in saturated porous media

    Energy Technology Data Exchange (ETDEWEB)

    Kanel, Sushil R. [Pegasus Technical Services, Inc. (United States); Al-Abed, Souhail R., E-mail: al-abed.souhail@epa.gov [National Risk Management Research Laboratory, U.S. Environmental Protection Agency (United States)

    2011-09-15

    Widespread use of nanoscale zinc oxide (nZnO) in various fields causes subsurface environment contamination. Even though the transport of dissolved zinc ions in subsurface environments such as soils and sediments has been widely studied, the transport mechanism of nZnO in such environments is poorly understood. In addition, nZnO is often combined with stabilizers or dispersing agents to prevent its aggregation in products. The purpose of this study is to determine the influence of pH on the transport properties of pristine nZnO and carboxymethyl cellulose (CMC) stabilized nZnO (CMC-nZnO) suspensions in silica sand packed column under saturated flow conditions. Transport data were collected at different pHs (pHs: 3, 7, 9, and 11) under 1 mL/min flow rate conditions in a 1.1 cm diameter column. It is found that the transport trends of pristine nZnO and CMC-nZnO were different. For pristine nZnO, mobility of total Zn reached a minimum around its point of zero charge (pH 8.9). Whereas in the case of CMC-nZnO, the mobility of total Zn decreased as the pH of the solution pH increased from 3 to 11. ZnO and Zn ion mixture were separated using diafiltration membrane. It showed that most of the nZnO and CMC-nZnO exists as Zn ion at pH 3 before and after eluting from the sand packed column whereas at pH 11, they exist as particles. This study shows the strong influence of pH and stabilizing agents on nZnO transport. These factors should be considered during subsurface transport of nZnO.

  9. Influence of pH on the transport of nanoscale zinc oxide in saturated porous media

    International Nuclear Information System (INIS)

    Kanel, Sushil R.; Al-Abed, Souhail R.

    2011-01-01

    Widespread use of nanoscale zinc oxide (nZnO) in various fields causes subsurface environment contamination. Even though the transport of dissolved zinc ions in subsurface environments such as soils and sediments has been widely studied, the transport mechanism of nZnO in such environments is poorly understood. In addition, nZnO is often combined with stabilizers or dispersing agents to prevent its aggregation in products. The purpose of this study is to determine the influence of pH on the transport properties of pristine nZnO and carboxymethyl cellulose (CMC) stabilized nZnO (CMC–nZnO) suspensions in silica sand packed column under saturated flow conditions. Transport data were collected at different pHs (pHs: 3, 7, 9, and 11) under 1 mL/min flow rate conditions in a 1.1 cm diameter column. It is found that the transport trends of pristine nZnO and CMC–nZnO were different. For pristine nZnO, mobility of total Zn reached a minimum around its point of zero charge (pH 8.9). Whereas in the case of CMC–nZnO, the mobility of total Zn decreased as the pH of the solution pH increased from 3 to 11. ZnO and Zn ion mixture were separated using diafiltration membrane. It showed that most of the nZnO and CMC–nZnO exists as Zn ion at pH 3 before and after eluting from the sand packed column whereas at pH 11, they exist as particles. This study shows the strong influence of pH and stabilizing agents on nZnO transport. These factors should be considered during subsurface transport of nZnO.

  10. Modeling and sensitivity analysis on the transport of aluminum oxide nanoparticles in saturated sand: effects of ionic strength, flow rate, and nanoparticle concentration.

    Science.gov (United States)

    Rahman, Tanzina; Millwater, Harry; Shipley, Heather J

    2014-11-15

    Aluminum oxide nanoparticles have been widely used in various consumer products and there are growing concerns regarding their exposure in the environment. This study deals with the modeling, sensitivity analysis and uncertainty quantification of one-dimensional transport of nano-sized (~82 nm) aluminum oxide particles in saturated sand. The transport of aluminum oxide nanoparticles was modeled using a two-kinetic-site model with a blocking function. The modeling was done at different ionic strengths, flow rates, and nanoparticle concentrations. The two sites representing fast and slow attachments along with a blocking term yielded good agreement with the experimental results from the column studies of aluminum oxide nanoparticles. The same model was used to simulate breakthrough curves under different conditions using experimental data and calculated 95% confidence bounds of the generated breakthroughs. The sensitivity analysis results showed that slow attachment was the most sensitive parameter for high influent concentrations (e.g. 150 mg/L Al2O3) and the maximum solid phase retention capacity (related to blocking function) was the most sensitive parameter for low concentrations (e.g. 50 mg/L Al2O3). Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Transport and reprocessing of irradiated nuclear fuel

    International Nuclear Information System (INIS)

    Lenail, B.

    1981-01-01

    This contribution deals with transport and packaging of oxide fuel from and to the Cogema reprocessing plant at La Hague (France). After a general discussion of nuclear fuel and the fuel cycle, the main aspects of transport and reprocessing of oxide fuel are analysed. (Auth.)

  12. Oxidative alteration of uraninite at the Nopal I deposit, Mexico: Possible contaminant transport and source term constraints for the proposed repository at Yucca Mountain

    International Nuclear Information System (INIS)

    Leslie, B.W.; Pearcy, E.C.; Prikryl, J.D.

    1993-01-01

    The Nopal I uranium deposit at Pena Blanca, Mexico is being studied as a natural analog of the proposed high-level nuclear waste repository at Yucca Mountain. Identification of secondary uranium phases at Nopal I, and the sequence of their formation after uraninite oxidation, provides insight into the source term for uranium, and suggests that uranophane may control uranium release and transport in a silici, tuffaceous, chemically oxidizing, and hydrologically unsaturated environment. Possible constraints on contaminant transport at Nopal I are derived from the spatial distribution of uranium and from measurements of 238 U decay-series isotopes. The analyses indicate that flow of U-bearing fluids was influenced strongly by fracture density, but that the flow of these fluids was not restricted to fractures. Gamma spectroscopic measurements of 238 U decay-series isotopes indicates secular equilibrium, which suggests undetectable U transport under present conditions

  13. United Kingdom experience in plutonium transportation

    International Nuclear Information System (INIS)

    1978-11-01

    This paper describes the extensive experience of the UKAEA and British Nuclear Fuels Limited in transporting plutonium within the UK over the last 20 years and to destinations overseas since the early 1960s. The aspects covered include: the form of plutonium transported (nitrate, oxide, mixed oxide etc.); UK and international regulations (e.g. covering safety and safeguards matters); insurance; container design; mode of transport; physical protection; and a safety analysis. Costs are estimated to be largely independent of quantity

  14. Kinetic modeling of antimony(III) oxidation and sorption in soils.

    Science.gov (United States)

    Cai, Yongbing; Mi, Yuting; Zhang, Hua

    2016-10-05

    Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Biomimetic Catalysts for Oxidation of Veratryl Alcohol, a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Marcelino Maneiro

    2013-03-01

    Full Text Available Kraft pulp has to be bleached to eliminate the chromophoric structures, which cause a darkening of the pulp. In Nature, an equivalent role is assumed by ligninolytic enzymes such as lignin peroxidases, manganese peroxidases and laccases. The development of low molecular weight manganese peroxidase mimics may achieve environmentally-safe bleaching catalysts for the industry. Herein we report the synthesis and characterization of six manganese(III complexes 1–6, incorporating dianionic hexadentate Schiff base ligands (H2L1-H2L4 and different anions. Complex 4, Mn2L22(H2O2(DCA2 was crystallographically characterized. Complexes 1–4 behave as more efficient mimics of peroxidase in contrast to 5–6. We have studied the use of these complexes as catalysts for the degradation of the lignin model compound veratryl alcohol. The biomimetic catalysts were used in conjunction with chlorine-free inexpensive co-oxidants as dioxygen or hydrogen peroxide. Yields up to 30% of veratryl alcohol conversion to veratraldehyde have been achieved at room temperature in presence of air flow using 0.5% of catalyst.

  16. Inhibition of cellulase-catalyzed lignocellulosic hydrolysis by iron and oxidative metal ions and complexes.

    Science.gov (United States)

    Tejirian, Ani; Xu, Feng

    2010-12-01

    Enzymatic lignocellulose hydrolysis plays a key role in microbially driven carbon cycling and energy conversion and holds promise for bio-based energy and chemical industries. Cellulases (key lignocellulose-active enzymes) are prone to interference from various noncellulosic substances (e.g., metal ions). During natural cellulolysis, these substances may arise from other microbial activities or abiotic events, and during industrial cellulolysis, they may be derived from biomass feedstocks or upstream treatments. Knowledge about cellulolysis-inhibiting reactions is of importance for the microbiology of natural biomass degradation and the development of biomass conversion technology. Different metal ions, including those native to microbial activity or employed for biomass pretreatments, are often tested for enzymatic cellulolysis. Only a few metal ions act as inhibitors of cellulases, which include ferrous and ferric ions as well as cupric ion. In this study, we showed inhibition by ferrous/ferric ions as part of a more general effect from oxidative (or redox-active) metal ions and their complexes. The correlation between inhibition and oxidation potential indicated the oxidative nature of the inhibition, and the dependence on air established the catalytic role that iron ions played in mediating the dioxygen inhibition of cellulolysis. Individual cellulases showed different susceptibilities to inhibition. It is likely that the inhibition exerted its effect more on cellulose than on cellulase. Strong iron ion chelators and polyethylene glycols could mitigate the inhibition. Potential microbiological and industrial implications of the observed effect of redox-active metal ions on enzymatic cellulolysis, as well as the prevention and mitigation of this effect in industrial biomass conversion, are discussed.

  17. The use of the average plutonium-content for criticality evaluation of boiling water reactor mixed oxide-fuel transport and storage packages

    International Nuclear Information System (INIS)

    Mattera, C.

    2003-01-01

    Currently in France, criticality studies in transport configurations for Boiling Water Reactor Mixed Oxide fuel assemblies are based on conservative hypothesis assuming that all rods (Mixed Oxide (Uranium and Plutonium), Uranium Oxide, Uranium and (Gadolinium Oxide rods) are Mixed Oxide rods with the same Plutonium-content, corresponding to the maximum value. In that way, the real heterogeneous mapping of the assembly is masked and covered by an homogenous Plutonium-content assembly, enriched at the maximum value. As this calculation hypothesis is extremely conservative, Cogema Logistics (formerly Transnucleaire) has studied a new calculation method based on the use of the average Plutonium-content in the criticality studies. The use of the average Plutonium-content instead of the real Plutonium-content profiles provides a highest reactivity value that makes it globally conservative. This method can be applied for all Boiling Water Reactor Mixed Oxide complete fuel assemblies of type 8 x 8, 9 x 9 and 10 x 10 which Plutonium-content in mass weight does not exceed 15%; it provides advantages which are discussed in the paper. (author)

  18. Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

    Science.gov (United States)

    Zhang, Chun; Feng, Peng; Jiao, Ning

    2013-10-09

    The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

  19. Radio-Oxidation in Polyolefins: Non-Stationary Kinetic Conditions

    International Nuclear Information System (INIS)

    Dely, N.

    2006-01-01

    In the last fifty years, many authors have been interested in the radio-oxidation processes occurring in polymers. The polymer degradation under ionising radiations in presence of dioxygen is well described by a radical chemistry. The radio-oxidation process occurs in three steps: the first one is the production of radicals P degree by interaction between the polymer and the ionising radiations; then radicals P degree react spontaneously with O 2 solved in the polymer giving a peroxy radical POO degree which attacks the polymer forming a hydroperoxide POOH and a new radical P degree (propagation). The third step corresponds to the termination step, that is bimolecular reactions between radicals. It is generally assumed that the stationary state is rapidly reached and consequently that the oxidation induced during the built-up period of the radical concentration can be neglected. However, to our best knowledge, the temporal evolution of radical concentrations before reaching the steady state regime has never been studied in details. We recently performed a complete study of oxygen consumption under electron irradiation for an EPDM elastomer. An analysis, as function of dose rate and oxygen pressure, and assuming steady state conditions, allowed extracting all the kinetic constants. Starting for these experimental data, we calculated the build-up of the radical concentration by solving numerically the differential equations with help of the Minichem code. We conclude that, in fact, the oxidation induced during the built-up period is negligible. In this paper we show that [P degree] could present a quasi-stationary plateau before reaching its stationary level. Consequently, the full radical time evolution is essentially determined by two characteristic times for reaching the quasi and stationary levels and three concentrations: [P degree] and [POO degree] at the stationary level and [P degree] at the quasi-stationary plateau. We show that realistic approximations can

  20. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  1. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  2. Electrochemistry of hydrous oxide films

    International Nuclear Information System (INIS)

    Burke, L.D.; Lyons, M.E.G.

    1986-01-01

    The formation, acid-base properties, structural aspects, and transport processes of hydrous oxide films are discussed. Classical and nonclassical theoretical models of the oxide-solution interface are compared. Monolayer oxidation, behavior, and crystal growth of oxides on platinum, palladium, gold, iridium, rhodium, ruthenium, and some non-noble metals, including tungsten, are reviewed and compared

  3. Spectrophotometric investigation on the kinetics of oxidation of adrenaline by dioxygen of μ-dioxytetrakis(histidinato)-dicobalt(II) complex

    Science.gov (United States)

    Rafiquee, M. Z. A.; Siddiqui, Masoom R.; Ali, Mohd. Sajid; Al-Lohedan, Hamad A.

    The cobalt(II)histidine complex binds molecular oxygen reversibly to form an oxygen adduct complex, μ-dioxytetrakis-(histidinato)dicobalt(II). The molecular oxygen can be released from the oxygenated complex by heating it or by passing N2, He or Ar gas through its solution. μ-Dioxytetrakis-(histidinato)dicobalt(II) complex oxidizes adrenaline into leucoadrenochrome at 25 °C while at higher temperature (>40 °C) adrenochrome with λmax at 490 nm is formed. The rate of formation of leucoadrenochrome was found to be independent of [bis(histidinato)cobalt(II)]. The rate of reaction for the formation of leucoadrenochrome and adrenochrome increased with the increase in [adrenaline] at its lower concentration but become independent at higher concentration. Similarly, the rate of formation of both leucoadrenochrome and adrenochrome was linearly dependent upon [NaOH]. The values of activation parameters i.e. ΔEa, ΔH‡ and ΔS‡ for the formation of leucoadrenochrome are reported.

  4. Magneto-transport properties of oriented Mn{sub 2}CoAl films sputtered on thermally oxidized Si substrates

    Energy Technology Data Exchange (ETDEWEB)

    Xu, G. Z.; Du, Y.; Zhang, X. M.; Liu, E. K.; Wang, W. H., E-mail: wenhong.wang@iphy.ac.cn; Wu, G. H. [State Key Laboratory for Magnetism, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190 (China); Zhang, H. G. [College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124 (China)

    2014-06-16

    Spin gapless semiconductors are interesting family of materials by embracing both magnetism and semiconducting due to their unique band structure. Its potential application in future spintronics requires realization in thin film form. In this Letter, we report fabrication and transport properties of spin gapless Mn{sub 2}CoAl films prepared on thermally oxidized Si substrates by magnetron sputtering deposition. The films deposited at 673 K are well oriented to (001) direction and display a uniform-crystalline surface. Magnetotransport measurements on the oriented films reveal a semiconducting-like resistivity, small anomalous Hall conductivity, and linear magnetoresistance representative of the transport signatures of spin gapless semiconductors. The magnetic properties of the films have also been investigated and compared to that of bulk Mn{sub 2}CoAl, showing small discrepancy induced by the composition deviation.

  5. Cellular Oxygen Sensing: Crystal Structure of Hypoxia-Inducible Factor Prolyl Hydroxylase (PHD2)

    Energy Technology Data Exchange (ETDEWEB)

    McDonough,M.; Li, V.; Flashman, E.; Chowdhury, R.; Mohr, C.; Lienard, B.; Zondlo, J.; Oldham, N.; Clifton, I.; et al.

    2006-01-01

    Cellular and physiological responses to changes in dioxygen levels in metazoans are mediated via the posttranslational oxidation of hypoxia-inducible transcription factor (HIF). Hydroxylation of conserved prolyl residues in the HIF-{alpha} subunit, catalyzed by HIF prolyl-hydroxylases (PHDs), signals for its proteasomal degradation. The requirement of the PHDs for dioxygen links changes in dioxygen levels with the transcriptional regulation of the gene array that enables the cellular response to chronic hypoxia; the PHDs thus act as an oxygen-sensing component of the HIF system, and their inhibition mimics the hypoxic response. We describe crystal structures of the catalytic domain of human PHD2, an important prolyl-4-hydroxylase in the human hypoxic response in normal cells, in complex with Fe(II) and an inhibitor to 1.7 Angstroms resolution. PHD2 crystallizes as a homotrimer and contains a double-stranded {beta}-helix core fold common to the Fe(II) and 2-oxoglutarate-dependant dioxygenase family, the residues of which are well conserved in the three human PHD enzymes (PHD 1-3). The structure provides insights into the hypoxic response, helps to rationalize a clinically observed mutation leading to familial erythrocytosis, and will aid in the design of PHD selective inhibitors for the treatment of anemia and ischemic disease.

  6. Inhibitory effect of Piper betel leaf extracts on copper-mediated LDL oxidation and oxLDL-induced lipid accumulation via inducing reverse cholesterol transport in macrophages.

    Science.gov (United States)

    Ma, Gwo-Chin; Wu, Pei-Fang; Tseng, Hsien-Chun; Chyau, Charng-Cherng; Lu, Hsiu-Chin; Chou, Fen-Pi

    2013-12-15

    Piper betel leaf (PBL) has the biological capabilities of detoxification and can work as an anti-inflammatory agent and an anti-oxidant. In this study, we evaluated the anti-oxidative activity of the extract of Piper betel leaves (PBLs) on the basis of Cu(2+)-mediated oxidation, and its ability to prevent foam cell formation in a model for oxidised low density lipoprotein (oxLDL)-induced lipid accumulation in macrophages. Our data demonstrated that PBLs were able to inhibit LDL oxidation in vitro and are able to reduce the lipid accumulation in macrophages. We showed the underlying mechanisms to be the following: PBLs up-regulated the protein levels of the class A and class B scavenger receptors, the membrane lipid transporter ABCA1, and its upstream regulator Liver X receptor (LXR) in the macrophages exposed to oxLDL. The results suggested that PBLs activated the reverse cholesterol transport mechanism to enhance the metabolism of the oxLDL that could prevent both lipid accumulation and foam cell formation and further minimise the possible damage of vessels caused by the oxLDL. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Transport of oxide spent fuel. Industrial experience of COGEMA

    International Nuclear Information System (INIS)

    Lenail, B.

    1985-01-01

    COGEMA, the world leading Company in the reprocessing industry who is also involved in the transport activity, is ruling all transports of spent fuel to La Hague reprocessing plant. The paper summarizes some aspects of the experience gained in this field (road, rail and sea transports) and describes the standards defined by COGEMA as regards transport casks. These standards are as follows: - casks of dry type, - casks of the maximum size compatible with rail transports, - capability to be unloaded with standardized equipment and following standard procedures. Considering: 1) the extremely large experience of COGEMA for all transport modes and, 2) the fact that all these transports are performed in full compliance with the IAEA recommendations, COGEMA is convinced that its experience could serve to help countries or utilities willing to undertake to establish a transport system within their own country COGEMA is prepared to contribute to this task on terms to be agreed [fr

  8. 49 CFR 172.426 - OXIDIZER label.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false OXIDIZER label. 172.426 Section 172.426... SECURITY PLANS Labeling § 172.426 OXIDIZER label. (a) Except for size and color, the OXIDIZER label must be... OXIDIZER label must be yellow. [Amdt. 172-123, 56 FR 66257, Dec. 20, 1991] ...

  9. Efficient Long-Range Hole Transport Through G-Quadruplexes.

    Science.gov (United States)

    Wu, Jingyuan; Meng, Zhenyu; Lu, Yunpeng; Shao, Fangwei

    2017-10-09

    DNA offers a means of long-range charge transport for biology and electric nanodevices. Here, a series of tetra-stranded G-quadruplexes were assembled within a dendritic DNA architecture to explore oxidative charge transport (hole transport) through the G-quadruplex. Efficient charge transport was achieved over 28 Å upon UV irradiation. Over a longer G-quadruplex bridge, hole transport was escalated to a higher efficiency, which resulted in a higher yield than that of the optimal duplex DNA for charge transport, that is, the adenine tract. Efficient long-range hole transport suggests tetra-stranded G-quadruplexes, instead of an oxidation hotspot, hold better potential as an electron conduit than duplex DNA. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  11. Three-dimensional hole transport in nickel oxide by alloying with MgO or ZnO

    Science.gov (United States)

    Alidoust, Nima; Carter, Emily A.

    2015-11-01

    It has been shown previously that the movement of a hole in nickel oxide is confined to two dimensions, along a single ferromagnetic plane. Such confinement may hamper hole transport when NiO is used as a p-type transparent conductor in various solar energy conversion technologies. Here, we use the small polaron model, along with unrestricted Hartree-Fock and complete active space self-consistent field calculations to show that forming substitutional MxNi1-xO alloys with M = Mg or Zn reduces the barrier for movement of a hole away from the ferromagnetic plane to which it is confined. Such reduction occurs for hole transfer alongside one or two M ions that have been substituted for Ni ions. Furthermore, the Mg and Zn ions do not trap holes on O sites in their vicinity, and NiO's transparency is preserved upon forming the alloys. Thus, forming MxNi1-xO alloys with M = Mg or Zn may enhance NiO's potential as a p-type transparent conducting oxide, by disrupting the two-dimensional confinement of holes in pure NiO.

  12. Numerical simulation of mass and energy transport phenomena in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Arpino, F. [Dipartimento di Meccanica, Strutture, Ambiente e Territorio (DiMSAT), University of Cassino, via Di Biasio 43, Cassino (Italy); Massarotti, N. [Dipertimento per le Tecnologie (DiT), University of Naples ' ' Parthenope' ' , Centro Direzionale, isola C4, 80143 Napoli (Italy)

    2009-12-15

    Solid Oxide Fuel Cells (SOFCs) represent a very promising technology for near future energy conversion thanks to a number of advantages, including the possibility of using different fuels. In this paper, a detailed numerical model, based on a general mathematical description and on a finite element Characteristic based Split (CBS) algorithm code is employed to simulate mass and energy transport phenomena in SOFCs. The model predicts the thermodynamic quantity of interest in the fuel cell. Full details of the numerical solution obtained are presented both in terms of heat and mass transfer in the cell and in terms of electro-chemical reactions that occur in the system considered. The results obtained with the present algorithm is compared with the experimental data available in the literature for validation, showing an excellent agreement. (author)

  13. Perovskite oxide SrTiO3 as an efficient electron transporter for hybrid perovskite solar cells

    KAUST Repository

    Bera, Ashok

    2014-12-11

    In this work, we explored perovskite oxide SrTiO3 (STO) for the first time as the electron-transporting layer in organolead trihalide perovskite solar cells. The steady-state photoluminescence (PL) quenching and transient absorption experiments revealed efficient photoelectron transfer from CH3NH3PbI3-xClx to STO. Perovskite solar cells with meso-STO exhibit an open circuit voltage of 1.01 V, which is 25% higher than the value of 0.81 V achieved in the control device with the conventional meso-TiO2. In addition, an increase of 17% in the fill factor was achieved by tailoring the thickness of the meso-STO layer. We found that the application of STO leads to uniform perovskite layers with large grains and complete surface coverage, leading to a high shunt resistance and improved performance. These findings suggest STO as a competitive candidate as electron transport material in organometal perovskite solar cells.

  14. Perovskite oxide SrTiO3 as an efficient electron transporter for hybrid perovskite solar cells

    KAUST Repository

    Bera, Ashok; Wu, Kewei; Sheikh, Arif D.; Alarousu, Erkki; Mohammed, Omar F.; Wu, Tao

    2014-01-01

    In this work, we explored perovskite oxide SrTiO3 (STO) for the first time as the electron-transporting layer in organolead trihalide perovskite solar cells. The steady-state photoluminescence (PL) quenching and transient absorption experiments revealed efficient photoelectron transfer from CH3NH3PbI3-xClx to STO. Perovskite solar cells with meso-STO exhibit an open circuit voltage of 1.01 V, which is 25% higher than the value of 0.81 V achieved in the control device with the conventional meso-TiO2. In addition, an increase of 17% in the fill factor was achieved by tailoring the thickness of the meso-STO layer. We found that the application of STO leads to uniform perovskite layers with large grains and complete surface coverage, leading to a high shunt resistance and improved performance. These findings suggest STO as a competitive candidate as electron transport material in organometal perovskite solar cells.

  15. Theoretical and spectroscopic investigation of the oxidation and degradation of protocatechuic acid

    International Nuclear Information System (INIS)

    Hatzipanayioti, Despina; Karaliota, Alexandra; Kamariotaki, Mary; Aletras, Vasilios; Petropouleas, Panayiotis

    2006-01-01

    In this work, we report a combined experimental and theoretical study on molecular structure and spectroscopic properties of the most stable conformers of PCA. 1 H, 13 C NMR and 2D COSY NMR, ESR, IR and electronic spectroscopies were coupled with DFT theoretical calculations performed at the B3LYP/6-31G** level. The calculated geometrical parameters for the neutral protocatechuic acid PCA-H 3 , its anions, its oxidized forms and the peroxo-derivative [PCA-H-O 2 ] 2- are in line with the experimental data. The neutral catecholate is the most stable form of PCA-H 3 whilst the dianion [PCA-H] 2- presents higher energy. This anion is (experimentally) stable only under argon, reacting with dioxygen, in the presence of air. The semiquinone [PCA-H-sq(3)] - is very close in energy from [PCA-H-sq(4)] - form and an equilibrium between these two oxidized radical forms might be expected. The energetically advantageous pathway for preparation of the symmetrically delocalized [PCA-sq] 2- is to oxidize the [PCA] 3- . The occurrence of this radical dianion form was justified experimentally by ESR, IR, UV-vis and NMR spectra. The structural calculations for [PCA-H-O 2 ] 2- indicate that C 3 (and to a lesser extent C1) may undergo a nucleophilic attack from the 'co-ordinated' peroxo-group. The conditions for the non-enzymatic degradation of PCA have been established and some new products are observed: ionization of PCA-H 3 , the presence of O 2 and aprotic solvents provide the semiquinone-superoxo adduct which is then degraded to lactones, while in protic solvents, addition of H 2 O 2 and the presence of air, are essential, providing aliphatic degradation products

  16. Heat indicators of oxidative stress, inflammation and metal transport show dependence of cadmium pollution history in the liver of female zebrafish.

    Science.gov (United States)

    Zhu, Qing-Ling; Guo, Sai-Nan; Yuan, Shuang-Shuang; Lv, Zhen-Ming; Zheng, Jia-Lang; Xia, Hu

    2017-10-01

    Environmental stressors such as high temperature and metal exposure may occur sequentially, simultaneously, previously in aquatic ecosystems. However, information about whether responses to high temperature depend on Cd exposure history is still unknown in fish. Zebrafish were exposed to 0 (group 1), 2.5 (group 2) and 5μg/L (group 3) cadmium (Cd) for 10 weeks, and then each group was subjected to Cd-free water maintained at 26°C and 32°C for 7days respectively. 26 indicators were used to compare differences between 26°C and 32°C in the liver of female zebrafish, including 5 biochemical indicators (activity of Cu/Zn-SOD, CAT and iNOS; LPO; MT protein), 8 molecular indicators of oxidative stress (mRNA levels of Nrf2, Cu/Zn-SOD, CAT, HSF1, HSF2, HSP70, MTF-1 and MT), 5 molecular indicators of inflammation (mRNA levels of IL-6, IL-1β, TNF-α, iNOS and NF-κB), 8 molecular indicators of metal transport (mRNA levels of, ZnT1, ZnT5, ZIP8, ZIP10, ATP7A, ATP7B and CTR1). All biochemical indicators were unchanged in group 1 and changed in group 2 and 3. Contrarily, differences were observed in almost all of molecular indicators of inflammation and metal transport in group 1, about half in group 2, and few in group 3. We also found that all molecular indicators of oxidative stress in group 2 and fewer in group 1 and 3 were significantly affected by heat. Our data indicated that heat indicators of oxidative stress, inflammation and metal transport showed dependence of previous cadmium exposure in the liver of zebrafish, emphasizing metal pollution history should be carefully considered when evaluating heat stress in fish. Copyright © 2017. Published by Elsevier B.V.

  17. Transport of oxide spent fuel. Industrial experience of COGEMA

    International Nuclear Information System (INIS)

    Lenail, B.

    1983-01-01

    COGEMA is ruling all transports of spent fuel to La Hague reprocessing plant. The paper summarizes some aspects of the experience gained in this field (road, rail and sea transports) and describes the standards defined by COGEMA as regards transport casks. These standards are as follows: - casks of dry type, - casks of the maximum size compatible with rail transports, - capability to be unloaded with standardized equipment and following standard procedures

  18. Electrocatalysis of chemically synthesized noble metal nanoparticles on carbon electrodes

    DEFF Research Database (Denmark)

    Zhang, Ling; Ulstrup, Jens; Zhang, Jingdong

    Noble metal nanoparticles (NPs), such as platinum (Pt) and palladium (Pd) NPs are promising catalysts for dioxygen reduction and oxidation of molecules such as formic acid and ethanol in fuel cells. Carbon nanomaterials are ideal supporting materials for electrochemical catalysts due to their good...... by electrochemical SPM. This study offers promise for development of new high-efficiency catalyst types with low-cost for fuel cell technology...

  19. Review on modeling development for multiscale chemical reactions coupled transport phenomena in solid oxide fuel cells

    International Nuclear Information System (INIS)

    Andersson, Martin; Yuan, Jinliang; Sunden, Bengt

    2010-01-01

    A literature study is performed to compile the state-of-the-art, as well as future potential, in SOFC modeling. Principles behind various transport processes such as mass, heat, momentum and charge as well as for electrochemical and internal reforming reactions are described. A deeper investigation is made to find out potentials and challenges using a multiscale approach to model solid oxide fuel cells (SOFCs) and combine the accuracy at microscale with the calculation speed at macroscale to design SOFCs, based on a clear understanding of transport phenomena, chemical reactions and functional requirements. Suitable methods are studied to model SOFCs covering various length scales. Coupling methods between different approaches and length scales by multiscale models are outlined. Multiscale modeling increases the understanding for detailed transport phenomena, and can be used to make a correct decision on the specific design and control of operating conditions. It is expected that the development and production costs will be decreased and the energy efficiency be increased (reducing running cost) as the understanding of complex physical phenomena increases. It is concluded that the connection between numerical modeling and experiments is too rare and also that material parameters in most cases are valid only for standard materials and not for the actual SOFC component microstructures.

  20. Ambipolar transport of silver nanoparticles decorated graphene oxide field effect transistors

    Science.gov (United States)

    Sarkar, Kalyan Jyoti; Sarkar, K.; Pal, B.; Kumar, Aparabal; Das, Anish; Banerji, P.

    2018-05-01

    In this article, we report ambipolar field effect transistor (FET) by using graphene oxide (GO) as a gate dielectric material for silver nanoparticles (AgNPs) decorated GO channel layer. GO was synthesized by Hummers' method. The AgNPs were prepared via photochemical reduction of silver nitrate solution by using monoethanolamine as a reducing agent. Morphological properties of channel layer were characterized by Field Effect Scanning Electron Microscopy (FESEM). Fourier Transform Infrared Spectroscopy (FTIR) was carried out to characterize GO thin film. For device fabrication gold (Au) was deposited as source-drain contact and aluminum (Al) was taken as bottom contact. Electrical measurements were performed by back gate configuration. Ambipolar transport behavior was explained from transfer characteristics. A maximum electron mobiliy of 6.65 cm2/Vs and a hole mobility of 2.46 cm2/Vs were extracted from the transfer characteristics. These results suggest that GO is a potential candidate as a gate dielectric material for thin film transistor applications and also provides new insights in GO based research.

  1. Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

    DEFF Research Database (Denmark)

    Dale, A.W.; Regnier, P.; Knab, N.J.

    2008-01-01

    A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction...... methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ...

  2. An alternative pathway for production of acetonitrile: ruthenium catalysed aerobic dehydrogenation of ethylamine

    DEFF Research Database (Denmark)

    Corker, Emily; Mentzel, Uffe Vie; Mielby, Jerrik Jørgen

    2013-01-01

    The oxidative synthesis of acetonitrile from ethylamine was studied using a supported ruthenium catalyst. The reaction was conducted in both batch and flow processes and high conversions (over 85%) were achieved in both cases. Selectivity of both reactions was improved by optimisation of reaction...... conditions, achieving over 90% selectivity in the batch process and 80% selectivity in the continuous flow process. The use of a selective solid catalyst that utilises a feedstock that can be derived from biomass, dioxygen as the oxidant and water as the solvent represents a new, green route...

  3. Proteomics Analysis Reveals Abnormal Electron Transport and Excessive Oxidative Stress Cause Mitochondrial Dysfunction in Placental Tissues of Early-Onset Preeclampsia.

    Science.gov (United States)

    Xu, Zhongwei; Jin, Xiaohan; Cai, Wei; Zhou, Maobin; Shao, Ping; Yang, Zhen; Fu, Rong; Cao, Jin; Liu, Yan; Yu, Fang; Fan, Rong; Zhang, Yan; Zou, Shuang; Zhou, Xin; Yang, Ning; Chen, Xu; Li, Yuming

    2018-04-20

    Early-onset preeclampsia (EOS-PE) refers to preeclampsia that occurred before 34 gestation weeks. This study was conducted to explore the relationship between mitochondrial dysfunction and the pathogenesis of EOS-PE using proteomic strategy. To identify altering expressed mitochondrial proteins between severe EOS-PE and healthy pregnancies, enrichment of mitochondria coupled with iTRAQ-based quantitative proteomic method was performed. IHC and western blot were performed to detect the alteration of changing expression proteins, and confirmed the accuracy of proteomic results. We totally quantified 1372 proteins and screened 132 altering expressed mitochondrial proteins, including 86 down-regulated expression proteins and 46 up-regulated expression proteins (pelectron transport chain and oxidative phosphorylation. Especially, mitochondrial related molecules, PRDX2, PARK7, BNIP3, BCL2, PDHA1, SUCLG1, ACADM and NDUFV1, were involved in energy production process in the matrix and membrane of mitochondria. Our results showed that abnormal electron transport, excessive oxidative stress and mitochondrion disassembly might be the main cause of mitochondrial dysfunction, and was related to the pathogenesis of EOS-PE. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  4. Oxidation of zirconium-aluminum alloys

    International Nuclear Information System (INIS)

    Cox, B.

    1967-10-01

    Examination of the processes occurring during the oxidation of Zr-1% A1, Zr-3% A1, and Zr-1.5% A1-0.5% Mo alloys has shown that in steam rapid oxidation occurs predominantly around the Zr 3 A1 particles, which at low temperatures appear to be relatively unattacked. The unoxidised particles become incorporated in the oxide, and become fully oxidised as the film thickens. This rapid localised oxidation is preceded by a short period of uniform film growth, during which the oxide film thickness does not exceed ∼200A-o. Thus the high oxidation rates can probably be ascribed to aluminum in solution in the zirconium matrix, although its precise mode of operation has not been determined. Once the solubility limit of aluminum is exceeded, the size, distribution and number of intermetallic particles affects the oxidation rate merely by altering the distribution of regions of metal giving high oxidation rates. The controlling process during the early stages of oxidation is electron transport and not ionic transport. Thus, the aluminum in the oxide film is presumably increasing the ionic conductivity more than the electronic. The oxidation rates in atmospheric pressure steam are very high and their irregular temperature dependence suggests that the oxidation rate will be pressure dependent. This was confirmed, in part, by a comparison with oxidation in moist air. It was found that the rate of development of white oxide around intermetallic particles was considerably reduced by the decrease in the partial pressure of H 2 O; the incubation period was not much different, however. (author)

  5. Atomistic structure of cobalt-phosphate nanoparticles for catalytic water oxidation.

    Science.gov (United States)

    Hu, Xiao Liang; Piccinin, Simone; Laio, Alessandro; Fabris, Stefano

    2012-12-21

    Solar-driven water splitting is a key photochemical reaction that underpins the feasible and sustainable production of solar fuels. An amorphous cobalt-phosphate catalyst (Co-Pi) based on earth-abundant elements has been recently reported to efficiently promote water oxidation to protons and dioxygen, a main bottleneck for the overall process. The structure of this material remains largely unknown. We here exploit ab initio and classical atomistic simulations combined with metadynamics to build a realistic and statistically meaningful model of Co-Pi nanoparticles. We demonstrate the emergence and stability of molecular-size ordered crystallites in nanoparticles initially formed by a disordered Co-O network and phosphate groups. The stable crystallites consist of bis-oxo-bridged Co centers that assemble into layered structures (edge-sharing CoO(6) octahedra) as well as in corner- and face-sharing cubane units. These layered and cubane motifs coexist in the crystallites, which always incorporate disordered phosphate groups at the edges. Our computational nanoparticles, although limited in size to ~1 nm, can contain more than one crystallite and incorporate up to 18 Co centers in the cubane/layered structures. The crystallites are structurally stable up to high temperatures. We simulate the extended X-ray absorption fine structure (EXAFS) of our nanoparticles. Those containing several complete and incomplete cubane motifs-which are believed to be essential for the catalytic activity-display a very good agreement with the experimental EXAFS spectra of Co-Pi grains. We propose that the crystallites in our nanoparticles are reliable structural models of the Co-Pi catalyst surface. They will be useful to reveal the origin of the catalytic efficiency of these novel water-oxidation catalysts.

  6. Probing the structural basis of oxygen binding in a cofactor-independent dioxygenase.

    Science.gov (United States)

    Li, Kunhua; Fielding, Elisha N; Condurso, Heather L; Bruner, Steven D

    2017-07-01

    The enzyme DpgC is included in the small family of cofactor-independent dioxygenases. The chemistry of DpgC is uncommon as the protein binds and utilizes dioxygen without the aid of a metal or organic cofactor. Previous structural and biochemical studies identified the substrate-binding mode and the components of the active site that are important in the catalytic mechanism. In addition, the results delineated a putative binding pocket and migration pathway for the co-substrate dioxygen. Here, structural biology is utilized, along with site-directed mutagenesis, to probe the assigned dioxygen-binding pocket. The key residues implicated in dioxygen trafficking were studied to probe the process of binding, activation and chemistry. The results support the proposed chemistry and provide insight into the general mechanism of dioxygen binding and activation.

  7. Lung vitamin E transport processes are affected by both age and environmental oxidants in mice

    International Nuclear Information System (INIS)

    Valacchi, Giuseppe; Vasu, Vihas T.; Yokohama, Wallace; Corbacho, Ana M.; Phung, Anh; Lim, Yunsook; Aung, Hnin Hnin; Cross, Carroll E.; Davis, Paul A.

    2007-01-01

    Despite the physiological importance of alpha-tocopherol (AT), the molecular mechanisms involved in maintaining cellular and tissue tocopherol levels remain to be fully characterized. Scavenger receptor B1 (SRB1), one of a large family of scavenger receptors, has been shown to facilitate AT transfer from HDL to peripheral tissues via apo A-1-mediated processes and to be important in the delivery of AT to the lung cells. In the present studies the effects of age and two environmental oxidants ozone (O 3 ) (0.25 ppm 6 h/day) and cigarette smoke (CS) (60 mg/m 3 6 h/day) for 4 days on selected aspects of AT transport in murine lung tissues were assessed. While AT levels were 25% higher (p 3 or CS at the doses used had no effect. Gene expression levels, determined by RT-PCR of AT transport protein (ATTP), SRB1, CD36, ATP binding cassette 3 (ABCA3) and ABCA1 and protein levels, determined by Western blots for SRB1, ATTP and ABCA1 were assessed. Aged mouse lung showed a lower levels of ATTP, ABCA3 and SRB1 and a higher level CD36 and ABCA1. Acute exposure to either O 3 or CS induced declines in ATTP and SRB1 in both aged and young mice lung. CD36 increased in both young and aged mice lung upon exposure to O 3 and CS. These findings suggest that both age and environmental oxidant exposure affect pathways related to lung AT homeostasis and do so in a way that favors declines in lung AT. However, given the approach taken, the effects cannot be traced to changes in these pathways or AT content in any specific lung associated cell type and thus highlight the need for further follow-up studies looking at specific lung associated cell types

  8. Seasonal Transport in Mars' Mesosphere-Thermosphere revealed by Nitric Oxide nightglow

    Science.gov (United States)

    Royer, E. M.; Stiepen, A.; Schneider, N. M.; Jain, S.; Milby, Z.; Deighan, J.; Gonzalez-Galindo, F.; Bougher, S. W.; Gerard, J. C. M. C.; Stevens, M. H.; Evans, J. S.; Stewart, I. F.; Chaffin, M.; McClintock, B.; Clarke, J. T.; Montmessin, F.; Holsclaw, G.; Lefèvre, F.; Forget, F.; Lo, D.; Hubert, B. A.; Jakosky, B. M.

    2017-12-01

    We analyze the ultraviolet nightglow in the atmosphere of Mars through the Nitric Oxide (NO) δ and γ band emissions observed by the Imaging Ultraviolet Spectrograph (IUVS, McClintock et al., 2015) when the Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft is at apoapsis and periapsis. On the dayside thermosphere of Mars, solar extreme ultraviolet radiation dissociates CO2 and N2 molecules. O(3P) and N(4S) atoms are carried by the day-to-night hemispheric transport. They descend in the nightside mesosphere, where they can radiatively recombine to form NO(C2Π). The excited molecules rapidly relax by emitting UV photons in the δ and γ bands. These emissions are thus indicators of the N and O atom fluxes transported from the dayside to Mars' nightside and the descending circulation pattern from the nightside thermosphere to the mesosphere (e.g. Bertaux et al., 2005 ; Bougher et al., 1990 ; Cox et al., 2008 ; Gagné et al., 2013 ; Gérard et al., 2008 ; Stiepen et al., 2015, 2017). A large dataset of nightside disk images and vertical limb scans during southern winter, fall equinox and southern summer conditions have been accumulated since the beginning of the mission. We will present a discussion regarding the variability of the brightness and altitude of the emission with season, geographical position (longitude) and local time and possible interpretation for local and global changes in the mesosphere dynamics. We show the possible impact of atmospheric waves structuring the emission longitudinally and indicating a wave-3 structure in Mars' nightside mesosphere. Quantitative comparison with calculations from the LMD-MGCM (Laboratoire de Météorologie Dynamique-Mars Global Climate Model) show that the model globally reproduces the trends of the NO nightglow emission and its seasonal variation but also indicates large discrepancies (up to a factor 50 fainter in the model) suggesting that the predicted transport is too efficient toward the night winter pole

  9. Gas-phase transport of fission products

    International Nuclear Information System (INIS)

    Tang, I.N.; Munkelwitz, H.R.

    1982-01-01

    The paper presents the results of an experimental investigation to show the importance of nuclear aerosol formation as a mechanism for semi-volatile fission product transport under certain postulated HTGR accident conditions. Simulated fission product Sr and Ba as oxides are impregnated in H451 graphite and released at elevated temperatures into a dry helium flow. In the presence of graphite, the oxides are quantitatively reduced to metals, which subsequently vaporize at temperatures much lower than required for the oxides alone to vaporize in the absence of graphite. A substantial fraction of the released material is associated with particulate matter, which is collected on filters located downstream at ambient temperatures. Increasing carrier-gas flow rate greatly enhances the extent of particulate transport. The release and transport of simulated fission product Ag as metal are also investigated. Electron microscopic examinations of the collected Sr and Ag aerosols show large agglomerates composed of primary particles roughly 0.06 to 0.08 μm in diameter

  10. Amorphous Tin Oxide as a Low-Temperature-Processed Electron-Transport Layer for Organic and Hybrid Perovskite Solar Cells

    KAUST Repository

    Barbe, Jeremy

    2017-02-08

    Chemical bath deposition (CBD) of tin oxide (SnO) thin films as an electron-transport layer (ETL) in a planar-heterojunction n-i-p organohalide lead perovskite and organic bulk-heterojunction (BHJ) solar cells is reported. The amorphous SnO (a-SnO) films are grown from a nontoxic aqueous bath of tin chloride at a very low temperature (55 °C) and do not require postannealing treatment to work very effectively as an ETL in a planar-heterojunction n-i-p organohalide lead perovskite or organic BHJ solar cells, in lieu of the commonly used ETL materials titanium oxide (TiO) and zinc oxide (ZnO), respectively. Ultraviolet photoelectron spectroscopy measurements on the glass/indium-tin oxide (ITO)/SnO/methylammonium lead iodide (MAPbI)/2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene device stack indicate that extraction of photogenerated electrons is facilitated by a perfect alignment of the conduction bands at the SnO/MAPbI interface, while the deep valence band of SnO ensures strong hole-blocking properties. Despite exhibiting very low electron mobility, the excellent interfacial energetics combined with high transparency (E > 4 eV) and uniform substrate coverage make the a-SnO ETL prepared by CBD an excellent candidate for the potentially low-cost and large-scale fabrication of organohalide lead perovskite and organic photovoltaics.

  11. Mars’ seasonal mesospheric transport seen through nitric oxide nightglow

    Science.gov (United States)

    Milby, Zachariah; Stiepen, Arnaud; Jain, Sonal; Schneider, Nicholas M.; Deighan, Justin; Gonzalez-Galindo, Francisco; Gerard, Jean-Claude; Stevens, Michael H.; Bougher, Stephen W.; Evans, J. Scott; Stewart, A. Ian; Chaffin, Michael; Crismani, Matteo; McClintock, William E.; Clarke, John T.; Holsclaw, Greg; Montmessin, Franck; Lefevre, Franck; Forget, Francois; Lo, Daniel Y.; Hubert, Benoît; Jakosky, Bruce

    2017-10-01

    We analyze the ultraviolet nightglow in the atmosphere of Mars through nitric oxide (NO) δ and γ band emissions as observed by the Imaging UltraViolet Spectrograph (IUVS) instrument onboard the Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft when it is at apoapse and periapse.In the dayside thermosphere of Mars, solar extreme-ultraviolet radiation dissociates CO2 and N2 molecules. O(3P) and N(4S) atoms are carried from the dayside to the nightside by the day-night hemispheric transport process, where they descend through the nightside mesosphere and can radiatively recombine to form NO(C2Π). The excited molecules rapidly relax by emitting photons in the UV δ and γ bands. These emissions are indicators of the N and O atom fluxes from the dayside to Mars’ nightside and the descending circulation pattern from the nightside thermosphere to the mesosphere (e.g. Bertaux et al., 2005 ; Bougher et al., 1990 ; Cox et al., 2008 ; Gagné et al., 2013 ; Gérard et al., 2008 ; Stiepen et al., 2015, 2017).Observations of these emissions are gathered from a large dataset spanning different seasonal conditions.We present discussion on the variability in the brightness and altitude of the emission with season, geographical position (longitude), and local time, along with possible interpretation by local and global changes in the mesosphere dynamics. We show the possible impact of atmospheric waves forcing longitudinal variability and data-to-model comparisons indicating a wave-3 structure in Mars’ nightside mesosphere. Quantitative comparison with calculations of the Laboratoire de Météorologie Dynamique-Mars Global Climate Model (LMD-MGCM) suggests the model reproduces both the global trend of NO nightglow emission and its seasonal variation. However, it also indicates large discrepancies, with the emission up to a factor 50 times fainter in the model, suggesting that the predicted transport is too efficient toward the night winter pole in the thermosphere by

  12. 49 CFR 173.323 - Ethylene oxide.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Ethylene oxide. 173.323 Section 173.323... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging § 173.323 Ethylene oxide. (a) For packaging ethylene oxide in non-bulk packagings, silver mercury or any of its alloys or copper may not be used in any...

  13. Innovative oxide materials for electrochemical energy conversion and oxygen separation

    Science.gov (United States)

    Belousov, V. V.

    2017-10-01

    Ion-conducting solid metal oxides are widely used in high-temperature electrochemical devices for energy conversion and oxygen separation. However, liquid metal oxides possessing unique electrochemical properties still remain of limited use. The review demonstrates the potential for practical applications of molten oxides. The transport properties of molten oxide materials are discussed. The emphasis is placed on the chemical diffusion of oxygen in the molten oxide membrane materials for electrochemical energy conversion and oxygen separation. The thermodynamics of these materials is considered. The dynamic polymer chain model developed to describe the oxygen ion transport in molten oxides is discussed. Prospects for further research into molten oxide materials are outlined. The bibliography includes 145 references.

  14. SPH based modelling of oxide and oxide film formation in gravity die castings

    International Nuclear Information System (INIS)

    Ellingsen, K; M'Hamdi, M; Coudert, T

    2015-01-01

    Gravity die casting is an important casting process which has the capability of making complicated, high-integrity components for e.g. the automotive industry. Oxides and oxide films formed during filling affect the cast product quality. The Smoothed particle hydrodynamics (SPH) method is particularly suited to follow complex flows. The SPH method has been used to study filling of a gravity die including the formation and transport of oxides and oxide films for two different filling velocities. A low inlet velocity leads to a higher amount of oxides and oxide films in the casting. The study demonstrates the usefulness of the SPH method for an increased understanding of the effect of different filling procedures on the cast quality. (paper)

  15. Reactive transport model of the formation of oxide-type Ni-laterite profiles (Punta Gorda, Moa Bay, Cuba)

    Science.gov (United States)

    Domènech, Cristina; Galí, Salvador; Villanova-de-Benavent, Cristina; Soler, Josep M.; Proenza, Joaquín A.

    2017-10-01

    Oxide-type Ni-laterite deposits are characterized by a dominant limonite zone with goethite as the economically most important Ni ore mineral and a thin zone of hydrous Mg silicate-rich saprolite beneath the magnesium discontinuity. Fe, less soluble, is mainly retained forming goethite, while Ni is redeposited at greater depth in a Fe(III) and Ni-rich serpentine (serpentine II) or in goethite, where it adsorbs or substitutes for Fe in the mineral structure. Here, a 1D reactive transport model, using CrunchFlow, of Punta Gorda oxide-type Ni-laterite deposit (Moa Bay, Cuba) formation is presented. The model reproduces the formation of the different laterite horizons in the profile from an initial, partially serpentinized peridotite, in 106 years, validating the conceptual model of the formation of this kind of deposits in which a narrow saprolite horizon rich in Ni-bearing serpentine is formed above peridotite parent rock and a thick limonite horizon is formed over saprolite. Results also confirm that sorption of Ni onto goethite can explain the weight percent of Ni found in the Moa goethite. Sensitivity analyses accounting for the effect of key parameters (composition, dissolution rate, carbonate concentration, quartz precipitation) on the model results are also presented. It is found that aqueous carbonate concentration and quartz precipitation significantly affects the laterization process rate, while the effect of the composition of secondary serpentine or of mineral dissolution rates is minor. The results of this reactive transport modeling have proven useful to validate the conceptual models derived from field observations.

  16. Synthesis and structural, magnetic, thermal, and transport properties of several transition metal oxides and aresnides

    Energy Technology Data Exchange (ETDEWEB)

    Das, Supriyo [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    Oxide compounds containing the transition metal vanadium (V) have attracted a lot of attention in the field of condensed matter physics owing to their exhibition of interesting properties including metal-insulator transitons, structural transitions, ferromagnetic and an- tiferromagnetic orderings, and heavy fermion behavior. Binary vanadium oxides VnO2n-1 where 2 ≤ n ≤ 9 have triclinic structures and exhibit metal-insulator and antiferromagnetic transitions.[1–6] The only exception is V7O13 which remains metallic down to 4 K.[7] The ternary vanadium oxide LiV2O4 has the normal spinel structure, is metallic, does not un- dergo magnetic ordering and exhibits heavy fermion behavior below 10 K.[8] CaV2O4 has an orthorhombic structure[9, 10] with the vanadium spins forming zigzag chains and has been suggested to be a model system to study the gapless chiral phase.[11, 12] These provide great motivation for further investigation of some known vanadium compounds as well as to ex- plore new vanadium compounds in search of new physics. This thesis consists, in part, of experimental studies involving sample preparation and magnetic, transport, thermal, and x- ray measurements on some strongly correlated eletron systems containing the transition metal vanadium. The compounds studied are LiV2O4, YV4O8, and YbV4O8. The recent discovery of superconductivity in RFeAsO1-xFx (R = La, Ce, Pr, Gd, Tb, Dy, Sm, and Nd), and AFe2As2 (A = Ba, Sr, Ca, and Eu) doped with K, Na, or Cs at the A site with relatively high Tc has sparked tremendous activities in the condensed matter physics community and a renewed interest in the area of superconductivity as occurred following the discovery of the layered cuprate high Tc superconductors in 1986. To discover more supercon- ductors

  17. The kinetics of iodide oxidation by the manganese oxide mineral birnessite

    Science.gov (United States)

    Fox, P.M.; Davis, J.A.; Luther, G. W.

    2009-01-01

    The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

  18. Numerical simulation of vertical transport and oxidation of methane in Arctic Ocean

    Science.gov (United States)

    Stepanenko, Victor; Iakovlev, Nikolai

    2013-04-01

    The high abundance of methane in shelf of East Siberian Arctic Seas (ESAS) has been a subject of a number of field studies (e.g. Shakhova et al., 2010). This experimental evidence provoked discussions on probable origins of that methane and possible feedbacks to modern climate change. For instance, the hypothesis of methane hydrates degradation under current ocean warming was tested recently in several modeling studies none of which supported this degradation to be significant feedback for climate change. Regardless the origin of methane the knowledge of its budget in the water column is important to link its bottom flux with emission to the atmosphere (and vice versa). It is frequently assumed that all methane released from a seabed of ESAS shelf reaches the atmosphere. When using ocean circulation models (Biastoch et al., 2011) this simplification is cancelled out but the vertical resolution of 3D models at the shelf (that is several tens meters deep) is not enough to accurately resolve turbulent transport of methane and other gases. Moreover, up the knowledge of authors none of the ocean models includes explicitly bubble transport of gases. These constrains motivate this study. In this study a high-resolution 1D single column ocean model is constructed to explicitly simulate the methane transport, oxidation and emission to the atmosphere. The model accounts for both vertical turbulent transport (using k-ɛ closure) and bubble transport of gases. The ground under the seabed is represented by multilayer heat and moisture transfer model, including methane hydrate evolution. It is forced by time series of atmospheric variables from NCEP reanalysis and horizontal advection terms taken from FEMAO-1 3D ocean model. The baseline simulation is performed for the period 1948-2011. The model is validated using temperature profiles measured at research vessels in ESAS. The annual cycle and multiyear variability of methane profiles in water are studied and compared to

  19. Role of vitamin C transporters and biliverdin reductase in the dual pro-oxidant and anti-oxidant effect of biliary compounds on the placental-fetal unit in cholestasis during pregnancy

    International Nuclear Information System (INIS)

    Perez, Maria J.; Castano, Beatriz; Jimenez, Silvia; Serrano, Maria A.; Gonzalez-Buitrago, Jose M.; Marin, Jose J.G.

    2008-01-01

    Maternal cholestasis causes oxidative damage to the placental-fetal unit that may challenge the outcome of pregnancy. This has been associated with the accumulation of biliary compounds able to induce oxidative stress. However, other cholephilic compounds such as ursodeoxycholic acid (UDCA) and bilirubin have direct anti-oxidant properties. In the present study we investigated whether these compounds exert a protective effect on cholestasis-induced oxidative stress in placenta as compared to maternal and fetal livers, and whether this is due in part to the activation of anti-oxidant mechanisms involving vitamin C uptake and biliverdin/bilirubin recycling. In human placenta (JAr) and liver (HepG2) cells, deoxycholic acid (DCA) similar rates of free radical generation. In JAr (not HepG2), the mitochondrial membrane potential and cell viability were impaired by low DCA concentrations; this was partly prevented by bilirubin and UDCA. In HepG2, taurocholic acid (TCA) and UDCA up-regulated biliverdin-IXα reductase (BVRα) and the vitamin C transporter SVCT2 (not SVCT1), whereas bilirubin up-regulated both SVCT1 and SVCT2. In JAr, TCA and UDCA up-regulated BVRα, SVCT1 and SVCT2, whereas bilirubin up-regulated only SVCT2. A differential response to these compounds of nuclear receptor expression (SXR, CAR, FXR and SHP) was found in both cell types. When cholestasis was induced in pregnant rats, BVRα, SVCT1 and SVCT2 expression in maternal and fetal livers was stimulated, and this was further enhanced by UDCA treatment. In placenta, only BVRα was up-regulated. In conclusion, bilirubin accumulation and UDCA administration may directly and indirectly protect the placental-fetal unit from maternal cholestasis-induced oxidative stress

  20. Gas Transport and Exchange through Wetland Plant Aerenchyma

    DEFF Research Database (Denmark)

    Sorrell, Brian Keith; Brix, Hans

    2013-01-01

    Aerenchyma, the large airspaces in aquatic plants, is a rapid gas transport pathway between atmosphere and soil in wetlands. Oxygen transport aerates belowground tissue and oxidizes rhizosphere soil, an important process in wetland biogeochemistry. Most plant O2 transport occurs by diffusion...

  1. Circulating biologically active oxidized phospholipids show on-going and increased oxidative stress in older male mice

    Directory of Open Access Journals (Sweden)

    Jinbo Liu

    2013-01-01

    Significance: Oxidatively modified phospholipids are increased in the circulation during common, mild oxidant stresses of aging, or in male compared to female animals. Turnover of these biologically active phospholipids by rapid transport into liver and kidney is unchanged, so circulating levels reflect continuously increased production.

  2. Microbial iron reduction and methane oxidation in subsurface sediments of the Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Fernandes, C.E.G.; Judith, M.; Gonsalves, M.J.B.D.; Nazareth, D.R.; Nagarchi, L.; Kamaleson, A.S.

    as it has productivity driven seasonal pattern of dioxygen-deficient waters. It is one of the most biologically productive regions of the world’s ocean having a characteristic seasonal upwelling followed by the production of an oxygen minimum zone... in the water body (Wyrtki, 1971; Madhupratap et al., 1996; Naidu, 1998). The seasonal upwelling in return has been reported to have prolonged and distinct effect on biological production and sedimentation (Madhupratap et al., 1996). Another important feature...

  3. Aspirin increases mitochondrial fatty acid oxidation

    International Nuclear Information System (INIS)

    Uppala, Radha; Dudiak, Brianne; Beck, Megan E.; Bharathi, Sivakama S.; Zhang, Yuxun; Stolz, Donna B.; Goetzman, Eric S.

    2017-01-01

    The metabolic effects of salicylates are poorly understood. This study investigated the effects of aspirin on fatty acid oxidation. Aspirin increased mitochondrial long-chain fatty acid oxidation, but inhibited peroxisomal fatty acid oxidation, in two different cell lines. Aspirin increased mitochondrial protein acetylation and was found to be a stronger acetylating agent in vitro than acetyl-CoA. However, aspirin-induced acetylation did not alter the activity of fatty acid oxidation proteins, and knocking out the mitochondrial deacetylase SIRT3 did not affect the induction of long-chain fatty acid oxidation by aspirin. Aspirin did not change oxidation of medium-chain fatty acids, which can freely traverse the mitochondrial membrane. Together, these data indicate that aspirin does not directly alter mitochondrial matrix fatty acid oxidation enzymes, but most likely exerts its effects at the level of long-chain fatty acid transport into mitochondria. The drive on mitochondrial fatty acid oxidation may be a compensatory response to altered mitochondrial morphology and inhibited electron transport chain function, both of which were observed after 24 h incubation of cells with aspirin. These studies provide insight into the pathophysiology of Reye Syndrome, which is known to be triggered by aspirin ingestion in patients with fatty acid oxidation disorders. - Highlights: • Aspirin increases mitochondrial—but inhibits peroxisomal—fatty acid oxidation. • Aspirin acetylates mitochondrial proteins including fatty acid oxidation enzymes. • SIRT3 does not influence the effect of aspirin on fatty acid oxidation. • Increased fatty acid oxidation is likely due to altered mitochondrial morphology and respiration.

  4. Amorphous indium-gallium-zinc-oxide as electron transport layer in organic photodetectors

    International Nuclear Information System (INIS)

    Arora, H.; Malinowski, P. E.; Chasin, A.; Cheyns, D.; Steudel, S.; Schols, S.; Heremans, P.

    2015-01-01

    Amorphous indium-gallium-zinc-oxide (a-IGZO) is demonstrated as an electron transport layer (ETL) in a high-performance organic photodetector (OPD). Dark current in the range of 10 nA/cm 2 at a bias voltage of −2 V and a high photoresponse in the visible spectrum were obtained in inverted OPDs with poly(3-hexylthiophene) and phenyl-C 61 -butyric acid methyl ester active layer. The best results were obtained for the optimum a-IGZO thickness of 7.5 nm with specific detectivity of 3 × 10 12 Jones at the wavelength of 550 nm. The performance of the best OPD devices using a-IGZO was shown to be comparable to state-of-the-art devices based on TiO x as ETL, with higher rectification achieved in reverse bias. Yield and reproducibility were also enhanced with a-IGZO, facilitating fabrication of large area OPDs. Furthermore, easier integration with IGZO-based readout backplanes can be envisioned, where the channel material can be used as photodiode buffer layer after additional treatment

  5. Amorphous indium-gallium-zinc-oxide as electron transport layer in organic photodetectors

    Energy Technology Data Exchange (ETDEWEB)

    Arora, H. [IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Phelma–Grenoble INP, 3 Parvis Louis Néel, 38016 Grenoble Cedex 01 (France); Malinowski, P. E., E-mail: pawel.malinowski@imec.be; Chasin, A.; Cheyns, D.; Steudel, S.; Schols, S. [IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Heremans, P. [IMEC, Kapeldreef 75, 3001 Leuven (Belgium); ESAT, Katholieke Universiteit Leuven, Kasteelpark Arenberg 10, B-3001 Leuven (Belgium)

    2015-04-06

    Amorphous indium-gallium-zinc-oxide (a-IGZO) is demonstrated as an electron transport layer (ETL) in a high-performance organic photodetector (OPD). Dark current in the range of 10 nA/cm{sup 2} at a bias voltage of −2 V and a high photoresponse in the visible spectrum were obtained in inverted OPDs with poly(3-hexylthiophene) and phenyl-C{sub 61}-butyric acid methyl ester active layer. The best results were obtained for the optimum a-IGZO thickness of 7.5 nm with specific detectivity of 3 × 10{sup 12} Jones at the wavelength of 550 nm. The performance of the best OPD devices using a-IGZO was shown to be comparable to state-of-the-art devices based on TiO{sub x} as ETL, with higher rectification achieved in reverse bias. Yield and reproducibility were also enhanced with a-IGZO, facilitating fabrication of large area OPDs. Furthermore, easier integration with IGZO-based readout backplanes can be envisioned, where the channel material can be used as photodiode buffer layer after additional treatment.

  6. Selective downregulation of mitochondrial electron transport chain activity and increased oxidative stress in human atrial fibrillation.

    Science.gov (United States)

    Emelyanova, Larisa; Ashary, Zain; Cosic, Milanka; Negmadjanov, Ulugbek; Ross, Gracious; Rizvi, Farhan; Olet, Susan; Kress, David; Sra, Jasbir; Tajik, A Jamil; Holmuhamedov, Ekhson L; Shi, Yang; Jahangir, Arshad

    2016-07-01

    Mitochondria are critical for maintaining normal cardiac function, and a deficit in mitochondrial energetics can lead to the development of the substrate that promotes atrial fibrillation (AF) and its progression. However, the link between mitochondrial dysfunction and AF in humans is still not fully defined. The aim of this study was to elucidate differences in the functional activity of mitochondrial oxidative phosphorylation (OXPHOS) complexes and oxidative stress in right atrial tissue from patients without (non-AF) and with AF (AF) who were undergoing open-heart surgery and were not significantly different for age, sex, major comorbidities, and medications. The overall functional activity of the electron transport chain (ETC), NADH:O2 oxidoreductase activity, was reduced by 30% in atrial tissue from AF compared with non-AF patients. This was predominantly due to a selective reduction in complex I (0.06 ± 0.007 vs. 0.09 ± 0.006 nmol·min(-1)·citrate synthase activity(-1), P = 0.02) and II (0.11 ± 0.012 vs. 0.16 ± 0.012 nmol·min(-1)·citrate synthase activity(-1), P = 0.003) functional activity in AF patients. Conversely, complex V activity was significantly increased in AF patients (0.21 ± 0.027 vs. 0.12 ± 0.01 nmol·min(-1)·citrate synthase activity(-1), P = 0.005). In addition, AF patients exhibited a higher oxidative stress with increased production of mitochondrial superoxide (73 ± 17 vs. 11 ± 2 arbitrary units, P = 0.03) and 4-hydroxynonenal level (77.64 ± 30.2 vs. 9.83 ± 2.83 ng·mg(-1) protein, P = 0.048). Our findings suggest that AF is associated with selective downregulation of ETC activity and increased oxidative stress that can contribute to the progression of the substrate for AF. Copyright © 2016 the American Physiological Society.

  7. Effect of water soluble vitamins on Zn transport of Caco-2 cells and their implications under oxidative stress conditions.

    Science.gov (United States)

    Tupe, Rashmi Santosh; Agte, Vaishali Vilas

    2010-02-01

    The role of different water soluble vitamins in Zn metabolism beyond intestinal Zn absorption is poorly explored. Using Caco-2 cells, effects of different vitamins on intestinal Zn transport and their implications under oxidative stress (OS) were investigated. Cells were apically treated with Zn (25 muM) and vitamins (Folic acid (FA), Nicotinic acid (NA), Ascorbic acid (AA), riboflavin, thiamine, pyridoxine) for 60 min. The effect of most promising vitamins on zinc transport, antioxidant enzymes (Catalase, Glutathione peroxidase, and superoxide dismutase), and intracellular OS status (ROS generation and mitochondrial transmembrane potential) were investigated. OS was generated by tert-butyl hydro peroxide and results for each vitamin were compared with respective Zn containing controls with and without OS. Without OS, Zn transport was slightly enhanced in presence of NA, while it was significantly reduced by thiamine, riboflavin, and pyridoxine. Under OS, NA significantly (P vitamins. With Zn + FA + OS, enzyme activities decreased maximally, with twofold increase in 2',7'-dichlorofluorescin diacetate (DCF-DA) (P < 0.01) and lowering of rhodamine fluorescence (P < 0.05). In Zn + AA + OS, DCF-DA fluorescence increased (P < 0.05) but with NA, cellular enzymes, and antioxidant profile were improved. Results for the first time demonstrate advantageous effects of NA and deleterious consequences of FA with no effect by AA on Zn transport, especially under OS. These observed changes in the transport of Zn seem to have an impact on OS markers.

  8. Gas Transport and Exchange through Wetland Plant Aerenchyma

    DEFF Research Database (Denmark)

    Sorrell, Brian Keith; Brix, Hans

    2013-01-01

    Aerenchyma, the large airspaces in aquatic plants, is a rapid gas transport pathway between atmosphere and soil in wetlands. Oxygen transport aerates belowground tissue and oxidizes rhizosphere soil, an important process in wetland biogeochemistry. Most plant O2 transport occurs by diffusion......, and the major challenge for its accurate measurement is avoiding disturbing small-scale gradients in O2 concentration and demand in the pathway. Small O2 sensors with rapid response times and high spatial resolution are the most popular methods for quantifying O2 transport and rhizosphere oxidation...... such as stirring of solutions. In some species, pressurized gas flows develop in shoots and rhizomes, and their contribution to gas fluxes can be assessed with pressure transducers and flow meters. Other gases produced in wetlands (e.g., CO2, CH4, and N2O) are also transported in aerenchyma. Their fluxes...

  9. Ternary Oxides in the TiO2-ZnO System as Efficient Electron-Transport Layers for Perovskite Solar Cells with Efficiency over 15.

    Science.gov (United States)

    Yin, Xiong; Xu, Zhongzhong; Guo, Yanjun; Xu, Peng; He, Meng

    2016-11-02

    Perovskite solar cells, which utilize organometal-halide perovskites as light-harvesting materials, have attracted great attention due to their high power conversion efficiency (PCE) and potentially low cost in fabrication. A compact layer of TiO 2 or ZnO is generally applied as electron-transport layer (ETL) in a typical perovskite solar cell. In this study, we explored ternary oxides in the TiO 2 -ZnO system to find new materials for the ETL. Compact layers of titanium zinc oxides were readily prepared on the conducting substrate via spray pyrolysis method. The optical band gap, valence band maximum and conduction band minimum of the ternary oxides varied significantly with the ratio of Ti to Zn, surprisingly, in a nonmonotonic way. When a zinc-rich ternary oxide was applied as ETL for the device, a PCE of 15.10% was achieved, comparable to that of the device using conventional TiO 2 ETL. Interestingly, the perovskite layer deposited on the zinc-rich ternary oxide is stable, in sharp contrast with that fabricated on a ZnO layer, which will turn into PbI 2 readily when heated. These results indicate that potentially new materials with better performance can be found for ETL of perovskite solar cells in ternary oxides, which deserve more exploration.

  10. The properties and transport phenomena in oxide films on iron, nickel, chromium and their alloys in aqueous environments

    International Nuclear Information System (INIS)

    Laitinen, T.; Bojinov, M.; Betova, I.; Maekelae, K.; Saario, T.

    1999-01-01

    . In addition, the films are to a large extent influenced by the kinetic factors determining their growth rate and steady state thickness. Thus a thermodynamic consideration of the film is not sufficient to model and predict its growth and dissolution. Instead, kinetic models based on in situ experimental data are required. The kinetic models presented in the literature for both ambient and high-temperature aqueous oxidation of metals lack a correlation between the structure of the oxide films and their electronic and ionic properties. Also, a quantitative treatment and thus the capability to predict material behaviour in varying conditions is lacking. A comprehensive understanding of the correlation between applied water chemistry, the behaviour of oxide films and optimum performance of the plant is thus also lacking. The situation calls for more experimental work combined with comprehensive modelling of the behaviour of both the compact and the porous part of the oxide film formed on a metal surface. This will make it possible to recognise the rate-limiting steps of the processes in the film, and thus to influence the rate of activity incorporation and different corrosion phenomena related to transport of species in the film. (author)

  11. The properties and transport phenomena in oxide films on iron, nickel, chromium and their alloys in aqueous environments

    Energy Technology Data Exchange (ETDEWEB)

    Laitinen, T.; Bojinov, M.; Betova, I.; Maekelae, K.; Saario, T. [VTT Manufacturing Technology, Espoo (Finland)

    1999-01-01

    . In addition, the films are to a large extent influenced by the kinetic factors determining their growth rate and steady state thickness. Thus a thermodynamic consideration of the film is not sufficient to model and predict its growth and dissolution. Instead, kinetic models based on in situ experimental data are required. The kinetic models presented in the literature for both ambient and high-temperature aqueous oxidation of metals lack a correlation between the structure of the oxide films and their electronic and ionic properties. Also, a quantitative treatment and thus the capability to predict material behaviour in varying conditions is lacking. A comprehensive understanding of the correlation between applied water chemistry, the behaviour of oxide films and optimum performance of the plant is thus also lacking. The situation calls for more experimental work combined with comprehensive modelling of the behaviour of both the compact and the porous part of the oxide film formed on a metal surface. This will make it possible to recognise the rate-limiting steps of the processes in the film, and thus to influence the rate of activity incorporation and different corrosion phenomena related to transport of species in the film. (author) 210 refs.

  12. Fat gain with physical detraining is correlated with increased glucose transport and oxidation in periepididymal white adipose tissue in rats

    Energy Technology Data Exchange (ETDEWEB)

    Sertié, R.A.L.; Andreotti, S. [Departamento de Fisiologia e Biofísica, Instituto de Ciências Biomédicas, Universidade de São Paulo, São Paulo, SP (Brazil); Proença, A.R.G. [Laboratório de Biotecnologia, Faculdade de Ciências Aplicadas, Universidade Estadual de Campinas, Limeira, SP (Brazil); Campaña, A.B.; Lima, F.B. [Departamento de Fisiologia e Biofísica, Instituto de Ciências Biomédicas, Universidade de São Paulo, São Paulo, SP (Brazil)

    2015-05-26

    As it is a common observation that obesity tends to occur after discontinuation of exercise, we investigated how white adipocytes isolated from the periepididymal fat of animals with interrupted physical training transport and oxidize glucose, and whether these adaptations support the weight regain seen after 4 weeks of physical detraining. Male Wistar rats (45 days old, weighing 200 g) were divided into two groups (n=10): group D (detrained), trained for 8 weeks and detrained for 4 weeks; and group S (sedentary). The physical exercise was carried out on a treadmill for 60 min/day, 5 days/week for 8 weeks, at 50-60% of the maximum running capacity. After the training protocol, adipocytes isolated from the periepididymal adipose tissue were submitted to glucose uptake and oxidation tests. Adipocytes from detrained animals increased their glucose uptake capacity by 18.5% compared with those from sedentary animals (P<0.05). The same cells also showed a greater glucose oxidation capacity in response to insulin stimulation (34.55%) compared with those from the S group (P<0.05). We hypothesize that, owing to the more intense glucose entrance into adipose cells from detrained rats, more substrate became available for triacylglycerol synthesis. Furthermore, this increased glucose oxidation rate allowed an increase in energy supply for triacylglycerol synthesis. Thus, physical detraining might play a role as a possible obesogenic factor for increasing glucose uptake and oxidation by adipocytes.

  13. Fat gain with physical detraining is correlated with increased glucose transport and oxidation in periepididymal white adipose tissue in rats

    International Nuclear Information System (INIS)

    Sertié, R.A.L.; Andreotti, S.; Proença, A.R.G.; Campaña, A.B.; Lima, F.B.

    2015-01-01

    As it is a common observation that obesity tends to occur after discontinuation of exercise, we investigated how white adipocytes isolated from the periepididymal fat of animals with interrupted physical training transport and oxidize glucose, and whether these adaptations support the weight regain seen after 4 weeks of physical detraining. Male Wistar rats (45 days old, weighing 200 g) were divided into two groups (n=10): group D (detrained), trained for 8 weeks and detrained for 4 weeks; and group S (sedentary). The physical exercise was carried out on a treadmill for 60 min/day, 5 days/week for 8 weeks, at 50-60% of the maximum running capacity. After the training protocol, adipocytes isolated from the periepididymal adipose tissue were submitted to glucose uptake and oxidation tests. Adipocytes from detrained animals increased their glucose uptake capacity by 18.5% compared with those from sedentary animals (P<0.05). The same cells also showed a greater glucose oxidation capacity in response to insulin stimulation (34.55%) compared with those from the S group (P<0.05). We hypothesize that, owing to the more intense glucose entrance into adipose cells from detrained rats, more substrate became available for triacylglycerol synthesis. Furthermore, this increased glucose oxidation rate allowed an increase in energy supply for triacylglycerol synthesis. Thus, physical detraining might play a role as a possible obesogenic factor for increasing glucose uptake and oxidation by adipocytes

  14. Role of glutathione transport processes in kidney function

    International Nuclear Information System (INIS)

    Lash, Lawrence H.

    2005-01-01

    The kidneys are highly dependent on an adequate supply of glutathione (GSH) to maintain normal function. This is due, in part, to high rates of aerobic metabolism, particularly in the proximal tubules. Additionally, the kidneys are potentially exposed to high concentrations of oxidants and reactive electrophiles. Renal cellular concentrations of GSH are maintained by both intracellular synthesis and transport from outside the cell. Although function of specific carriers has not been definitively demonstrated, it is likely that multiple carriers are responsible for plasma membrane transport of GSH. Data suggest that the organic anion transporters OAT1 and OAT3 and the sodium-dicarboxylate 2 exchanger (SDCT2 or NaDC3) mediate uptake across the basolateral plasma membrane (BLM) and that the organic anion transporting polypeptide OATP1 and at least one of the multidrug resistance proteins mediate efflux across the brush-border plasma membrane (BBM). BLM transport may be used pharmacologically to provide renal proximal tubular cells with exogenous GSH to protect against oxidative stress whereas BBM transport functions physiologically in turnover of cellular GSH. The mitochondrial GSH pool is derived from cytoplasmic GSH by transport into the mitochondrial matrix and is mediated by the dicarboxylate and 2-oxoglutarate exchangers. Maintenance of the mitochondrial GSH pool is critical for cellular and mitochondrial redox homeostasis and is important in determining susceptibility to chemically induced apoptosis. Hence, membrane transport processes are critical to regulation of renal cellular and subcellular GSH pools and are determinants of susceptibility to cytotoxicity induced by oxidants and electrophiles

  15. Efficient and Air-Stable Planar Perovskite Solar Cells Formed on Graphene-Oxide-Modified PEDOT:PSS Hole Transport Layer

    Science.gov (United States)

    Luo, Hui; Lin, Xuanhuai; Hou, Xian; Pan, Likun; Huang, Sumei; Chen, Xiaohong

    2017-10-01

    As a hole transport layer, PEDOT:PSS usually limits the stability and efficiency of perovskite solar cells (PSCs) due to its hygroscopic nature and inability to block electrons. Here, a graphene-oxide (GO)-modified PEDOT:PSS hole transport layer was fabricated by spin-coating a GO solution onto the PEDOT:PSS surface. PSCs fabricated on a GO-modified PEDOT:PSS layer exhibited a power conversion efficiency (PCE) of 15.34%, which is higher than 11.90% of PSCs with the PEDOT:PSS layer. Furthermore, the stability of the PSCs was significantly improved, with the PCE remaining at 83.5% of the initial PCE values after aging for 39 days in air. The hygroscopic PSS material at the PEDOT:PSS surface was partly removed during spin-coating with the GO solution, which improves the moisture resistance and decreases the contact barrier between the hole transport layer and perovskite layer. The scattered distribution of the GO at the PEDOT:PSS surface exhibits superior wettability, which helps to form a high-quality perovskite layer with better crystallinity and fewer pin holes. Furthermore, the hole extraction selectivity of the GO further inhibits the carrier recombination at the interface between the perovskite and PEDOT:PSS layers. Therefore, the cooperative interactions of these factors greatly improve the light absorption of the perovskite layer, the carrier transport and collection abilities of the PSCs, and especially the stability of the cells.

  16. Direct Simulation of Transport Properties from Three-Dimensional (3D) Reconstructed Solid-Oxide Fuel-Cell (SOFC) Electrode Microstructures

    International Nuclear Information System (INIS)

    Gunda, Naga Siva Kumar; Mitra, Sushanta K

    2012-01-01

    A well-known approach to develop a high efficiency solid-oxide fuel-cell (SOFC) consists of extracting the microstructure and transport properties such as volume fractions, internal surface area, geometric connectivity, effective gas diffusivity, effective electronic conductivity and geometric tortuosities from three-dimensional (3D) microstructure of the SOFC electrodes; thereafter, performing the SOFC efficiency calculations using previously mentioned quantities. In the present work, dual-beam focused ion beam - scanning electron microscopy (FIB-SEM) is applied on one of the SOFC cathodes, a lanthanum strontium manganite (LSM) electrode, to estimate the aforementioned properties. A framework for calculating transport properties is presented in this work. 3D microstructures of LSM electrode are reconstructed from a series of two-dimensional (2D) cross-sectional FIB-SEM images. Volume percentages of connected, isolated and dead-ends networks of pore and LSM phases are estimated. Different networks of pore and LSM phases are discretized with tetrahedral elements. Finally, the finite element method (FEM) is applied to calculate effective gas diffusivity and electronic conductivity of pore and LSM phases, respectively. Geometric tortuosities are estimated from the porosity and effective transport properties. The results obtained using FEM are compared with the finite volume method (FVM) results obtained by Gunda et al. [J. Power Sources, 196(7), 35929(2011)] and other numerical results obtained on randomly generated porous medium. Effect of consideration of dead-ends and isolated-ends networks on calculation of effective transport properties is studied.

  17. Yeast two-hybrid screens imply involvement of Fanconi anemia proteins in transcription regulation, cell signaling, oxidative metabolism, and cellular transport.

    Science.gov (United States)

    Reuter, Tanja Y; Medhurst, Annette L; Waisfisz, Quinten; Zhi, Yu; Herterich, Sabine; Hoehn, Holger; Gross, Hans J; Joenje, Hans; Hoatlin, Maureen E; Mathew, Christopher G; Huber, Pia A J

    2003-10-01

    Mutations in one of at least eight different genes cause bone marrow failure, chromosome instability, and predisposition to cancer associated with the rare genetic syndrome Fanconi anemia (FA). The cloning of seven genes has provided the tools to study the molecular pathway disrupted in Fanconi anemia patients. The structure of the genes and their gene products provided few clues to their functional role. We report here the use of 3 FA proteins, FANCA, FANCC, and FANCG, as "baits" in the hunt for interactors to obtain clues for FA protein functions. Using five different human cDNA libraries we screened 36.5x10(6) clones with the technique of the yeast two-hybrid system. We identified 69 proteins which have not previously been linked to the FA pathway as direct interactors of FANCA, FANCC, or FANCG. Most of these proteins are associated with four functional classes including transcription regulation (21 proteins), signaling (13 proteins), oxidative metabolism (10 proteins), and intracellular transport (11 proteins). Interaction with 6 proteins, DAXX, Ran, IkappaBgamma, USP14, and the previously reported SNX5 and FAZF, was additionally confirmed by coimmunoprecipitation and/or colocalization studies. Taken together, our data strongly support the hypothesis that FA proteins are functionally involved in several complex cellular pathways including transcription regulation, cell signaling, oxidative metabolism, and cellular transport.

  18. Upgrading of syngas hydrotreated fractionated oxidized bio-oil to transportation grade hydrocarbons

    International Nuclear Information System (INIS)

    Luo, Yan; Hassan, El Barbary; Guda, Vamshi; Wijayapala, Rangana; Steele, Philip H.

    2016-01-01

    Highlights: • Hydrotreating of fractionated oxidized bio-oil with syngas was feasible. • Hydrocarbon properties were similar with all syngas H_2/CO molar ratios except viscosity. • Syngas with H_2/CO molar ratio of (4:6) produced the highest hydrocarbon yield. • The produced hydrocarbons were in the range of gasoline, jet fuel and diesel boiling points. - Abstract: Fast pyrolysis bio-oils have the potential to replace a part of transportation fuels obtained from fossil. Bio-oil can be successfully upgraded into stable hydrocarbons (gasoline, jet fuel and diesel) through a two-stage hydrodeoxygenation process. Consumption large amount of expensive hydrogen during this process is the major hurdle for commercialization of this technology. Applying syngas in the hydrotreating step can significantly reduce the cost of the whole process and make it competitive. In this study, four different models of syngas with different H_2 concentrations (H_2/CO molar ratios = 2:8, 4:6, 6:4 and 8:2) were used for the 1st-stage hydrotreating step of oxidized fractionated bio-oil (OFB). The 2nd-stage hydrocracking step was performed on the produced organic liquid products (OLPs) by using pure H_2 gas. The effect of syngas H_2 concentrations on the yields and properties of OLPs and the 2nd-stage hydrocarbons (HCs) was investigated. Physical and chemical properties of the 2nd-stage hydrocarbons were similar regardless syngas H_2 content, with the exception of the viscosity. Syngas with H_2/CO molar ratio of 4:6 gave significantly highest HCs yield (24.8 wt.%) based on the OFB. Simulated distillation analysis proved that all 2nd-stage hydrocarbons were mixture from a wide range boiling point fuels. These results also indicated that the successful 1st-stage syngas hydrotreating step was having the potential to produce different hydrocarbons.

  19. Performance evaluation of a biodiesel fuelled transportation engine retrofitted with a non-noble metal catalysed diesel oxidation catalyst for controlling unregulated emissions.

    Science.gov (United States)

    Shukla, Pravesh Chandra; Gupta, Tarun; Agarwal, Avinash Kumar

    2018-02-15

    In present study, engine exhaust was sampled for measurement and analysis of unregulated emissions from a four cylinder transportation diesel engine using a state-of-the-art FTIR (Fourier transform infrared spectroscopy) emission analyzer. Test fuels used were Karanja biodiesel blend (B20) and baseline mineral diesel. Real-time emission measurements were performed for raw exhaust as well as exhaust sampled downstream of the two in-house prepared non-noble metal based diesel oxidation catalysts (DOCs) and a baseline commercial DOC based on noble metals. Two prepared non-noble metal based DOCs were based on Co-Ce mixed oxide and Lanthanum based perovskite catalysts. Perovskite based DOC performed superior compared to Co-Ce mixed oxide catalyst based DOC. Commercial noble metal based DOC was found to be the most effective in reducing unregulated hydrocarbon emissions in the engine exhaust, followed by the two in-house prepared non-noble metal based DOCs. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Effects of Transportation on Antioxidant Status in Cynomolgus Macaques (Macaca fascicularis).

    Science.gov (United States)

    Pan, Xueying; Lu, Liang; Zeng, Xiancheng; Chang, Yan; Hua, Xiuguo

    2016-01-01

    To evaluate the effects of transportation on oxidative stress in cynomolgus monkeys, we measured serum levels of reduced glutathione (GSH), malondialdehyde, and protein carbonyl (PC) and the activities of total antioxidant capacity (TAOC), superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), and catalase in cynomolgus macaques before transportation (day 0), on the day of arrival (day 1), and on days 7, 14, and 21 after transportation. Compared with that on day 0, TAOC and catalase activities on days 1, 7, and 14 after transportation were significantly decreased, reached their nadirs on day 7, and increased thereafter to reach their pretransportation levels by day 21 after transportation. Compared with day 0 levels, mean SOD activity and GSH concentration were decreased significantly on day 1; they thereafter increased to reach their pretransportation measures by day 7 after transportation. In contrast, PC and malondialdehyde concentrations in serum and the activity of GSH-Px were increased on day 1 compared with day 0 and thereafter decreased to reach their pretransportation levels by day 14 after transportation. In summary, GSH, TAOC, catalase, and SOD levels decreased and malondialdehyde, PC, and GSH-Px concentrations increased in cynomolgus macaques after transportation. These results suggest that transportation might imbalance oxidant and antioxidant levels to create excess oxidative stress in cynomolgus macaques. Therefore, cynomolgus macaques should have at least 21 d to recover after transportation and regain their healthy status.

  1. Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

    Science.gov (United States)

    Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

    2015-10-01

    Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

  2. On the pull: periplasmic trapping of sugars before transport.

    Science.gov (United States)

    Thomas, Gavin H

    2017-06-01

    Bacteria have evolved many routes for taking up nutrients, demonstrating great versatility in the types and mechanism of uptake used in different physiological conditions. The discovery of a single transporter in the bacterium Advenella mimigardefordensis for the uptake of five different sugars, including L-glucose and D-xylose, is described in this issue (Meinert et al., ), providing yet another example of the surprising adaptability of bacterial transport strategies. The transporter identified is a tripartite ATP-independent (TRAP) transporter, not previously associated with sugar transport, and in fact does not transport the sugars directly at all, rather requiring them to be converted in the periplasm to their respective sugar acid forms before transport through what appears to be a novel general sugar acid transporter. In this commentary, I describe how this process is consistent with the known mechanisms of TRAP transporters and consider how the role of sugar oxidation, or oxidative fermentation, operates with multiple hexose and pentose sugars. Finally I suggest that the periplasmic conversion of nutrients acquired across the outer membrane, before transport across the inner membrane, could have potentially useful biological functions in Gram negative bacteria. © 2017 John Wiley & Sons Ltd.

  3. A detailed approach to model transport, heterogeneous chemistry, and electrochemistry in solid-oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Janardhanan, V.

    2007-07-01

    This dissertation layes out detailed descriptions for heterogeneous chemistry, electrochemistry, and porous media transport models to simulate solid oxide fuel cells (SOFCs). An elementary like heterogeneous reaction mechanism for the steam reforming of CH4 developed in our research group is used throughout this work. Based on assumption of hydrogen oxidation as the only electrochemical reaction and single step electron transfer reaction as rate limiting, a modified Butler-Volmer equation is used to model the electrochemistry. The pertinence of various porous media transport models such as Modified Fick Model (MFM), Dusty Gas Model (DGM), Mean Transport Pore Model, Modified Maxwell Stefan Model, and Generalized Maxwell Stefan Model under reaction conditions are studied. In general MFM and DGM predictions are in good agreement with experimental data. Physically realistic electrochemical model parameters are very important for fuel cell modeling. Button cell simulations are carried out to deduce the electrochemical model parameters, and those parameters are further used in the modeling of planar cells. Button cell simulations are carried out using the commercial CFD code FLUENT coupled with DETCHEM. For all temperature ranges the model works well in predicting the experimental observations in the high current density region. However, the model predicts much higher open circuit potentials than that observed in the experiments, mainly due to the absence of coking model in the elementary heterogeneous mechanism leading to nonequilibrium compositions. Furthermore, the study presented here employs Nernst equation for the calculation of reversible potential which is strictly valid only for electrochemical equilibrium. It is assumed that the electrochemical charge transfer reaction involving H2 is fast enough to be in equilibrium. However, the comparison of model prediction with thermodynamic equilibrium reveals that this assumption is violated under very low current

  4. Spin transport in oxygen adsorbed graphene nanoribbon

    Science.gov (United States)

    Kumar, Vipin

    2018-04-01

    The spin transport properties of pristine graphene nanoribbons (GNRs) have been most widely studied using theoretical and experimental tools. The possibilities of oxidation of fabricated graphene based nano electronic devices may change the device characteristics, which motivates to further explore the properties of graphene oxide nanoribbons (GONRs). Therefore, we present a systematic computational study on the spin polarized transport in surface oxidized GNR in antiferromagnetic (AFM) spin configuration using density functional theory combined with non-equilibrium Green's function (NEGF) method. It is found that the conductance in oxidized GNRs is significantly suppressed in the valance band and the conduction band. A further reduction in the conductance profile is seen in presence of two oxygen atoms on the ribbon plane. This change in the conductance may be attributed to change in the surface topology of the ribbon basal plane due to presence of the oxygen adatoms, where the charge transfer take place between the ribbon basal plane and the oxygen atoms.

  5. Transport parameters of thin, supported cathode layers in solid oxide fuel cells (SOFCs); Transportparameter duenner, getraegerter Kathodenschichten der oxidkeramischen Brennstoffzelle

    Energy Technology Data Exchange (ETDEWEB)

    Wedershoven, Christian

    2010-12-22

    The aim of this work was to determine the transport properties of thin cathode layers, which are part of the composite layer of a fabricated anode-supported solid oxide fuel cell (SOFC). The transport properties of the anode and cathode have a significant influence on the electrochemical performance of a fuel cell stack and therefore represent an important parameter when designing fuel cell stacks. In order to determine the transport parameters of the cathode layers in a fabricated SOFC, it is necessary to permeate the thin cathode layer deposited on the gas-tight electrolyte with a defined gas transport. These thin cathode layers cannot be fabricated as mechanically stable single layers and cannot therefore be investigated in the diffusion and permeation experiments usually used to determine transport parameters. The setup of these experiments - particularly the sample holder - was therefore altered in this work. The result of this altered setup was a three-dimensional flow configuration. Compared to the conventional setup, it was no longer possible to describe the gas transport in the experiments with an analytical one-dimensional solution. A numerical solution process had to be used to evaluate the measurements. The new setup permitted a sufficiently symmetrical gas distribution and thus allowed the description of the transport to be reduced to a two-dimensional description, which significantly reduced the computational effort required to evaluate the measurements. For pressure-induced transport, a parametrized coherent expression of transport could be derived. This expression is equivalent to the analytical description of the transport in conventional measurement setups, with the exception of parameters that describe the geometry of the gas diffusion. In this case, a numerical process is not necessary for the evaluation. Using the transport parameters of mechanically stable anode substrates, which can be measured both in the old and the new setups, the old and

  6. Control of lipid oxidation at the mitochondrial level

    DEFF Research Database (Denmark)

    Sahlin, Kent

    2009-01-01

    , but the mechanisms regulating fuel preferences remain unclear. During intense exercise, oxidation of long-chain fatty acids (LCFAs) decreases, and the major control is likely to be at the mitochondrial level. Potential mitochondrial sites for control of lipid oxidation include transport of LCFAs into mitochondrial......-oxidation by redox state is thought to be an important mechanism for the slowing of lipid oxidation during intensive exercise....

  7. 78 FR 6400 - Results of FAA Nitrous Oxide BLEVE Characterization Testing

    Science.gov (United States)

    2013-01-30

    ... DEPARTMENT OF TRANSPORTATION Federal Aviation Administration Results of FAA Nitrous Oxide BLEVE Characterization Testing AGENCY: Federal Aviation Administration (FAA), DOT. ACTION: Notice of public... FAA sponsored testing of nitrous oxide (N 2 O) characteristics. Nitrous oxide is an important oxidizer...

  8. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    Science.gov (United States)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  9. Mitochondrial oxidative function and type 2 diabetes

    DEFF Research Database (Denmark)

    Rabøl, Rasmus; Boushel, Robert; Dela, Flemming

    2006-01-01

    The cause of insulin resistance and type 2 diabetes is unknown. The major part of insulin-mediated glucose disposal takes place in the skeletal muscle, and increased amounts of intramyocellular lipid has been associated with insulin resistance and linked to decreased activity of mitochondrial...... oxidative phosphorylation. This review will cover the present knowledge and literature on the topics of the activity of oxidative enzymes and the electron transport chain (ETC) in skeletal muscle of patients with type 2 diabetes. Different methods of studying mitochondrial function are described, including...... biochemical measurements of oxidative enzyme and electron transport activity, isolation of mitochondria for measurements of respiration, and ATP production and indirect measurements of ATP production using nuclear magnetic resonance (NMR) - spectroscopy. Biochemical markers of mitochondrial content are also...

  10. Efficient and ultraviolet durable planar perovskite solar cells via a ferrocenecarboxylic acid modified nickel oxide hole transport layer.

    Science.gov (United States)

    Zhang, Jiankai; Luo, Hui; Xie, Weijia; Lin, Xuanhuai; Hou, Xian; Zhou, Jianping; Huang, Sumei; Ou-Yang, Wei; Sun, Zhuo; Chen, Xiaohong

    2018-03-28

    Planar perovskite solar cells (PSCs) that use nickel oxide (NiO x ) as a hole transport layer have recently attracted tremendous attention because of their excellent photovoltaic efficiencies and simple fabrication. However, the electrical conductivity of NiO x and the interface contact properties of the NiO x /perovskite layer are always limited for the NiO x layer fabricated at a relatively low annealing temperature. Ferrocenedicarboxylic acid (FDA) was firstly introduced to modify a p-type NiO x hole transport layer in PSCs, which obviously improves the crystallization of the perovskite layer and hole transport and collection abilities and reduces carrier recombination. PSCs with a FDA modified NiO x layer reached a PCE of 18.20%, which is much higher than the PCE (15.13%) of reference PSCs. Furthermore, PSCs with a FDA interfacial modification layer show better UV durability and a hysteresis-free effect and still maintain the original PCE value of 49.8%after being exposed to UV for 24 h. The enhanced performance of the PSCs is attributed to better crystallization of the perovskite layer, the passivation effect of FDA, superior interface contact at the NiO x /perovskite layers and enhancement of the electrical conductivity of the FDA modified NiO x layer. In addition, PSCs with FDA inserted at the interface of the perovskite/PCBM layers can also improve the PCE to 16.62%, indicating that FDA have dual functions to modify p-type and n-type carrier transporting layers.

  11. The Properties Of And Transport Phenomena In Oxide Films On Iron, Nickel, Chromium And Their Alloys In Aqueous Environments

    International Nuclear Information System (INIS)

    Saario, T.; Laitinen, T.; Maekelae, K.; Bojinov, M.; Betova, I.

    1998-07-01

    . In addition, the films are to a large extent influenced by the kinetic factors determining their growth rate and steady state thickness. Thus a thermodynamic consideration of the film is not sufficient to model and predict its growth and dissolution. Instead, kinetic models based on in situ experimental data are required. The kinetic models presented in the literature for both ambient and high-temperature aqueous oxidation of metals lack a correlation between the structure of the oxide films and their electronic and ionic properties. Also, a quantitative treatment and thus the capability to predict material behaviour in varying conditions is lacking. A comprehensive understanding of the correlation between applied water chemistry, the behaviour of oxide films and optimum performance of the plant is thus also lacking. The situation calls for more experimental work combined with comprehensive modelling of the behaviour of both the dense and the porous part of the oxide film formed on a metal surface. This will make it possible to recognise the rate-limiting steps of the processes in the film, and thus to influence the rate of activity incorporation and different corrosion phenomena related to transport of species in the film. (author)

  12. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"-, it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. [de

  13. Attenuation of pyrite oxidation with a fly ash pre-barrier: Reactive transport modelling of column experiments

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Lopez, R.; Cama, J.; Nieto, J.M.; Ayora, C.; Saaltink, M.W. [University of Huelva, Huelva (Spain). Dept. of Geology

    2009-09-15

    Conventional permeable reactive barriers (PRBs) for passive treatment of groundwater contaminated by acid mine drainage (AMD) use limestone as reactive material that neutralizes water acidity. However, the limestone-alkalinity potential ceases as inevitable precipitation of secondary metal-phases on grain surfaces occurs, limiting its efficiency. In the present study, fly ash derived from coal combustion is investigated as an alternative alkalinity generating material for the passive treatment of AMD using solution-saturated column experiments. Unlike conventional systems, the utilization of fly ash in a pre-barrier to intercept the non-polluted recharge water before this water reacts with pyrite-rich wastes is proposed. Chemical variation in the columns was interpreted with the reactive transport code RETRASO. In parallel, kinetics of fly ash dissolution at alkaline pH were studied using flow-through experiments and incorporated into the model. In a saturated column filled solely with pyritic sludge-quartz sand (1: 10), oxidation took place at acidic conditions (pH 3.7). According to SO{sub 4}{sup 2-} release and pH, pyrite dissolution occurred favourably in the solution-saturated porous medium until dissolved O{sub 2} was totally consumed. In a second saturated column, pyrite oxidation took place at alkaline conditions (pH 10.45) as acidity was neutralized by fly ash dissolution in a previous level. At this pH Fe release from pyrite dissolution was immediately depleted as Fe-oxy(hydroxide) phases that precipitated on the pyrite grains, forming Fe-coatings (microencapsulation). With time, pyrite microencapsulation inhibited oxidation in practically 97% of the pyritic sludge. Rapid pyrite-surface passivation decreased its reactivity, preventing AMD production in the relatively short term.

  14. Reaction and Transport Processes Controlling In Situ Chemical Oxidation of DNAPLs

    National Research Council Canada - National Science Library

    Siegrist, Robert L; Crimi, Michelle; Munakata-Marr, Junko; Illangasekare, Tissa; Dugan, Pamela; Heiderscheidt, Jeff; Jackson, Shannon; Petri, Ben; Sahl, Jason; Seitz, Sarah

    2006-01-01

    In situ chemical oxidation involves the introduction of chemical oxidants into the subsurface to destroy organic contaminants in soil and ground water, with the goal being to reduce the mass, mobility...

  15. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

    Science.gov (United States)

    Runkel, Robert L.; Kimball, Briant A.; McKnight, Diane M.; Bencala, Kenneth E.

    1999-01-01

    A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

  16. Redox-controlled dinitrosyl formation at the diiron-oxo center of NorA.

    Science.gov (United States)

    Cramm, Rainer; Strube, Katja

    2008-01-01

    In the denitrifying bacterium Ralstonia eutropha H16, the NorA protein is coproduced with the respiratory nitric oxide (NO) reductase. NorA contains a diiron-oxo center, which can form stable adducts with dioxygen and NO. In contrast to other diiron proteins, the formation of NorA-NO requires both fully reduced protein and additional electrons. A minor fraction of in vitro NorA-NO represents a paramagnetic dinitrosyl iron complex (DNIC), while the major fraction is attributed to a DNIC of the structure {Fe(NO)(2)}, which shows no electron paramagnetic resonance. The NorA-DNIC may be formed either upon direct reaction of the protein with NO or upon incubation with nitrite due to an intrinsic nitrite reduction activity of NorA that liberates NO. NorA can be purified rapidly as a six histidine-tagged derivative from overproducing cells of Escherichia coli. This chapter describes procedures for the preparation of different redox forms of NorA for the formation of NorA adducts with NO, dioxygen, and azide, as well as for the quantification of NorA-bound NO.

  17. Technological alternatives for plutonium transport

    International Nuclear Information System (INIS)

    1978-12-01

    This paper considers alternative transport modes (air, sea, road, rail) for moving (1) plutonium from a reprocessing plant to a store or a fuel fabrication facility, and (2) MOX fuel from the latter to a reactor. These transport modes and differing forms of plutonium are considered in terms of: their proliferation resistance and safeguards; environmental and safety aspects; and economic aspects. It is tentatively proposed that the transport of plutonium could continue by air or sea where long distances are involved and by road or rail over shorter distances; this would be acceptable from the non-proliferation, environmental impact and economic aspects - there may be advantages in protection if plutonium is transported in the form of mixed oxide

  18. Radio-oxidation of an EPDM elastomer under weak or strong ionising radiations: measurement and modelling of dioxygen consumption; Radio-oxydation d'un elastomere de type EPDM lors d'irradiations faiblement ou fortement ionisantes: mesure et modelisation de la consommation de dioxygene

    Energy Technology Data Exchange (ETDEWEB)

    Dely, N

    2005-10-15

    Usually, the irradiation of polymers under ionising radiations occurs in air that is in the presence of oxygen. This leads to a radio oxidation process and to oxygen consumption. Our material is an EPDM elastomer (ethylene propylene 1,4 hexadiene) used as insulator in control-command cables in nuclear plants (Pressurised Water Reactor). A specific device has been conceived and built up during this PhD work for measuring very small oxygen consumptions with an accuracy of around 10%. Ionising radiations used are electrons at 1 MeV and carbon ions at 11 MeV per nucleon. Under both electron and ion irradiations, the influence of oxygen pressure on oxygen consumption has been studied in a very large range: between 1 and 200 mbar. In both cases, the yield of oxygen consumption is constant in-between 200 and 5 mbar. Then, at lower pressures, it decreases appreciably. On the other hand, the oxygen consumption during ion irradiation is four times smaller than during electron irradiation. This emphasizes the role of the heterogeneity of the energy deposition at a nano-metric scale. The adjustment of the experimental results obtained during electron irradiation with the general homogeneous steady-state kinetic model has allowed extracting all the values of the kinetic parameters for the chosen mechanism of radio oxidation. The knowledge of these numbers will allow us to face our results obtained during ion irradiation with a heterogeneous kinetic model under development. (author)

  19. A conceptual model for the fuel oxidation of defective fuel

    International Nuclear Information System (INIS)

    Higgs, J.D.; Lewis, B.J.; Thompson, W.T.; He, Z.

    2007-01-01

    A mechanistic conceptual model has been developed to predict the fuel oxidation behaviour in operating defective fuel elements for water-cooled nuclear reactors. This theoretical work accounts for gas-phase transport and sheath reactions in the fuel-to-sheath gap to determine the local oxygen potential. An improved thermodynamic analysis has also been incorporated into the model to describe the equilibrium state of the oxidized fuel. The fuel oxidation kinetics treatment accounts for multi-phase transport including normal diffusion and thermodiffusion for interstitial oxygen migration in the solid, as well as gas-phase transport in the fuel pellet cracks. The fuel oxidation treatment is further coupled to a heat conduction equation. A numerical solution of the coupled transport equations is obtained by a finite-element technique with the FEMLAB 3.1 software package. The model is able to provide radial-axial profiles of the oxygen-to-uranium ratio and the fuel temperatures as a function of time in the defective element for a wide range of element powers and defect sizes. The model results are assessed against coulometric titration measurements of the oxygen-to-metal profile for pellet samples taken from ten spent defective elements discharged from the National Research Universal Reactor at the Chalk River Laboratories and commercial reactors

  20. The ameliorative effect of ascorbic acid on the oxidative status, live weight and recovery rate in road transport stressed goats in a hot humid tropical environment.

    Science.gov (United States)

    Nwunuji, Tanko Polycarp; Mayowa, Opeyemi Onilude; Yusoff, Sabri Mohd; Bejo, Siti-Khairani; Salisi, Shahrom; Mohd, Effendy Abd Wahid

    2014-05-01

    The ameliorative effect of ascorbic acid (AA) on live weight following transportation is vital in animal husbandry. This study investigated the influence of AA on live weight, rectal temperature (rt), and oxidative status of transport stressed goats in a hot humid tropical environment. Twenty-four goats were divided into four groups, A, B, C and D of six animals each. Group A were administered AA 100 mg/kg intramuscularly 30 min prior to 3.5 h transportation. Group B was administered AA following transportation. Group C were transported but not administered AA as positive controls while group D were not transported but were administered normal saline as negative controls. Live weight, rt and blood samples were collected before, immediately post-transport (pt), 24 h, 3 days, 7 days and 10 days pt. Plasma was used for malondialdehyde (MDA) analysis while hemolysates were used for superoxide dismutase (SOD) analysis. There was minimal live weight loss in group A compared to groups B and C. Group A recorded reduced MDA activities and increased SOD activities compared to groups B and C which recorded significantly high MDA activities. This study revealed that AA administration ameliorated the stress responses induced by transportation in animals in hot humid tropical environments. The administration of AA to goats prior to transportation could ameliorate stress and enhance productivity. © 2014 Japanese Society of Animal Science.

  1. Mathematical modelling of transport of gaseous and liquid substances induced by pyrite oxidation in spoil banks of lignite mines; Mathematische Modellierung der durch Pyritoxidation induzierten Stofftransporte in Braunkohleabraumkippen in gasfoermiger und fluessiger Phase

    Energy Technology Data Exchange (ETDEWEB)

    Ludwig, R.

    2001-07-01

    Pyrite (FeS{sub 2}) oxidation due to open-pit lignite mining activities may result in acid mine drainage and dissolved metals in the soil and ground water of the overburden spoil piles. The pyrite oxidation takes place firstly during the mining process and at the temporary surfaces of the mine, secondly in deep zones of the overburden spoil pile as a result of gas transport through the unsaturated zone. The second process continues after mine closure possibly over several decades and therefore contaminates the environment for a long time. Whereas some studies deal with a minimisation by geochemical means, this research focuses on a minimisation by impacting the physical boundary conditions. Special attention is given to the transport of oxygen from the soil surface to the pyrite oxidation zone. Soil column experiments with columns of 2.90 m height yield experimental data concerning the pyrite oxidation and the related transport processes in the unsaturated zone. Experimental data are compared to simulation results obtained with the model MUSIC; it calculates coupled reaction and transport processes in a one-dimensional soil profile using the finite volume method. Pyrite oxidation is described by means of a first order kinetics, the gas transport takes place by diffusion as well as convection. The transport of solutes in the soil water is described by the convection-dispersion equation (Cl{sup -}, Fe{sup 2+} and SO{sub 4}{sup 2-}). The simulations are able to reproduce the measured time series of oxygen concentrations in the soil profile. (orig.) [German] Die durch Braunkohlegewinnung im Tagebau hervorgerufene Pyritoxidation (Pyrit: FeS{sub 2}) kann zu Versauerung, Schwermetallfreisetzung und Aufmineralisierung des Boden- und Grundwassers in den Abraumkippen fuehren. Die Pyritoxidation findet zum einen waehrend des Abbaubetriebs und an den temporaeren Oberflaechen des Tagebaus statt, zum anderen in tieferen Bereichen der Abraumkippe durch Gastransport durch die

  2. Transport experience of new ''TNF-XI'' powder package

    International Nuclear Information System (INIS)

    Nomura, I.; Fujiwara, T.; Naigeon, P.

    2004-01-01

    Since the Tokai criticality accident in 1999, there has been no specialized manufacturer conducting uranium re-conversion in Japan. For this reason, Nuclear Fuel Industries, Ltd. (NFI) imports from overseas almost all the uranium oxide powder used for manufacturing pellets for nuclear fuel assemblies. To date, an NT-IX package has been used for transporting the uranium oxide powder. However, due to the adoption of IAEA TS-R-1 into Japanese domestic regulations, we have begun to use a new TNF-XI powder package because the NT-IX package can suffer major deformation under the drop test III condition. The TNF-XI package was jointly developed by COGEMA LOGISTICS of France and NFI from 2000, and started to be used for actual transportation in 2003. This package has improved transport efficiency, handling operability and safety performance in comparison to its predecessor. This paper describes the characteristics of the new TNF-XI package and its actual transportation records and performance

  3. Oxygen-induced inhibition of silicon-on-insulator dewetting

    Energy Technology Data Exchange (ETDEWEB)

    Curiotto, S.; Leroy, F.; Cheynis, F.; Müller, P. [Aix Marseille Université, CNRS, CINaM UMR 7325, 13288 Marseille (France)

    2014-02-10

    We report that solid state dewetting of Si thin film on SiO{sub 2} can be reversibly inhibited by exposing the Si surface to a partial pressure of dioxygen (∼10{sup −7}Torr) at high temperature (∼1100K). Coupling in situ Low-Energy Electron Microscopy and ex situ atomic force microscopy we propose that the pinning of the contact line induced by the presence of small amounts of silicon oxide is the main physical process that inhibits the dewetting.

  4. The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

    Energy Technology Data Exchange (ETDEWEB)

    Chan, Clara Sze-Yue [Univ. of Delaware, Newark, DE (United States)

    2015-07-02

    Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Rifle aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles

  5. Response of Lemna minor L. to short-term cobalt exposure: The effect on photosynthetic electron transport chain and induction of oxidative damage

    International Nuclear Information System (INIS)

    Begović, Lidija; Mlinarić, Selma; Antunović Dunić, Jasenka; Katanić, Zorana; Lončarić, Zdenko; Lepeduš, Hrvoje; Cesar, Vera

    2016-01-01

    Highlights: • Cobalt (Co"2"+) impaired the function of oxygen evolving complex (OEC) in L. minor L. • Electron transport through PSII components varied depending on Co"2"+ concentration. • K-band was proven to be suitable parameter for investigation of Co"2"+ toxicity. • Increased lipid peroxidation level showed early oxidative damage induced by Co"2"+. - Abstract: The effect of two concentrations of cobalt (Co"2"+) on photosynthetic activity and antioxidative response in Lemna minor L. were assessed 24, 48 and 72 h after the start of the exposure. Higher concentration of cobalt (1 mM) induced growth inhibition while lower concentration (0.01 mM) increased photosynthetic pigments content. Analysis of chlorophyll a fluorescence transients revealed high sensitivity of photosystem II primary photochemistry to excess of Co"2"+ especially at the higher concentration where decreased electron transport beyond primary quinone acceptor Q_A"− and impaired function of oxygen evolving complex (OEC) was observed. Due to impairment of OEC, oxygen production was decreased at higher Co"2"+ concentration. Activity of superoxide dismutase was mainly inhibited while lipid peroxidation increased, at both concentrations, indicating that cobalt-induced oxidative damage after short exposure and moreover, susceptibility of the membranes in the cell to cobalt toxicity. Results obtained in this study suggest possible application of used parameters as tools in assessment of early damage caused by metals.

  6. The Oxidation of Rhenium(III) by Dioxygen in the Presence of Tri ...

    African Journals Online (AJOL)

    NICO

    Both compounds were characterized by 1H NMR and infrared spectroscopy, and ... Microanalyses were obtained on a Carlo Erba EA 1108 elemental .... Spectral Characterization ... of this signal so far downfield indicates the existence of the.

  7. Kelvin probe microscopy and electronic transport measurements in reduced graphene oxide chemical sensors

    Science.gov (United States)

    Kehayias, Christopher E.; MacNaughton, Samuel; Sonkusale, Sameer; Staii, Cristian

    2013-06-01

    Reduced graphene oxide (RGO) is an electronically hybrid material that displays remarkable chemical sensing properties. Here, we present a quantitative analysis of the chemical gating effects in RGO-based chemical sensors. The gas sensing devices are patterned in a field-effect transistor geometry, by dielectrophoretic assembly of RGO platelets between gold electrodes deposited on SiO2/Si substrates. We show that these sensors display highly selective and reversible responses to the measured analytes, as well as fast response and recovery times (tens of seconds). We use combined electronic transport/Kelvin probe microscopy measurements to quantify the amount of charge transferred to RGO due to chemical doping when the device is exposed to electron-acceptor (acetone) and electron-donor (ammonia) analytes. We demonstrate that this method allows us to obtain high-resolution maps of the surface potential and local charge distribution both before and after chemical doping, to identify local gate-susceptible areas on the RGO surface, and to directly extract the contact resistance between the RGO and the metallic electrodes. The method presented is general, suggesting that these results have important implications for building graphene and other nanomaterial-based chemical sensors.

  8. Kelvin probe microscopy and electronic transport measurements in reduced graphene oxide chemical sensors.

    Science.gov (United States)

    Kehayias, Christopher E; MacNaughton, Samuel; Sonkusale, Sameer; Staii, Cristian

    2013-06-21

    Reduced graphene oxide (RGO) is an electronically hybrid material that displays remarkable chemical sensing properties. Here, we present a quantitative analysis of the chemical gating effects in RGO-based chemical sensors. The gas sensing devices are patterned in a field-effect transistor geometry, by dielectrophoretic assembly of RGO platelets between gold electrodes deposited on SiO2/Si substrates. We show that these sensors display highly selective and reversible responses to the measured analytes, as well as fast response and recovery times (tens of seconds). We use combined electronic transport/Kelvin probe microscopy measurements to quantify the amount of charge transferred to RGO due to chemical doping when the device is exposed to electron-acceptor (acetone) and electron-donor (ammonia) analytes. We demonstrate that this method allows us to obtain high-resolution maps of the surface potential and local charge distribution both before and after chemical doping, to identify local gate-susceptible areas on the RGO surface, and to directly extract the contact resistance between the RGO and the metallic electrodes. The method presented is general, suggesting that these results have important implications for building graphene and other nanomaterial-based chemical sensors.

  9. A pore structure model for the gas transport property changes, initial oxidation rates and cumulative weight loss of AGR moderator graphite

    International Nuclear Information System (INIS)

    Johnson, P.A.V.

    1985-09-01

    A quantitative model has been developed for the gas transport property variation, cumulative weight loss and initial oxidation rates of AGR moderator graphite. The model utilises the theory of dynamic moments of the pore structure to calculate the changes in physical properties brought about by radiolytic corrosion taking place within the graphite porosity. In order to account for the behaviour of the initial rate curves, and the weight loss data obtained it is necessary to invoke the presence of a group of cylindrical pore and a group of small slab-shaped pores. The latter are methane depleted. This is in addition to the pore group involved in gas transport which is best represented by cylinders of mean radius 2.13 μm. The model satisfactorily predicts the experimental weight loss data obtained from experiments in the DIDO 6V3 and BFB loops. (author)

  10. Human transporter database: comprehensive knowledge and discovery tools in the human transporter genes.

    Directory of Open Access Journals (Sweden)

    Adam Y Ye

    Full Text Available Transporters are essential in homeostatic exchange of endogenous and exogenous substances at the systematic, organic, cellular, and subcellular levels. Gene mutations of transporters are often related to pharmacogenetics traits. Recent developments in high throughput technologies on genomics, transcriptomics and proteomics allow in depth studies of transporter genes in normal cellular processes and diverse disease conditions. The flood of high throughput data have resulted in urgent need for an updated knowledgebase with curated, organized, and annotated human transporters in an easily accessible way. Using a pipeline with the combination of automated keywords query, sequence similarity search and manual curation on transporters, we collected 1,555 human non-redundant transporter genes to develop the Human Transporter Database (HTD (http://htd.cbi.pku.edu.cn. Based on the extensive annotations, global properties of the transporter genes were illustrated, such as expression patterns and polymorphisms in relationships with their ligands. We noted that the human transporters were enriched in many fundamental biological processes such as oxidative phosphorylation and cardiac muscle contraction, and significantly associated with Mendelian and complex diseases such as epilepsy and sudden infant death syndrome. Overall, HTD provides a well-organized interface to facilitate research communities to search detailed molecular and genetic information of transporters for development of personalized medicine.

  11. European experience with spent fuel transport

    International Nuclear Information System (INIS)

    Hunter, I.A.

    1995-01-01

    Nuclear Transport Ltd has transported 5000 tonnes of spent fuel from 35 reactors in 8 European countries since 1972. Transport management is governed by the Quality Plan for: transport administration, packaging and shipment procedures at the shipping plant, operations at the power plant, and packaging and shipment organization at the power plant. Selection of a suitable carrier device is made with regard to the shipping plant requirements, physical limitations of the reactor, fuel characteristics, and transport route constraints. The transport plan is set up taking into account exploitation of the casks, reactor shut-down requirements, fuel acceptance plans at the reprocessing plant, and cask maintenance periods. A transport cycle involving spent fuel shipment to La Hague or to Sellafield takes typically two or four weeks, respectively. Most transports through Europe are by rail. A special-design railway ferry boat serves transports to the United Kingdom. Both wet or dry casks are employed. Modern casks are designed for high burnups and for oxide fuels. (J.B.)

  12. Pneumatic transport system development: residuals and releases program at Westinghouse Cheswick site

    International Nuclear Information System (INIS)

    Larouere, P.J.; Shoulders, J.L.

    1979-01-01

    Plutonium oxide and uranium oxide powders are processed within glove boxes or within confinement systems during the fabrication of mixed oxide (MOX) pellets for recycle fuel. The release of these powders to the glove box or to the confinement results in some airborne material that is deposited in the enclosure or is carried in the air streams to the effluent air filtration system. Release tests on simulated leaks in pneumatic transport equipment and release tests on simulated failures with powder blending equipment were conducted. A task to develop pneumatic transport for the movement of powders within an MOX fabrication plant has been underway at the Westinghouse Research Laboratories. While testing and evaluating selected pneumatic transport components on a full scale were in progress, it was deemed necessary that final verification of the technology would have to be performed with plutonium-bearing powders because of the marked differences in certain properties of plutonium from those of uranium oxides. A smaller was designed and constructed for the planned installation in glove boxes at the Westinghouse Plutonium Fuel Development Laboratory. However, prior to use with plutonium it was agreed that this system be set up and tested with uranium oxide powder. The test program conducted at the Westinghouse Cheswick site was divided into two major parts. The first of these examined the residuals left as a result of the pneumatic transport of nuclear fuel powders and verified the operability of this one-third scale system. The second part of the program studied the amount of powder released to the air when off-standard process procedures or maintenance operations were conducted on the pneumatic transport system. Air samplers located within the walk-in box housing the transport loop were used to measure the solids concentration in the air. From this information, the total amount of airborne powder was determined

  13. Graphene oxide/PEDOT:PSS composite hole transport layer for efficient and stable planar heterojunction perovskite solar cells.

    Science.gov (United States)

    Lee, Da-Young; Na, Seok-In; Kim, Seok-Soon

    2016-01-21

    We investigated a graphene oxide (GO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) ( PSS) composite as a promising candidate for the practical application of a 2-D carbonaceous hole transport layer (HTL) to planar heterojunction perovskite solar cells (PeSCs) consisting of a transparent electrode/HTL/perovskite/fullerene/metal electrode. Both the insulating properties of GO and the non-uniform coating of the transparent electrode with GO cause the poor morphology of perovskite induced low power conversion efficiency (PCE) of 6.4%. On the other hand, PeSCs with a GO/PEDOT:PSS composite HTL, exhibited a higher PCE of 9.7% than that of a device fabricated with conventional PSS showing a PCE of 8.2%. The higher performance is attributed to the decreased series resistance (RS) and increased shunt resistance (RSh). The well-matched work-function between GO (4.9 eV) and PSS (5.1 eV) probably results in more efficient charge transport and an overall decrease in RS. The existence of GO with a large bandgap of ∼3.6 eV might induce the effective blocking of electrons, leading to an increase of RSh. Moreover, improvement in the long-term stability under atmospheric conditions was observed.

  14. Influence of gravity on transport and retention of representative engineered nanoparticles in quartz sand.

    Science.gov (United States)

    Cai, Li; Zhu, Jinghan; Hou, Yanglong; Tong, Meiping; Kim, Hyunjung

    2015-10-01

    Four types of NPs: carbon nanotubes and graphene oxide (carbon-based NPs), titanium dioxide and zinc oxide metal-oxide NPs, were utilized to systematically determine the influence of gravity on the transport of NPs in porous media. Packed column experiments for two types of carbon-based NPs were performed under unfavorable conditions in both up-flow (gravity-negative) and down-flow (gravity-positive) orientations, while for two types of metal-oxide NPs, experiments were performed under both unfavorable and favorable conditions in both up-flow and down-flow orientations. Both breakthrough curves and retained profiles of two types of carbon-based NPs in up-flow orientation were equivalent to those in down-flow orientation, indicating that gravity had negligible effect on the transport and retention of carbon-based NPs under unfavorable conditions. In contrast, under both unfavorable and favorable conditions, the breakthrough curves for two types of metal-oxide NPs in down-flow orientation were lower relative to those in up-flow orientation, indicating that gravity could decrease the transport of metal-oxide NPs in porous media. The distinct effect of gravity on the transport and retention of carbon-based and metal-oxide NPs was mainly attributed to the contribution of gravity to the force balance on the NPs in quartz sand. The contribution of gravity was determined by the interplay of the density and sizes of NP aggregates under examined solution conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Mesoporous Transition Metal Oxides for Supercapacitors.

    Science.gov (United States)

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-10-14

    Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  16. Transport and Application of Heat-Activated Persulfate for In-situ Chemical Oxidation of Residual Trichloroethylene

    Science.gov (United States)

    Quig, L.; Johnson, G. R.

    2015-12-01

    Persulfate ISCO has been shown to treat a wide range of contaminants. While persulfate ISCO can be tailored to site and pollutant specific characteristics (e.g., activation via energy or catalysis), thermal activation of persulfate is particularly promising as it can be easily controlled and requires no additional reagents. A mechanistic study of the physical and chemical processes controlling the effectiveness of this remedial approach is not well documented in the literature with much therein focused on reactions in batch systems. The purpose of this research was twofold. Initial studies characterized the overall transport behavior of unactivated and thermally-activated persulfate (20, 60, and 90°C) in one-dimensional soil column systems. Finally, experiments were conducted to investigate persulfate ISCO as a remedial approach for residual-phase trichloroethylene (TCE). At all activation temperatures investigated, persulfate exhibited ideal transport behavior in miscible displacement experiments. Moment analysis of persulfate ion breakthrough curves indicated negligible interaction of persulfate with the natural sandy material. Persulfate ISCO for residual-phase TCE was characterized at two flow rates, 0.2 mL/min and 0.5 mL/min, resulting in two degrees of persulfate activation, 39.5% and 24.6%, respectively. Both ISCO soil column systems showed an initial, long-term plateau in effluent TCE concentrations indicating steady-state dissolution of pure phase TCE. Observed effluent concentrations decreased after 75 and 100 pore volumes (normalized for the measured residual NAPL fraction) compared to 110 pore volumes in the control study. Pseudo first-order reaction rate constants for the decreasing TCE concentrations equaled 0.063/hr and 0.083/hr, respectively, compared to 0.041/hr for the control. Moment analysis of the complete dissolution of TCE in the persulfate/activated persulfate remediation systems indicated approximately 33% oxidation of TCE mass present. By

  17. Antioxidant and oxidative stress parameters in brain of Heteropneustes fossilis under air exposure condition; role of mitochondrial electron transport chain.

    Science.gov (United States)

    Paital, Biswaranjan

    2013-09-01

    Many fishes are exposed to air in their natural habitat or during their commercial handling. In natural habitat or during commercial handling, the cat fish Heteropneustes fossilis is exposed to air for >24h. Data on its oxidative metabolism in the above condition are not available. Oxidative stress (OS) indices (lipid and protein oxidation), toxic reactive oxygen species (ROS: H2O2) generation, antioxidative status (levels of superoxide dismutase, catalase, glutathione peroxidase and reductase, ascorbic acid and non-protein sulfhydryl) and activities of electron transport chain (ETC) enzymes (complex I-IV) were investigated in brain tissue of H. fossilis under air exposure condition (0, 3, 6, 12 and 18 h at 25°C). Decreased activities of antioxidant (except catalase) and ETC enzymes (except complex II) with increased H2O2 and OS levels were observed in the tissue under water deprivation condition. Positive correlation was observed for complex II activity and non-protein thiol groups with time period of air exposure. The critical time period to induce OS and to reduce most of the studied antioxidant level in brain was found to be 3-6h air exposure. The data can be useful to minimize the stress generated during commercial handling of the live fishes those exposed to air in general and H. fossilis in particular. Copyright © 2013 Elsevier Inc. All rights reserved.

  18. Crystal Structure of Mammalian Cysteine dioxygenase: A Novel Mononuclear Iron Center for Cysteine Thiol Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Simmons,C.; Liu, Q.; Huang, Q.; Hao, Q.; Begley, T.; Karplus, P.; Stipanuk, M.

    2006-01-01

    Cysteine dioxygenase is a mononuclear iron-dependent enzyme responsible for the oxidation of cysteine with molecular oxygen to form cysteinesulfinate. This reaction commits cysteine to either catabolism to sulfate and pyruvate or to the taurine biosynthetic pathway. Cysteine dioxygenase is a member of the cupin superfamily of proteins. The crystal structure of recombinant rat cysteine dioxygenase has been determined to 1.5 Angstroms resolution, and these results confirm the canonical cupin {beta}-sandwich fold and the rare cysteinyl-tyrosine intramolecular crosslink (between Cys93 and Tyr157) seen in the recently reported murine cysteine dioxygenase structure. In contrast to the catalytically inactive mononuclear Ni(II) metallocenter present in the murine structure, crystallization of a catalytically competent preparation of rat cysteine dioxygenase revealed a novel tetrahedrally coordinated mononuclear iron center involving three histidines (His86, His88, and His140) and a water molecule. Attempts to acquire a structure with bound ligand using either co-crystallization or soaks with cysteine revealed the formation of a mixed disulfide involving Cys164 near the active site, which may explain previously observed substrate inhibition. This work provides a framework for understanding the molecular mechanisms involved in thiol dioxygenation and sets the stage for exploring the chemistry of both the novel mononuclear iron center and the catalytic role of the cysteinyl-tyrosine linkage.

  19. Nanocomposite oxide thin films grown by pulsed energy beam deposition

    International Nuclear Information System (INIS)

    Nistor, M.; Petitmangin, A.; Hebert, C.; Seiler, W.

    2011-01-01

    Highly non-stoichiometric indium tin oxide (ITO) thin films were grown by pulsed energy beam deposition (pulsed laser deposition-PLD and pulsed electron beam deposition-PED) under low oxygen pressure. The analysis of the structure and electrical transport properties showed that ITO films with a large oxygen deficiency (more than 20%) are nanocomposite films with metallic (In, Sn) clusters embedded in a stoichiometric and crystalline oxide matrix. The presence of the metallic clusters induces specific transport properties, i.e. a metallic conductivity via percolation with a superconducting transition at low temperature (about 6 K) and the melting and freezing of the In-Sn clusters in the room temperature to 450 K range evidenced by large changes in resistivity and a hysteresis cycle. By controlling the oxygen deficiency and temperature during the growth, the transport and optical properties of the nanocomposite oxide films could be tuned from metallic-like to insulating and from transparent to absorbing films.

  20. Response of Lemna minor L. to short-term cobalt exposure: The effect on photosynthetic electron transport chain and induction of oxidative damage

    Energy Technology Data Exchange (ETDEWEB)

    Begović, Lidija, E-mail: lbegovic@biologija.unios.hr [Josip Juraj Strossmayer University of Osijek, Department of Biology, Ulica cara Hadrijana 8/A, H R -31000 Osijek (Croatia); Mlinarić, Selma, E-mail: smlinaric@biologija.unios.hr [Josip Juraj Strossmayer University of Osijek, Department of Biology, Ulica cara Hadrijana 8/A, H R -31000 Osijek (Croatia); Antunović Dunić, Jasenka, E-mail: jantunovic@biologija.unios.hr [Josip Juraj Strossmayer University of Osijek, Department of Biology, Ulica cara Hadrijana 8/A, H R -31000 Osijek (Croatia); Katanić, Zorana, E-mail: zkatanic@biologija.unios.hr [Josip Juraj Strossmayer University of Osijek, Department of Biology, Ulica cara Hadrijana 8/A, H R -31000 Osijek (Croatia); Lončarić, Zdenko, E-mail: zdenko.loncaric@pfos.hr [Faculty of Agriculture, Josip Juraj Strossmayer University of Osijek, Ulica kralja Petra Svačića 1d, H R -31000 Osijek (Croatia); Lepeduš, Hrvoje, E-mail: hlepedus@yahoo.com [Faculty of Humanities and Social Sciences, Josip Juraj Strossmayer University of Osijek, Lorenza Jägera 9, HR-31000 Osijek (Croatia); Cesar, Vera, E-mail: vcesarus@yahoo.com [Josip Juraj Strossmayer University of Osijek, Department of Biology, Ulica cara Hadrijana 8/A, H R -31000 Osijek (Croatia)

    2016-06-15

    Highlights: • Cobalt (Co{sup 2+}) impaired the function of oxygen evolving complex (OEC) in L. minor L. • Electron transport through PSII components varied depending on Co{sup 2+} concentration. • K-band was proven to be suitable parameter for investigation of Co{sup 2+} toxicity. • Increased lipid peroxidation level showed early oxidative damage induced by Co{sup 2+}. - Abstract: The effect of two concentrations of cobalt (Co{sup 2+}) on photosynthetic activity and antioxidative response in Lemna minor L. were assessed 24, 48 and 72 h after the start of the exposure. Higher concentration of cobalt (1 mM) induced growth inhibition while lower concentration (0.01 mM) increased photosynthetic pigments content. Analysis of chlorophyll a fluorescence transients revealed high sensitivity of photosystem II primary photochemistry to excess of Co{sup 2+} especially at the higher concentration where decreased electron transport beyond primary quinone acceptor Q{sub A}{sup −} and impaired function of oxygen evolving complex (OEC) was observed. Due to impairment of OEC, oxygen production was decreased at higher Co{sup 2+} concentration. Activity of superoxide dismutase was mainly inhibited while lipid peroxidation increased, at both concentrations, indicating that cobalt-induced oxidative damage after short exposure and moreover, susceptibility of the membranes in the cell to cobalt toxicity. Results obtained in this study suggest possible application of used parameters as tools in assessment of early damage caused by metals.

  1. Simple solution-processed titanium oxide electron transport layer for efficient inverted polymer solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Liang [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Shen, Wenfei [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Institute of Hybrid Materials, Laboratory of New Fiber Materials and Modern Textile—The Growing Base for State Key Laboratory, Qingdao University, Qingdao 266071 (China); Chen, Weichao [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Bao, Xichang, E-mail: baoxc@qibebt.ac.cn [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Wang, Ning; Dou, Xiaowei; Han, Liangliang; Wen, Shuguang [CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China)

    2014-12-31

    Titanium oxide (TiO{sub X}) is an effective electron transport layer (ETL) in polymer solar cells (PSCs). We report efficient inverted PSCs with a simple solution-processed amorphous TiO{sub X} (s-TiO{sub X}) film as an ETL. The s-TiO{sub X} film with high light transmittance was prepared by spin-coating titanium (IV) isopropoxide isopropanol solution on indium tin oxide coated glass in inert and then placed in air under room temperature for 60 min. The introduction of s-TiO{sub X} ETL greatly improved the short circuit current density of the devices. PSCs based on poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester and poly(4,8-bis-alkyloxy-benzo[1,2-b:4,5-b′]dithiophene-alt-alkylcarbonyl -thieno[3,4-b]thiophene):[6,6]-phenyl- C71-butyric acid methyl ester using s-TiO{sub X} film as ETL shows high power conversion efficiency of 4.29% and 6.7% under the illumination of AM 1.5G, 100 mW/cm{sup 2}, which shows enhancements compared to the conventional PSCs with poly(styrenesulfonate)-doped poly(ethylenedioxythiophene) as anode buffer layer. In addition, the device exhibits good stability in a humid ambient atmosphere without capsulation. The results indicate that the annealing-free, simple solution processed s-TiO{sub X} film is an efficient ETL for high-performance PSCs. - Highlights: • High quality s-TiO{sub X} films were prepared by a simple, solution method without thermal treatment. • The s-TiO{sub X} films with high transmittance are very smooth. • The organic photovoltaic performance with s-TiO{sub X} film improved greatly and exhibited good stability. • The annealing-free, simple prepared s-TiO{sub X} film will be much compatible with flexible substrates.

  2. Thermal transport properties of polycrystalline tin-doped indium oxide films

    International Nuclear Information System (INIS)

    Ashida, Toru; Miyamura, Amica; Oka, Nobuto; Sato, Yasushi; Shigesato, Yuzo; Yagi, Takashi; Taketoshi, Naoyuki; Baba, Tetsuya

    2009-01-01

    Thermal diffusivity of polycrystalline tin-doped indium oxide (ITO) films with a thickness of 200 nm has been characterized quantitatively by subnanosecond laser pulse irradiation and thermoreflectance measurement. ITO films sandwiched by molybdenum (Mo) films were prepared on a fused silica substrate by dc magnetron sputtering using an oxide ceramic ITO target (90 wt %In 2 O 3 and 10 wt %SnO 2 ). The resistivity and carrier density of the ITO films ranged from 2.9x10 -4 to 3.2x10 -3 Ω cm and from 1.9x10 20 to 1.2x10 21 cm -3 , respectively. The thermal diffusivity of the ITO films was (1.5-2.2)x10 -6 m 2 /s, depending on the electrical conductivity. The thermal conductivity carried by free electrons was estimated using the Wiedemann-Franz law. The phonon contribution to the heat transfer in ITO films with various resistivities was found to be almost constant (λ ph =3.95 W/m K), which was about twice that for amorphous indium zinc oxide films

  3. Efficient polymer:fullerene bulk heterojunction solar cells with n-type doped titanium oxide as an electron transport layer

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Youna [Heeger Center for Advanced Material & Research Institute of Solar and Sustainable Energies, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Kim, Geunjin [School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Kim, Heejoo, E-mail: heejook@gist.ac.kr [Heeger Center for Advanced Material & Research Institute of Solar and Sustainable Energies, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Kim, Sun Hee [School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); Lee, Kwanghee, E-mail: klee@gist.ac.kr [Heeger Center for Advanced Material & Research Institute of Solar and Sustainable Energies, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of); School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 500-712 (Korea, Republic of)

    2015-05-29

    We have reported a highly n-type doped solution-processed titanium metal oxide (TiO{sub x}) for use as an efficient electron-transport layer (ETL) in polymer:fullerene bulk heterojunction (BHJ) solar cells. When the metal ions (Ti) in TiO{sub x} are partially substituted by niobium (Nb), the charge carrier density increased, by an order of magnitude, because of the large electronegativity of Nb compared to that of Ti. Therefore, the work function (WF) of Nb-doped metal oxide (Nb-TiO{sub x}) decreases from 4.75 eV (TiO{sub x}) to 4.66 eV (Nb-TiO{sub x}), leading to an enhancement in the power conversion efficiency (PCE) of BHJ solar cells with a Nb-TiO{sub x} ETL (from 7.99% to 8.40%). - Highlights: • Solution processable Nb-doped TiO{sub x} was developed by simple sol-gel synthesis. • Charge carrier density in TiO{sub x} is significantly increased by introducing Nb element. • The work function value of Nb-doped TiO{sub x} is reduced by introducing Nb element. • A charge recombination inside of PSC with Nb-TiO{sub x} was effectively suppressed.

  4. Molecular Basis for Converting (2S-Methylsuccinyl-CoA Dehydrogenase into an Oxidase

    Directory of Open Access Journals (Sweden)

    Simon Burgener

    2017-12-01

    Full Text Available Although flavoenzymes have been studied in detail, the molecular basis of their dioxygen reactivity is only partially understood. The members of the flavin adenosine dinucleotide (FAD-dependent acyl-CoA dehydrogenase and acyl-CoA oxidase families catalyze similar reactions and share common structural features. However, both enzyme families feature opposing reaction specificities in respect to dioxygen. Dehydrogenases react with electron transfer flavoproteins as terminal electron acceptors and do not show a considerable reactivity with dioxygen, whereas dioxygen serves as a bona fide substrate for oxidases. We recently engineered (2S-methylsuccinyl-CoA dehydrogenase towards oxidase activity by rational mutagenesis. Here we characterized the (2S-methylsuccinyl-CoA dehydrogenase wild-type, as well as the engineered (2S-methylsuccinyl-CoA oxidase, in detail. Using stopped-flow UV-spectroscopy and liquid chromatography-mass spectrometry (LC-MS based assays, we explain the molecular base for dioxygen reactivity in the engineered oxidase and show that the increased oxidase function of the engineered enzyme comes at a decreased dehydrogenase activity. Our findings add to the common notion that an increased activity for a specific substrate is achieved at the expense of reaction promiscuity and provide guidelines for rational engineering efforts of acyl-CoA dehydrogenases and oxidases.

  5. Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

    Directory of Open Access Journals (Sweden)

    Faria Ana

    2009-01-01

    Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

  6. Atomic transport properties

    International Nuclear Information System (INIS)

    Freyss, M.

    2015-01-01

    As presented in the first chapter of this book, atomic transport properties govern a large panel of nuclear fuel properties, from its microstructure after fabrication to its behaviour under irradiation: grain growth, oxidation, fission product release, gas bubble nucleation. The modelling of the atomic transport properties is therefore the key to understanding and predicting the material behaviour under irradiation or in storage conditions. In particular, it is noteworthy that many modelling techniques within the so-called multi-scale modelling scheme of materials make use of atomic transport data as input parameters: activation energies of diffusion, diffusion coefficients, diffusion mechanisms, all of which are then required to be known accurately. Modelling approaches that are readily used or which could be used to determine atomic transport properties of nuclear materials are reviewed here. They comprise, on the one hand, static atomistic calculations, in which the migration mechanism is fixed and the corresponding migration energy barrier is calculated, and, on the other hand, molecular dynamics calculations and kinetic Monte-Carlo simulations, for which the time evolution of the system is explicitly calculated. (author)

  7. Electrical Transport Ability of Nanostructured Potassium-Doped Titanium Oxide Film

    Science.gov (United States)

    Lee, So-Yoon; Matsuno, Ryosuke; Ishihara, Kazuhiko; Takai, Madoka

    2011-02-01

    Potassium-doped nanostructured titanium oxide films were fabricated using a wet corrosion process with various KOH solutions. The doped condition of potassium in TiO2 was confirmed by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Nanotubular were synthesized at a dopant concentration of 0.27%, these structures disappeared. To investigate the electrical properties of K-doped TiO2, pseudo metal-oxide-semiconductor field-effect transistor (MOSFET) samples were fabricated. The samples exhibited a distinct electrical behavior and p-type characteristics. The electrical behavior was governed by the volume of the dopant when the dopant concentration was 0.18%.

  8. Optoelectronic devices, low temperature preparation methods, and improved electron transport layers

    KAUST Repository

    Eita, Mohamed S.; El, Labban Abdulrahman; Usman, Anwar; Beaujuge, Pierre; Mohammed, Omar F.

    2016-01-01

    An optoelectronic device such as a photovoltaic device which has at least one layer, such as an electron transport layer, which comprises a plurality of alternating, oppositely charged layers including metal oxide layers. The metal oxide can be zinc

  9. Optimisation of oxygen ion transport in materials for ceramic membrane devices.

    Science.gov (United States)

    Kilner, J A

    2007-01-01

    Oxygen transport in ceramic oxide materials has received much attention over the past few decades. Much of this interest has stemmed from the desire to construct high temperature electrochemical devices for energy conversion, an example being the solid oxide fuel cell. In order to achieve high performance for these devices, insights are needed in how to achieve optimum performance from the functional components such as the electrolytes and electrodes. This includes the optimisation of oxygen transport through the crystal lattice of electrode and electrolyte materials and across the homogeneous (grain boundary) and heterogeneous interfaces that exist in real devices. Strategies are discussed for the optimisation of these quantities and current problems in the characterisation of interfacial transport are explored.

  10. Kinetics of Carbon Monoxide Electro-Oxidation in Solid-Oxide Fuel Cells from Ni-YSZ Patterned-Anode Measurements

    KAUST Repository

    Hanna, J.; Lee, W. Y.; Ghoniem, A. F.

    2013-01-01

    A mathematical model is developed around the framework of a reduced mechanism describing electrochemical oxidation of carbon monoxide on Ni-YSZ patterned anodes. The electro-oxidation mechanism involves three reactions, one describing adsorption/ desorption of COonNi, and two single-electron charge-transfer steps inwhich the surface adsorbate CO(Ni) participates directly. These steps are coupled with surface transport in a reaction-diffusion model for which analytic equilibrium and steady-state solutions are derived. As much as possible, we make use of existing, independent, published information about heterogeneous chemistry, surface transport, and other model parameters. The only unknowns in our model are taken to be the kinetic rate constants of the electrochemical reactions, which we evaluate by fitting the model predictions to previously published patterned-anode experiments [B. Habibzadeh, Ph.D. Thesis, University of Maryland, College Park, MD, USA (2007)]. The results show that diffusion of CO on the Ni surface to the three-phase boundary is the rate-controlling process for CO electro-oxidation. Moreover, from a reaction standpoint, the charge-transfer process is dominated by a slow step involving CO(Ni). These findings collectively demonstrate the critical dependence of the electro-oxidation process to the direct participation of CO. © 2013 The Electrochemical Society. All rights reserved.

  11. Kinetics of Carbon Monoxide Electro-Oxidation in Solid-Oxide Fuel Cells from Ni-YSZ Patterned-Anode Measurements

    KAUST Repository

    Hanna, J.

    2013-04-17

    A mathematical model is developed around the framework of a reduced mechanism describing electrochemical oxidation of carbon monoxide on Ni-YSZ patterned anodes. The electro-oxidation mechanism involves three reactions, one describing adsorption/ desorption of COonNi, and two single-electron charge-transfer steps inwhich the surface adsorbate CO(Ni) participates directly. These steps are coupled with surface transport in a reaction-diffusion model for which analytic equilibrium and steady-state solutions are derived. As much as possible, we make use of existing, independent, published information about heterogeneous chemistry, surface transport, and other model parameters. The only unknowns in our model are taken to be the kinetic rate constants of the electrochemical reactions, which we evaluate by fitting the model predictions to previously published patterned-anode experiments [B. Habibzadeh, Ph.D. Thesis, University of Maryland, College Park, MD, USA (2007)]. The results show that diffusion of CO on the Ni surface to the three-phase boundary is the rate-controlling process for CO electro-oxidation. Moreover, from a reaction standpoint, the charge-transfer process is dominated by a slow step involving CO(Ni). These findings collectively demonstrate the critical dependence of the electro-oxidation process to the direct participation of CO. © 2013 The Electrochemical Society. All rights reserved.

  12. Ferroelectric BiFeO3as an Oxide Dye in Highly Tunable Mesoporous All-Oxide Photovoltaic Heterojunctions

    KAUST Repository

    Wang, Lingfei

    2016-10-12

    As potential photovoltaic materials, transition-metal oxides such as BiFeO3 (BFO) are capable of absorbing a substantial portion of solar light and incorporating ferroic orders into solar cells with enhanced performance. But the photovoltaic application of BFO has been hindered by low energy-conversion efficiency due to poor carrier transport and collection. In this work, a new approach of utilizing BFO as a light-absorbing sensitizer is developed to interface with charge-transporting TiO2 nanoparticles. This mesoporous all-oxide architecture, similar to that of dye-sensitized solar cells, can effectively facilitate the extraction of photocarriers. Under the standard AM1.5 (100 mW cm−2) irradiation, the optimized cell shows an open-circuit voltage of 0.67 V, which can be enhanced to 1.0 V by tailoring the bias history. A fill factor of 55% is achieved, which is much higher than those in previous reports on BFO-based photovoltaic devices. The results provide here a new viable approach toward developing highly tunable and stable photovoltaic devices based on ferroelectric transition-metal oxides.

  13. Inhibition of macrophage oxidative stress prevents the reduction of ABCA-1 transporter induced by advanced glycated albumin.

    Science.gov (United States)

    de Souza Pinto, Raphael; Castilho, Gabriela; Paim, Bruno Alves; Machado-Lima, Adriana; Inada, Natalia M; Nakandakare, Edna Regina; Vercesi, Aníbal Eugênio; Passarelli, Marisa

    2012-05-01

    We investigated the role of aminoguanidine and benfotiamine on the inhibition of reactive oxygen species (ROS) generation in macrophages induced by advanced glycated albumin (AGE-albumin) and its relationship with cell cholesterol homeostasis, emphasizing the expression of the ATP binding cassette transporter A-1 (ABCA-1). AGE-albumin was made by incubating fatty acid-free albumin with 10 mM glycolaldehyde. ROS production and ABCA-1 protein level were determined by flow cytometry in J774 macrophages treated along time with control (C) or AGE-albumin alone or in the presence of aminoguanidine or benfotiamine. Mitochondrial function was evaluated by oxygraphy. Compared to C-albumin, AGE-albumin increased ROS production in macrophages, which was ascribed to the activities of NADPH oxidase and of the mitochondrial system. Mitochondrial respiratory chain activity was reduced in cells incubated with AGE-albumin. ROS generation along time was associated with the reduction in macrophage ABCA-1 protein level. Aminoguanidine prevented ROS elevation and restored the ABCA-1 content in macrophages; on the other hand, benfotiamine that promoted a lesser reduction in ROS generation was not able to restore ABCA-1 levels. Inhibition of oxidative stress induced by AGE-albumin prevents disturbances in reverse cholesterol transport by curbing the reduction of ABCA-1 elicited by advanced glycation in macrophages and therefore may contribute to the prevention of atherosclerosis in diabetes mellitus.

  14. A New Laccase Biosensor For Polyphenols Determination

    Directory of Open Access Journals (Sweden)

    M. J.F. Rebelo

    2003-06-01

    Full Text Available The relevance of polyphenols in human health is a well known fact. Prompted by that, a very intensive research has been directed to get a method to detect them, wich will improve the current ones. Laccase (p-diphenol:dioxygen oxidoreductase EC 1.10.3.2 is a multi-copper oxidase, wich couples catalytic oxidation of phenolic substrates with four electron reduction of dioxygen to water [1]. A maximum catalytic response in oxigenated electrolyte was observed between 4.5 and 5.5 [2], while for pH > 6.9 the laccase was found to be inactive [3]. We prepared a biosensor with laccase immobilised on a polyether sulphone membrane, at pH 4.5, wich was applied at Universal Sensors base electrode. Reduction of the product of oxidation of several polyphenols, catalysed by laccase, was done at a potential for wich the polyphenol of interest was found to respond. Reduction of catechol was found to occur at a potential of -200mV, wich is often referred to in the literature for polyphenolic biosensors. However other polyphenols did not respond at that potential. It was observed that (+- catechin produced a very large cathodic current when +100mV were applied to the laccase biosensor, both in aqueous acetate and 12% ethanol acetate buffer, whereas caffeic acid responded at -50mV. Other polyphenols tested were gallic acid, malvidin, quercetin, rutin, trans-resveratrol

  15. A systemic study of stepwise chlorination-chemical vapor transport characteristics of pure rare earth oxides from Sc2O3 to Lu2O3 mediated by alkaline chlorides as complex former

    International Nuclear Information System (INIS)

    Sun Yanhui; He Peng; Chen Huani

    2007-01-01

    A systematic study has been carried out for the stepwise chlorination-chemical vapor transport (SC-CVT) characteristics of pure rare earth oxides from Sc 2 O 3 to Lu 2 O 3 mediated by the vapor complexes KLnCl 4 and NaLnCl 4 (Ln = Sc, Y and La-Lu) used NaCl and KCl as complex former, respectively. The results showed that the SC-CVT characteristics are similarly for NaCl and KCl as complex former, the main deposition temperature of the rare earth chlorides LnCl 3 is in the increasing order ScCl 3 3 3 , and then with a systematically decreasing trend from the early lanthanide chlorides to the end one. The results also showed that the total transported amount of the produced chlorides is YCl 3 > ScCl 3 , and they are much higher than that of most lanthanoid chlorides. For lanthanoids, the total transported amount of chloride increases systematically from the early lanthanoid chlorides to the end one except for EuCl 3 and GdCl 3 mediated by KCl and NaCl as complex former, respectively, which showed the divergence effect of Gd in the total transport efficiency. But there are some differences in SC-CVT characteristics of pure rare earth oxide mediated by KCl and NaCl as complex former, that is the main deposition temperature region for the same rare earth element was lower for KCl than that for NaCl as complex former except for LaCl 3 , CeCl 3 , YbCl 3 and LuCl 3 , while the total transport amount of rare earth chloride for KCl as complex former is higher than that for NaCl except for LaCl 3 and EuCl 3 . More over, the discussion was carried out for Sc and Y on the one hand and the lanthanides contain 4f electron as another hand based on the 4f electron hybridization assumption. Further more, the transport characteristics of rare earth oxides with alkaline chlorides as complex former in this study were compared to that with AlCl 3 as complex former

  16. Landfill methane oxidation across climate types in the U.S.

    Science.gov (United States)

    Chanton, Jeffrey; Abichou, Tarek; Langford, Claire; Hater, Gary; Green, Roger; Goldsmith, Doug; Swan, Nathan

    2011-01-01

    Methane oxidation in landfill covers was determined by stable isotope analyses over 37 seasonal sampling events at 20 landfills with intermediate covers over four years. Values were calculated two ways: by assuming no isotopic fractionation during gas transport, which produces a conservative or minimum estimate, and by assuming limited isotopic fractionation with gas transport producing a higher estimate. Thus bracketed, the best assessment of mean oxidation within the soil covers from chamber captured emitted CH(4) was 37.5 ± 3.5%. The fraction of CH(4) oxidized refers to the fraction of CH(4) delivered to the base of the cover that was oxidized to CO(2) and partitioned to microbial biomass instead of being emitted to the atmosphere as CH(4) expressed as a percentage. Air samples were also collected at the surface of the landfill, and represent CH(4) from soil, from leaking infrastructure, and from cover defects. A similar assessment of this data set yields 36.1 ± 7.2% oxidation. Landfills in five climate types were investigated. The fraction oxidized in arid sites was significantly greater than oxidation in mediterranean sites, or cool and warm continental sites. Sub tropical sites had significantly lower CH(4) oxidation than the other types of sites. This relationship may be explained by the observed inverse relationship between cover loading and fractional CH(4) oxidation.

  17. Summary report on transportation of nuclear fuel materials in Japan : transportation infrastructure, threats identified in open literature, and physical protection regulations.

    Energy Technology Data Exchange (ETDEWEB)

    Cochran, John Russell; Ouchi, Yuichiro (Japan Atomic Energy Agency, Japan); Furaus, James Phillip; Marincel, Michelle K.

    2008-03-01

    This report summarizes the results of three detailed studies of the physical protection systems for the protection of nuclear materials transport in Japan, with an emphasis on the transportation of mixed oxide fuel materials1. The Japanese infrastructure for transporting nuclear fuel materials is addressed in the first section. The second section of this report presents a summary of baseline data from the open literature on the threats of sabotage and theft during the transport of nuclear fuel materials in Japan. The third section summarizes a review of current International Atomic Energy Agency, Japanese and United States guidelines and regulations concerning the physical protection for the transportation of nuclear fuel materials.

  18. Mesoporous Transition Metal Oxides for Supercapacitors

    Science.gov (United States)

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

  19. Mesoporous Transition Metal Oxides for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2015-10-01

    Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  20. Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

    International Nuclear Information System (INIS)

    Valarselvan, S.; Manisankar, P.

    2011-01-01

    Graphical abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . Highlights: → Hydroxyl derivatives of anthraquinones as electrocatalysts for dioxygen reduction. → AQ/PPy composite film on GC electrode exhibits potent electrocatalytic activity. → Substituent groups influence electrocatalytic dioxygen reduction. → Surface coverage varies the rate of electrocatalytic dioxygen reduction. - Abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O 2 reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.

  1. Iron oxide reduction in methane-rich deep Baltic Sea sediments

    DEFF Research Database (Denmark)

    Egger, Matthias; Hagens, Mathilde; Sapart, Celia J.

    2017-01-01

    /L transition. Our results reveal a complex interplay between production, oxidation and transport of methane showing that besides organoclastic Fe reduction, oxidation of downward migrating methane with Fe oxides may also explain the elevated concentrations of dissolved ferrous Fe in deep Baltic Sea sediments...... profiles and numerical modeling, we propose that a potential coupling between Fe oxide reduction and methane oxidation likely affects deep Fe cycling and related biogeochemical processes, such as burial of phosphorus, in systems subject to changes in organic matter loading or bottom water salinity....

  2. Multi-Copper Oxidases and Human Iron Metabolism

    Science.gov (United States)

    Vashchenko, Ganna; MacGillivray, Ross T. A.

    2013-01-01

    Multi-copper oxidases (MCOs) are a small group of enzymes that oxidize their substrate with the concomitant reduction of dioxygen to two water molecules. Generally, multi-copper oxidases are promiscuous with regards to their reducing substrates and are capable of performing various functions in different species. To date, three multi-copper oxidases have been detected in humans—ceruloplasmin, hephaestin and zyklopen. Each of these enzymes has a high specificity towards iron with the resulting ferroxidase activity being associated with ferroportin, the only known iron exporter protein in humans. Ferroportin exports iron as Fe2+, but transferrin, the major iron transporter protein of blood, can bind only Fe3+ effectively. Iron oxidation in enterocytes is mediated mainly by hephaestin thus allowing dietary iron to enter the bloodstream. Zyklopen is involved in iron efflux from placental trophoblasts during iron transfer from mother to fetus. Release of iron from the liver relies on ferroportin and the ferroxidase activity of ceruloplasmin which is found in blood in a soluble form. Ceruloplasmin, hephaestin and zyklopen show distinctive expression patterns and have unique mechanisms for regulating their expression. These features of human multi-copper ferroxidases can serve as a basis for the precise control of iron efflux in different tissues. In this manuscript, we review the biochemical and biological properties of the three human MCOs and discuss their potential roles in human iron homeostasis. PMID:23807651

  3. Applications of Oxide Coatings in Photovoltaic Devices

    Directory of Open Access Journals (Sweden)

    Sonya Calnan

    2014-03-01

    Full Text Available Metalloid and metal based oxides are an almost unavoidable component in the majority of solar cell technologies used at the time of writing this review. Numerous studies have shown increases of ≥1% absolute in solar cell efficiency by simply substituting a given layer in the material stack with an oxide. Depending on the stoichiometry and whether other elements are present, oxides can be used for the purpose of light management, passivation of electrical defects, photo-carrier generation, charge separation, and charge transport in a solar cell. In this review, the most commonly used oxides whose benefits for solar cells have been proven both in a laboratory and industrial environment are discussed. Additionally, developing trends in the use of oxides, as well as newer oxide materials, and deposition technologies for solar cells are reported.

  4. Sensor technology for hazardous cargo transportation safety.

    Science.gov (United States)

    2013-08-01

    The overall goal of this research project was to develop oxidant vapor detection devices that can be : used to ensure the safety of hazardous freight transportation systems. Two nanotechnology-based : systems originally developed for improvised explo...

  5. Development of Nanoscale Graphitic Devices and The Transport Characterization

    International Nuclear Information System (INIS)

    Gunasekaran, Venugopal

    2011-02-01

    This dissertation describes the development of graphitic based nanoscale devices with its fabrication and transport characterization results. It covers graphite nano-scale stacked-junctions fabricated using focused ion beam (FIB) 3-D etching technique, a single layer graphite layer (graphene) preparation and its electrical transport characterization results and the synthesis and investigation of electrical transport behavior of graphene oxide based thin film devices. The first chapter describes the basic information about the carbon family in detail in which the electronic properties and structure of graphite, graphene and graphene oxide are discussed. In addition, the necessity of developing nanoscale graphitic devices is given. The second chapter explains the experimental techniques used in this research for fabricating nanoscale devices which includes focused ion beam 3-D fabrication procedures, mechanical exfoliation technique and photolithographic methods. In third chapter, we have reported the results on temperature dependence of graphite planar-type structures fabricated along ab-plane. In the fourth and fifth chapters, the fabrication and electrical transport characteristics of large in-plane area graphite planar-type structures (fabricated along ab-plane and c-axis) were discussed and their transport anisotropy properties were investigated briefly. In the sixth chapter, we focused the fabrication of the submicron sized graphite stacked junctions and their electrical transport characterization studies. In which, FIB was used to fabricated the submicron junctions with various in-plane area (with same stack height) are and their transport characteristics were compared. The seventh chapter reports investigation of electrical transport results of nanoscale graphite stacked-junctions in which the temperature dependent transport (R-T) studies, current-voltage measurements for the various in-plane areas and for various stack height samples were analyzed. The

  6. Unidirectional oxide hetero-interface thin-film diode

    International Nuclear Information System (INIS)

    Park, Youngmin; Lee, Eungkyu; Lee, Jinwon; Lim, Keon-Hee; Kim, Youn Sang

    2015-01-01

    The unidirectional thin-film diode based on oxide hetero-interface, which is well compatible with conventional thin-film fabrication process, is presented. With the metal anode/electron-transporting oxide (ETO)/electron-injecting oxide (EIO)/metal cathode structure, it exhibits that electrical currents ohmically flow at the ETO/EIO hetero-interfaces for only positive voltages showing current density (J)-rectifying ratio of ∼10 5 at 5 V. The electrical properties (ex, current levels, and working device yields) of the thin-film diode (TFD) are systematically controlled by changing oxide layer thickness. Moreover, we show that the oxide hetero-interface TFD clearly rectifies an AC input within frequency (f) range of 10 2  Hz < f < 10 6  Hz, providing a high feasibility for practical applications

  7. Unidirectional oxide hetero-interface thin-film diode

    Energy Technology Data Exchange (ETDEWEB)

    Park, Youngmin; Lee, Eungkyu; Lee, Jinwon; Lim, Keon-Hee [Program in Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul 151-742 (Korea, Republic of); Kim, Youn Sang, E-mail: younskim@snu.ac.kr [Program in Nano Science and Technology, Graduate School of Convergence Science and Technology, Seoul National University, Seoul 151-742 (Korea, Republic of); Advanced Institute of Convergence Technology, Gyeonggi-do 443-270 (Korea, Republic of)

    2015-10-05

    The unidirectional thin-film diode based on oxide hetero-interface, which is well compatible with conventional thin-film fabrication process, is presented. With the metal anode/electron-transporting oxide (ETO)/electron-injecting oxide (EIO)/metal cathode structure, it exhibits that electrical currents ohmically flow at the ETO/EIO hetero-interfaces for only positive voltages showing current density (J)-rectifying ratio of ∼10{sup 5} at 5 V. The electrical properties (ex, current levels, and working device yields) of the thin-film diode (TFD) are systematically controlled by changing oxide layer thickness. Moreover, we show that the oxide hetero-interface TFD clearly rectifies an AC input within frequency (f) range of 10{sup 2} Hz < f < 10{sup 6} Hz, providing a high feasibility for practical applications.

  8. A model for the release of low-volatility fission products in oxidizing conditions

    International Nuclear Information System (INIS)

    Cox, D.S.; Hunt, C.E.L.; Liu, Z.; Keller, N.A.; Barrand, R.D.; O'Connor, R.F.

    1991-07-01

    A thermodynamic and kinetic model has been developed for calculating low-volatility fission-product releases from UO 2 at high temperatures in oxidizing conditions. Volatilization of the UO 2 matrix is assumed to be the rate controlling process. Oxidation kinetics of the UO 2 are modelled by either interfacial rate control, gas phase oxidant transport control, or solid-state diffusion of oxygen. The vapour pressure of UO 3 in equilibrium with the oxidizing fuel is calculated from thermodynamic data, and volatilization rates are determined using a model for forced convective mass transport. Low-volatility fission-product releases are calculated from the volume of vapourized fuel. Model calculations are conservative compared to experimental data for Zr, La, Ce and Nb fission-product releases from irradiated UO 2 exposed to air at 1973-2350 K. The implications of this conservatism are discussed in terms of possible rate control by processes other than convective mass transport of UO 3 . Coefficients for effective surface area (based on experimental data) and for heterogeneous rate controlling reaction kinetics are introduced to facilitate agreement between calculations and the experimental data.

  9. UFD Storage and Transportation - Transportation Working Group Report

    International Nuclear Information System (INIS)

    Maheras, Steven J.; Ross, Steven B.

    2011-01-01

    The Used Fuel Disposition (UFD) Transportation Task commenced in October 2010. As its first task, Pacific Northwest National Laboratory (PNNL) compiled a list of structures, systems, and components (SSCs) of transportation systems and their possible degradation mechanisms during extended storage. The list of SSCs and the associated degradation mechanisms (known as features, events, and processes (FEPs)) were based on the list of used nuclear fuel (UNF) storage system SSCs and degradation mechanisms developed by the UFD Storage Task (Hanson et al. 2011). Other sources of information surveyed to develop the list of SSCs and their degradation mechanisms included references such as Evaluation of the Technical Basis for Extended Dry Storage and Transportation of Used Nuclear Fuel (NWTRB 2010), Transportation, Aging and Disposal Canister System Performance Specification, Revision 1 (OCRWM 2008), Data Needs for Long-Term Storage of LWR Fuel (EPRI 1998), Technical Bases for Extended Dry Storage of Spent Nuclear Fuel (EPRI 2002), Used Fuel and High-Level Radioactive Waste Extended Storage Collaboration Program (EPRI 2010a), Industry Spent Fuel Storage Handbook (EPRI 2010b), and Transportation of Commercial Spent Nuclear Fuel, Issues Resolution (EPRI 2010c). SSCs include items such as the fuel, cladding, fuel baskets, neutron poisons, metal canisters, etc. Potential degradation mechanisms (FEPs) included mechanical, thermal, radiation and chemical stressors, such as fuel fragmentation, embrittlement of cladding by hydrogen, oxidation of cladding, metal fatigue, corrosion, etc. These degradation mechanisms are discussed in Section 2 of this report. The degradation mechanisms have been evaluated to determine if they would be influenced by extended storage or high burnup, the need for additional data, and their importance to transportation. These categories were used to identify the most significant transportation degradation mechanisms. As expected, for the most part, the

  10. A field study on chemistry, S(IV) oxidation rates and vertical transport during fog conditions

    Science.gov (United States)

    Joos, F.; Baltensperger, U.

    An extensive fog study was carried out in the central plateu of Switzerland. Ninety-seven fog samples were collected along with aerosol filter and cascade impactor samples, and measurements of O 3, SO 2, NO, NO x, PAN, temperature, and wind speed and direction. Maximum levels in fogwater were 4.3, 4.4., 0.033, 1.7, 0.5, 0.024 and 9.2 mmol ℓ -1 for Cl -, NO 3-, NO 2-, SO 42-, S(IV), oxalate and NH 4+, respectively. pH varied between 2.9 and 7.1. Sixteen additional elements were determined in the fog samples by ICP. The sum of the concentrations of SO 42- and S(IV) agreed very with the total sulfur concentration as determined by ICP. A substantial excess of S(IV) (up to 0.2 mmol ℓ -1) compared to Henry and acid-base equilibrium calculations was found, which can probably be attributed to complex formations with aldehydes. S(IV) oxidation rates of up to 650 nmol ℓ -1 s -1 with ozone and of up to 100 nmol ℓ -1 s -1 with NO 2 were calculated. S(IV) oxidation due to PAN, NO 2- and Fe(III) was of minor importance. A substantial fraction of the major ions was present in the intersitial aerosol (aerosol particles < 4 μm) even during fog conditions. High correlations were found for NH 4+, NO 32-. From their ratios in the fog water and the aerosol (< 4 μm) it could be concluded that at least 40% of NO 3- and 20% of NH 4+ in fog water was due to gas phase scavenging. Increasing concentrations in fog water were found during fog dissipation. Concentrations decreased with increasing height. A vertical transport model including turbulent diffusion and droplet sedimentation is introduced, which matches the experimental data of this vertical profile.

  11. The transport of fuel assemblies. New containers for transport the used nuclear material in Juzbado factory

    International Nuclear Information System (INIS)

    2005-01-01

    Juzbado Manufacturing Facility is designed to be versatile and flexible. It is manufactured different kind of fuel assemblies PWR, BWR and VVER, beginning by the uranium oxide coming from the conversion facilities. The transport of these products (radioactive material fissile) requires the availability of different kind of packages; our models variety is similar to the big manufacturers. It is required a depth knowledge of the licensing process, approvals, manufacturing and handling instruction to be confident. Moreover, the recently changes on the Transport Regulations and the demands for the approval by the Competent Authorities have required the renovation of most of the package designs for the transport of radioactive material fissile worldwide. ENUSA assumed time ago this renovation and it is nowadays in the pick moment of this process. If we also consider the complexity on the management of multimodal international transportations, the Logistic task for the transport of nuclear material associated to the Juzbado factory results in a real changeling area. (Author)

  12. Diffusional aspects of the high-temperature oxidation of protective coatings

    Science.gov (United States)

    Nesbitt, J. A.

    1989-01-01

    The role of diffusional transport associated with the high-temperature oxidation of coatings is examined, with special attention given to the low-pressure plasma spraying MCrAl-type overlay coatings and similar Ni-base alloys which form protective AlO3 scales. The use of diffusional analysis to predict the minimum solute concentration necessary to form and grow a solute oxide scale is illustrated. Modeling procedures designed to simulate the diffusional transport in coatings and substrates are presented to show their use in understanding coating degradation, predicting the protective life of a coating, and evaluating various coating parameters to guide coating development.

  13. Mathematical modeling of the coupled transport and electrochemical reactions in solid oxide steam electrolyzer for hydrogen production

    International Nuclear Information System (INIS)

    Ni, Meng; Leung, Michael K.H.; Leung, Dennis Y.C.

    2007-01-01

    A mathematical model was developed to simulate the coupled transport/electrochemical reaction phenomena in a solid oxide steam electrolyzer (SOSE) at the micro-scale level. Ohm's law, dusty gas model (DGM), Darcy's law, and the generalized Butler Volmer equation were employed to determine the transport of electronic/ionic charges and gas species as well as the electrochemical reactions. Parametric analyses were performed to investigate the effects of operating parameters and micro-structural parameters on SOSE potential. The results substantiated the fact that SOSE potential could be effectively decreased by increasing the operating temperature. In addition, higher steam molar fraction would enhance the operation of SOSE with lower potential. The effect of particle sizes on SOSE potential was studied with due consideration on the SOSE activation and concentration overpotentials. Optimal particle sizes that could minimize the SOSE potential were obtained. It was also found that decreasing electrode porosity could monotonically decrease the SOSE potential. Besides, optimal values of volumetric fraction of electronic particles were found to minimize electrode total overpotentials. In order to optimize electrode microstructure to minimize SOSE electricity consumption, the concept of 'functionally graded materials (FGM)' was introduced to lower the SOSE potential. The advanced design of particle size graded SOSE was found effective for minimizing electrical energy consumption resulting in efficient SOSE hydrogen production. The micro-scale model was capable of predicting SOSE hydrogen production performance and would be a useful tool for design optimization

  14. Ferroelectric BiFeO3 as an Oxide Dye in Highly Tunable Mesoporous All-Oxide Photovoltaic Heterojunctions.

    Science.gov (United States)

    Wang, Lingfei; Ma, He; Chang, Lei; Ma, Chun; Yuan, Guoliang; Wang, Junling; Wu, Tom

    2017-01-01

    As potential photovoltaic materials, transition-metal oxides such as BiFeO 3 (BFO) are capable of absorbing a substantial portion of solar light and incorporating ferroic orders into solar cells with enhanced performance. But the photovoltaic application of BFO has been hindered by low energy-conversion efficiency due to poor carrier transport and collection. In this work, a new approach of utilizing BFO as a light-absorbing sensitizer is developed to interface with charge-transporting TiO 2 nanoparticles. This mesoporous all-oxide architecture, similar to that of dye-sensitized solar cells, can effectively facilitate the extraction of photocarriers. Under the standard AM1.5 (100 mW cm -2 ) irradiation, the optimized cell shows an open-circuit voltage of 0.67 V, which can be enhanced to 1.0 V by tailoring the bias history. A fill factor of 55% is achieved, which is much higher than those in previous reports on BFO-based photovoltaic devices. The results provide here a new viable approach toward developing highly tunable and stable photovoltaic devices based on ferroelectric transition-metal oxides. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Direct comparison of the electrical properties in metal/oxide/nitride/oxide/silicon and metal/aluminum oxide/nitride/oxide/silicon capacitors with equivalent oxide thicknesses

    Energy Technology Data Exchange (ETDEWEB)

    An, Ho-Myoung; Seo, Yu Jeong; Kim, Hee Dong; Kim, Kyoung Chan; Kim, Jong-Guk [School of Electrical Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Cho, Won-Ju; Koh, Jung-Hyuk [Department of Electronic Materials Engineering, Kwangwoon University, Seoul 139-701 (Korea, Republic of); Sung, Yun Mo [Department of Materials and Science Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Kim, Tae Geun, E-mail: tgkim1@korea.ac.k [School of Electrical Engineering, Korea University, Seoul 136-713 (Korea, Republic of)

    2009-07-31

    We examine the electrical properties of metal/oxide/nitride/oxide/silicon (MONOS) capacitors with two different blocking oxides, SiO{sub 2} and Al{sub 2}O{sub 3}, under the influence of the same electric field. The thickness of the Al{sub 2}O{sub 3} layer is set to 150 A, which is electrically equivalent to a thickness of the SiO{sub 2} layer of 65 A, in the MONOS structure for this purpose. The capacitor with the Al{sub 2}O{sub 3} blocking layer shows a larger capacitance-voltage memory window of 8.6 V, lower program voltage of 7 V, faster program/erase speeds of 10 ms/1 {mu}s, lower leakage current of 100 pA and longer data retention than the one with the SiO{sub 2} blocking layer does. These improvements are attributed to the suppression of the carrier transport to the gate electrode afforded by the use of an Al{sub 2}O{sub 3} blocking layer physically thicker than the SiO{sub 2} one, as well as the effective charge-trapping by Al{sub 2}O{sub 3} at the deep energy levels in the nitride layer.

  16. Emissions of road transport

    International Nuclear Information System (INIS)

    Maekelae, K.; Tuominen, A.

    2001-01-01

    Information on the emissions and energy consumption of different vehicles per transported amount of goods has up to last years been minimal. The unit emissions mean the amount of harmful compounds in the flue gases of a vehicle per service, time or energy unit. National three-year MOBILE 2-research program, started in 1999, determines the unit emissions of all the traffic sectors in Finland. VTT Building and Transport mainly carry out the research, but the Institute of Transportation Engineering of the Tampere University of Technology (TTKK) is responsible for a part of the research. The objective of the project is to create common rules for the determination of unit emissions values, and to determine the best possible values for Finnish conditions. Unit emission data is mainly needed for evaluation of the environmental impacts of production plants and other activities containing transportation of commodities. At the web sites of VTT Building and Transport there are about 60 pages of text and tables (about 4000 values) on unit emissions. The URL of the pages is http://www.vtt.fi/rte/projects/lipastoe/index.htm. These web pages present data on all the transportation sectors (road, railroad, water and air transportation), most of the materials concerning road transportation. Following compounds and values are included: CO, HC, NO x , particulates, SO 2 , CO 2 and energy consumption. Methane and nitrous oxide emissions values have also been presented

  17. Method of making a hydrogen transport membrane, and article

    Science.gov (United States)

    Schwartz, Joseph M.; Corpus, Joseph M.; Lim, Hankwon

    2015-07-21

    The present invention relates to a method of manufacturing a hydrogen transport membrane and the composite article itself. More specifically, the invention relates to producing a membrane substrate, wherein the ceramic substrate is coated with a metal oxide slurry, thereby eliminating the need for an activation step prior to plating the ceramic membrane through an electroless plating process. The invention also relates to modifying the pore size and porosity of the substrate by oxidation or reduction of the particles deposited by the metal oxide slurry.

  18. DISCHARGE OXIDE STORAGE CAPACITY AND VOLTAGE LOSS IN LI-AIR BATTERY

    International Nuclear Information System (INIS)

    Wang, Yun; Wang, Zhe; Yuan, Hao; Li, Tianqi

    2015-01-01

    Air cathodes, where oxygen reacts with Li ions and electrons with discharge oxide stored in their pore structure, are often considered as the most challenging component in nonaqueous Lithium-air batteries. In non-aqueous electrolytes, discharge oxides are usually insoluble and hence precipitate at local reaction site, raising the oxygen transport resistance in the pore network. Due to their low electric conductivity, their presence causes electrode passivation. This study aims to investigate the air cathode’s performance through analytically obtaining oxygen profiles, modeling electrode passivation, evaluating the transport polarization raised by discharge oxide precipitate, and developing analytical formulas for insoluble Li oxides storage capacity. The variations of cathode quantities, including oxygen content and temperature, are evaluated and related to a single dimensionless parameter — the Damköhler Number (Da). An approximate model is developed to predict discharge voltage loss, along with validation against two sets of experimental data. Air cathode properties, including tortuosity, surface coverage factor and the Da number, and their effects on the cathode’s capacity of storing Li oxides are formulated and discussed.

  19. Inkjet printed ambipolar transistors and inverters based on carbon nanotube/zinc tin oxide heterostructures

    International Nuclear Information System (INIS)

    Kim, Bongjun; Jang, Seonpil; Dodabalapur, Ananth; Geier, Michael L.; Prabhumirashi, Pradyumna L.; Hersam, Mark C.

    2014-01-01

    We report ambipolar field-effect transistors (FETs) consisting of inkjet printed semiconductor bilayer heterostructures utilizing semiconducting single-walled carbon nanotubes (SWCNTs) and amorphous zinc tin oxide (ZTO). The bilayer structure allows for electron transport to occur principally in the amorphous oxide layer and hole transport to occur exclusively in the SWCNT layer. This results in balanced electron and hole mobilities exceeding 2 cm 2 V −1 s −1 at low operating voltages ( 10). This work provides a pathway for realizing solution processable, inkjet printable, large area electronic devices, and systems based on SWCNT-amorphous oxide heterostructures

  20. Mechanistic insight into oxide-promoted palladium catalysts for the electro-oxidation of ethanol.

    Science.gov (United States)

    Martinez, Ulises; Serov, Alexey; Padilla, Monica; Atanassov, Plamen

    2014-08-01

    Recent advancements in the development of alternatives to proton exchange membrane fuel cells utilizing less-expensive catalysts and renewable liquid fuels, such as alcohols, has been observed for alkaline fuel cell systems. Alcohol fuels present the advantage of not facing the challenge of storage and transportation encountered with hydrogen fuel. Oxidation of alcohols has been improved by the promotion of alloyed or secondary phases. Nevertheless, currently, there is no experimental understanding of the difference between an intrinsic and a synergistic promotion effect in high-pH environments. This report shows evidence of different types of promotion effects on palladium electrocatalysts obtained from the presence of an oxide phase for the oxidation of ethanol. The correlation of mechanistic in situ IR spectroscopic studies with electrochemical voltammetry studies on two similar electrocatalytic systems allow the role of either an alloyed or a secondary phase on the mechanism of oxidation of ethanol to be elucidated. Evidence is presented for the difference between an intrinsic effect obtained from an alloyed system and a synergistic effect produced by the presence of an oxide phase. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Aquifer Thermal Energy Storage as an ecosystem service for Brussels, Belgium: investigating iron (hydr)oxide precipitation with reactive transport modeling

    Science.gov (United States)

    Anibas, Christian; Possemiers, Mathias; Huysmans, Marijke

    2016-04-01

    In an evolving energy system it is important that urbanized areas contribute to their own energy demands. To reduce greenhouse gas emissions sustainable energy systems with a high efficiency are required, e.g. using urban aquifers as an ecosystem service. Here the potential of seasonal aquifer thermal energy storage and recovery (ATES) for the Brussels-Capital Region, Belgium is investigated. An important shallow geologic formation in the Brussels Capital Region is the Brussels Sand formation, a 20-60 m thick phreatic aquifer. The Brussels Sand Formation is known for its potential for ATES systems, but also for its varying redox and hydraulic conditions. Important limiting factors for ATES systems in the Brussels Sand Formation therefore are the hydraulic conductivity and the geochemical composition of the groundwater. Near the redox boundary iron hydroxide precipitation can negatively influence ATES well performance due to clogging. The interactions between physical processes (e.g. particle transport and clogging in the wider proximity of the ATES well) and chemical processes (e.g. influence of the operation temperatures on precipitation processes) during ATES operation are complex but not well understood. Therefore we constructed numerical groundwater flow models in MODFLOW to estimate maximum pumping and injection rates of different hydraulic conditions and competing water uses in the Brussels Sand Formation. In further steps the thermal potential for ATES was quantified using MT3DMS and the reactive transport model PHT3D was applied to assess the effects of operating ATES systems near the redox boundary. Results show that initial mixing plays an important role in the development of iron(hydr)oxide precipitation around the ATES wells, with the highest concentrations around the cold wells. This behavior is enhanced by the temperature effect; temperature differences of ΔT≈10°C already influence the iron (hydr)oxide concentration. The initial injection into the

  2. A review: oxidative stress in fish induced by pesticides.

    Science.gov (United States)

    Slaninova, Andrea; Smutna, Miriam; Modra, Helena; Svobodova, Zdenka

    2009-01-01

    The knowledge in oxidative stress in fish has a great importance for environmental and aquatic toxicology. Because oxidative stress is evoked by many chemicals including some pesticides, pro-oxidant factors' action in fish organism can be used to assess specific area pollution or world sea pollution. Hepatotoxic effect of DDT may be related with lipid peroxidation. Releasing of reactive oxygen species (ROS) after HCB exposure can be realized via two ways: via the uncoupling of the electron transport chain from monooxygenase activity and via metabolism of HCB major metabolite pentachlorophenol. Chlorothalonil disrupts mitochondrial metabolism due to the impairment of NADPH oxidase function. Activation of spleen macrophages and a decrease of catalase (CAT) activity have been observed after endosulfan exposure. Excessive release of superoxide radicals after etoxazole exposure can cause a decrease of CAT activity and increase phagocytic activity of splenocytes. Anticholinergic activity of organophosphates leads to the accumulation of ROS and resulting lipid peroxidation. Carbaryl induces changes in the content of glutathione and antioxidant enzymes activities. The antioxidant enzymes changes have been observed after actuation of pesticides deltamethrin and cypermethrin. Bipyridyl herbicides are able to form redox cycles and thereby cause oxidative stress. Low concentrations of simazine do not cause oxidative stress in carps during sub-chronic tests while sublethal concentrations of atrazin can induce oxidative stress in bluegill sunfish. Butachlor causes increased activity of superoxide dismutase -catalase system in the kidney. Rotenon can inhibit the electron transport in mitochondria and thereby increase ROS production. Dichloroaniline, the metabolite of diuron, has oxidative effects. Oxidative damage from fenpyroximate actuation is related to the disruption of mitochondrial redox respiratory chain. Low concentration of glyphosate can cause mild oxidative stress.

  3. The oxidative hypothesis of senescence

    Directory of Open Access Journals (Sweden)

    Gilca M

    2007-01-01

    Full Text Available The oxidative hypothesis of senescence, since its origin in 1956, has garnered significant evidence and growing support among scientists for the notion that free radicals play an important role in ageing, either as "damaging" molecules or as signaling molecules. Age-increasing oxidative injuries induced by free radicals, higher susceptibility to oxidative stress in short-lived organisms, genetic manipulations that alter both oxidative resistance and longevity and the anti-ageing effect of caloric restriction and intermittent fasting are a few examples of accepted scientific facts that support the oxidative theory of senescence. Though not completely understood due to the complex "network" of redox regulatory systems, the implication of oxidative stress in the ageing process is now well documented. Moreover, it is compatible with other current ageing theories (e.g., those implicating the mitochondrial damage/mitochondrial-lysosomal axis, stress-induced premature senescence, biological "garbage" accumulation, etc. This review is intended to summarize and critically discuss the redox mechanisms involved during the ageing process: sources of oxidant agents in ageing (mitochondrial -electron transport chain, nitric oxide synthase reaction- and non-mitochondrial- Fenton reaction, microsomal cytochrome P450 enzymes, peroxisomal β -oxidation and respiratory burst of phagocytic cells, antioxidant changes in ageing (enzymatic- superoxide dismutase, glutathione-reductase, glutathion peroxidase, catalase- and non-enzymatic glutathione, ascorbate, urate, bilirubine, melatonin, tocopherols, carotenoids, ubiquinol, alteration of oxidative damage repairing mechanisms and the role of free radicals as signaling molecules in ageing.

  4. Tunneling rates in electron transport through double-barrier molecular junctions in a scanning tunneling microscope

    OpenAIRE

    Nazin, G. V.; Wu, S. W.; Ho, W.

    2005-01-01

    The scanning tunneling microscope enables atomic-scale measurements of electron transport through individual molecules. Copper phthalocyanine and magnesium porphine molecules adsorbed on a thin oxide film grown on the NiAl(110) surface were probed. The single-molecule junctions contained two tunneling barriers, vacuum gap, and oxide film. Differential conductance spectroscopy shows that electron transport occurs via vibronic states of the molecules. The intensity of spectral peaks correspondi...

  5. Charge transport in amorphous InGaZnO thin-film transistors

    NARCIS (Netherlands)

    Germs, W.C.; Adriaans, W.H.; Tripathi, A.K.; Roelofs, W.S.C.; Cobb, B.; Janssen, R.A.J.; Gelinck, G.H.; Kemerink, M.

    2012-01-01

    We investigate the mechanism of charge transport in indium gallium zinc oxide (a-IGZO), an amorphous metal-oxide semiconductor. We measured the field-effect mobility and the Seebeck coefficient (S=ΔV/ΔT) of a-IGZO in thin-film transistors as a function of charge-carrier density for different

  6. Charge transport in amorphous InGaZnO thin film transistors

    NARCIS (Netherlands)

    Germs, W.C.; Adriaans, W.H.; Tripathi, A.K.; Roelofs, W.S.C.; Cobb, B.; Janssen, R.A.J.; Gelinck, G.H.; Kemerink, M.

    2012-01-01

    We investigate the mechanism of charge transport in indium gallium zinc oxide (a-IGZO), an amorphous metal-oxide semiconductor. We measured the field-effect mobility and the Seebeck coefficient (S=¿V/¿T) of a-IGZO in thin-film transistors as a function of charge-carrier density for different

  7. Considering a Threshold Energy in Reactive Transport Modeling of Microbially Mediated Redox Reactions in an Arsenic-Affected Aquifer

    Directory of Open Access Journals (Sweden)

    Marco Rotiroti

    2018-01-01

    Full Text Available The reductive dissolution of Fe-oxide driven by organic matter oxidation is the primary mechanism accepted for As mobilization in several alluvial aquifers. These processes are often mediated by microorganisms that require a minimum Gibbs energy available to conduct the reaction in order to sustain their life functions. Implementing this threshold energy in reactive transport modeling is rarely used in the existing literature. This work presents a 1D reactive transport modeling of As mobilization by the reductive dissolution of Fe-oxide and subsequent immobilization by co-precipitation in iron sulfides considering a threshold energy for the following terminal electron accepting processes: (a Fe-oxide reduction, (b sulfate reduction, and (c methanogenesis. The model is then extended by implementing a threshold energy on both reaction directions for the redox reaction pairs Fe(III reduction/Fe(II oxidation and methanogenesis/methane oxidation. The optimal threshold energy fitted in 4.50, 3.76, and 1.60 kJ/mol e− for sulfate reduction, Fe(III reduction/Fe(II oxidation, and methanogenesis/methane oxidation, respectively. The use of models implementing bidirectional threshold energy is needed when a redox reaction pair can be transported between domains with different redox potentials. This may often occur in 2D or 3D simulations.

  8. Numerical simulation of in-situ chemical oxidation (ISCO) and biodegradation of petroleum hydrocarbons using a coupled model for bio-geochemical reactive transport

    Science.gov (United States)

    Marin, I. S.; Molson, J. W.

    2013-05-01

    Petroleum hydrocarbons (PHCs) are a major source of groundwater contamination, being a worldwide and well-known problem. Formed by a complex mixture of hundreds of organic compounds (including BTEX - benzene, toluene, ethylbenzene and xylenes), many of which are toxic and persistent in the subsurface and are capable of creating a serious risk to human health. Several remediation technologies can be used to clean-up PHC contamination. In-situ chemical oxidation (ISCO) and intrinsic bioremediation (IBR) are two promising techniques that can be applied in this case. However, the interaction of these processes with the background aquifer geochemistry and the design of an efficient treatment presents a challenge. Here we show the development and application of BIONAPL/Phreeqc, a modeling tool capable of simulating groundwater flow, contaminant transport with coupled biological and geochemical processes in porous or fractured porous media. BIONAPL/Phreeqc is based on the well-tested BIONAPL/3D model, using a powerful finite element simulation engine, capable of simulating non-aqueous phase liquid (NAPL) dissolution, density-dependent advective-dispersive transport, and solving the geochemical and kinetic processes with the library Phreeqc. To validate the model, we compared BIONAPL/Phreeqc with results from the literature for different biodegradation processes and different geometries, with good agreement. We then used the model to simulate the behavior of sodium persulfate (NaS2O8) as an oxidant for BTEX degradation, coupled with sequential biodegradation in a 2D case and to evaluate the effect of inorganic geochemistry reactions. The results show the advantages of a treatment train remediation scheme based on ISCO and IBR. The numerical performance and stability of the integrated BIONAPL/Phreeqc model was also verified.

  9. Assessment of the environmental impact of plutonium transport within the European Community

    International Nuclear Information System (INIS)

    1978-11-01

    Assessment is given of the environmental impact of plutonium transport within the European Community in the 1990's. This includes shipments of plutonium, raw materials, fresh and spent mixed oxide fuel assemblies and plutonium contaminated solid wastes. The consequences on general traffic, the radiation doses to transport workers and the general public and the heat release during transport are presented

  10. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    Science.gov (United States)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

  11. In-Situ Chemical Oxidation

    Science.gov (United States)

    2006-08-01

    wells at a bioremediation field site (Weisner et al., 1996). Colloidal clay particles mobilized during injec- tion have resulted in permeability losses...phase material. Nevertheless, O3 was readily delivered and transported through unsaturated porous media where phenanthrene and diesel range...tion, but is not currently a well-developed technology. Bioremediation : Sequencing oxidation and reduction reactions may be achieved through

  12. Performance limitations of polymer electrolytes based on ethylene oxide polymers

    International Nuclear Information System (INIS)

    Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

    1999-01-01

    Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles

  13. Synthesis and properties of hexafluoroisopropylidene-containing sulfonated poly(arylene thioether phosphine oxide)s for proton exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Gui, Longyong; Zhang, Chunjie; Kang, Sen; Tan, Ning; Xiao, Guyu; Yan, Deyue [College of Chemistry and Chemical Engineering, The State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China)

    2010-03-15

    A series of novel sulfonated poly(arylene thioether phosphine oxide)s with hexafluoroisopropylidene moieties (sPTPOF) were prepared by polycondensation of sulfonated bis(4-fluorophenyl)phenyl phosphine oxide and bis(4-fluorophenyl)phenyl phosphine oxide with 4,4'-(hexafluoroisopropylidene) diphenthiol. The incorporation of hexafluoroisopropylidene moieties to the resulting polymers is effective to increase the hydrophobicity of non-sulfonated segments and to decrease the swelling while maintaining high proton conductivity. For instance, sPTPOF-100 showed a proton conductivity of 0.090 S/cm as well as a swelling of 5.3% at 80 C. In addition, the sPTPOF polymers exhibited excellent thermal properties and oxidative stability. AFM phase images illustrated that the sPTPOF membranes show a special nanophase-separated morphology, namely, the connectivity of ionic channels increased obviously but their width only slightly increased with increasing sulfonation degree. This special microstructure is favorable for promoting proton transport and restraining the swelling. The sPTPOF polymers are a promising material for proton exchange membranes. (author)

  14. Controlling Oxygen Mobility in Ruddlesden–Popper Oxides

    Directory of Open Access Journals (Sweden)

    Dongkyu Lee

    2017-03-01

    Full Text Available Discovering new energy materials is a key step toward satisfying the needs for next-generation energy conversion and storage devices. Among the various types of oxides, Ruddlesden–Popper (RP oxides (A2BO4 are promising candidates for electrochemical energy devices, such as solid oxide fuel cells, owing to their attractive physicochemical properties, including the anisotropic nature of oxygen migration and controllable stoichiometry from oxygen excess to oxygen deficiency. Thus, understanding and controlling the kinetics of oxygen transport are essential for designing optimized materials to use in electrochemical energy devices. In this review, we first discuss the basic mechanisms of oxygen migration in RP oxides depending on oxygen nonstoichiometry. We then focus on the effect of changes in the defect concentration, crystallographic orientation, and strain on the oxygen migration in RP oxides. We also briefly review their thermal and chemical stability. Finally, we conclude with a perspective on potential research directions for future investigation to facilitate controlling oxygen ion migration in RP oxides.

  15. Oxidative stress in duckweed (Lemna minor L.) induced by glyphosate: Is the mitochondrial electron transport chain a target of this herbicide?

    Science.gov (United States)

    Gomes, Marcelo Pedrosa; Juneau, Philippe

    2016-11-01

    We investigated the physiological responses of Lemna minor plants exposed to glyphosate. The deleterious effects of this herbicide on photosynthesis, respiration, and pigment concentrations were related to glyphosate-induced oxidative stress through hydrogen peroxide (H 2 O 2 ) accumulation. By using photosynthetic and respiratory electron transport chain (ETC) inhibitors we located the primary site of reactive oxygen species (ROS) production in plants exposed to 500 mg glyphosate l -1 . Inhibition of mitochondrial ETC Complex I by rotenone reduced H 2 O 2 concentrations in glyphosate-treated plants. Complex III activity was very sensitive to glyphosate which appears to act much like antimycin A (an inhibitor of mitochondrial ETC Complex III) by shunting electrons from semiquinone to oxygen, with resulting ROS formation. Confocal evaluations for ROS localization showed that ROS are initially produced outside of the chloroplasts upon initial glyphosate exposure. Our results indicate that in addition to interfering with the shikimate pathway, glyphosate can induce oxidative stress in plants through H 2 O 2 formation by targeting the mitochondrial ETC, which would explain its observed effects on non-target organisms. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Combined evaluation. Plutonium transports in France. Problems of safety and reliability of transport container FS47; Evaluation Conjointe. Transports de plutonium en France. Problemes de surete et de securite du container de transport FS47

    Energy Technology Data Exchange (ETDEWEB)

    Marignac, Y.; Coeytaux, X. [Wise-Paris, 75 (France); Large, J.H. [Nuclear Engineer, Large and Associates, Londres (United Kingdom)

    2004-09-15

    This report concerns the safety and the protection of plutonium dioxide transported from Cogema La Hague to the mixed oxide fuel plant of Marcoule and Cadarache. The French approach of the transport safety is based on the combining of two essential principles: the first one affirms that the performances of the FS47 container in regard of containment (norms TS-R-1 from IAEA for the accidental conditions) is conceived to resist in any situation even terrorism or sabotage. In fact, the IAEA norm follows a probabilistic study without a voluntary attack such a terrorist one. The second principle rests on the ability to prevent the treat of terrorism acts, because of a secrecy policy on the plutonium transport. It appeared that the Green peace association has succeeded several times to know exactly the hours, the trips of the plutonium transport and this simple thing raises more questions than it solves. (N.C.)

  17. Oxidation process of AlOx-based magnetic tunnel junctions studied by photoconductance

    NARCIS (Netherlands)

    Koller, P.H.P.; Vanhelmont, F.W.M.; Boeve, H.; Lumens, P.G.E.; Jonge, de W.J.M.

    2003-01-01

    The oxidation process of Co/AlOx/Co magnetic tunnel junctions has been investigated by photoconductance, in addition to traditional transport measurements. The shape of the photoconductance curves is explained within the framework of a simple qualitative model, assuming an oxidation time dependent

  18. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  19. Neuronal nitric oxide synthase mediates insulin- and oxidative stress-induced glucose uptake in skeletal muscle myotubes.

    Science.gov (United States)

    Kellogg, Dean L; McCammon, Karen M; Hinchee-Rodriguez, Kathryn S; Adamo, Martin L; Roman, Linda J

    2017-09-01

    Previously published studies strongly suggested that insulin- and exercise-induced skeletal muscle glucose uptake require nitric oxide (NO) production. However, the signal transduction mechanisms by which insulin and contraction regulated NO production and subsequent glucose transport are not known. In the present study, we utilized the myotube cell lines treated with insulin or hydrogen peroxide, the latter to mimic contraction-induced oxidative stress, to characterize these mechanisms. We found that insulin stimulation of neuronal nitric oxide synthase (nNOS) phosphorylation, NO production, and GLUT4 translocation were all significantly reduced by inhibition of either nNOS or Akt2. Hydrogen peroxide (H 2 O 2 ) induced phosphorylation of nNOS at the same residue as did insulin, and also stimulated NO production and GLUT4 translocation. nNOS inhibition prevented H 2 O 2 -induced GLUT4 translocation. AMP activated protein kinase (AMPK) inhibition prevented H 2 O 2 activation and phosphorylation of nNOS, leading to reduced NO production and significantly attenuated GLUT4 translocation. We conclude that nNOS phosphorylation and subsequently increased NO production are required for both insulin- and H 2 O 2 -stimulated glucose transport. Although the two stimuli result in phosphorylation of the same residue on nNOS, they do so through distinct protein kinases. Thus, insulin and H 2 O 2 -activated signaling pathways converge on nNOS, which is a common mediator of glucose uptake in both pathways. However, the fact that different kinases are utilized provides a basis for the use of exercise to activate glucose transport in the face of insulin resistance. Copyright © 2017. Published by Elsevier Inc.

  20. Impact of Bacterial NO>3- Transport on Sediment Biogeochemistry

    DEFF Research Database (Denmark)

    Nielsen, Lars Peter

    2005-01-01

    Experiments demonstrated that Beggiatoa could induce a H2S-depleted suboxic zone of more than 10 mm in marine sediments and cause a divergence in sediment NO3- reduction from denitrification to dissimilatory NO3- reduction to ammonium. pH, O2, and H2S profiles indicated that the bacteria oxidized H......2S with NO3- and transported S0 to the sediment surface for aerobic oxidation....

  1. Oxidation of zirconium alloys in steam: influence of tetragonal zirconia on oxide growth mechanism

    International Nuclear Information System (INIS)

    Godlewski, J.

    1990-07-01

    The oxidation of zirconium alloys in presence of steam, presents after a 'parabolic' growth law, an acceleration of the oxidation velocity. This phenomenon limits the use of zirconium alloys as nuclear fuel cladding element. In order to determine the physico-chemical process leading to this kinetic transition, two approaches have been carried out: the first one has consisted to determine the composition of the oxide layer and its evolution with the oxidation time; and the second one to determine the oxygen diffusion coefficients in the oxide layers of pre- and post-transition as well as their evolution with the oxidation time. The composition of the oxide layers has been determined by two analyses techniques: the X-ray diffraction and the laser Raman spectroscopy. This last method has allowed to confirm the presence of tetragonal zirconium oxide in the oxide layers. Analyses carried out by laser Raman spectroscopy on oxides oblique cuttings have revealed that the tetragonal zirconium oxide is transformed in monoclinic phase during the kinetic transition. A quantitative approach has allowed to corroborate the results obtained by these two techniques. In order to determine the oxygen diffusion coefficients in the oxides layers, two diffusion treatments have been carried out: 1)under low pressure with D 2 18 O 2 ) under high pressure in an autoclave with H 2 18 O. The oxygen 18 concentration profiles have been obtained by two analyses techniques: the nuclear microprobe and the secondary ions emission spectroscopy. The obtained profiles show that the mass transport is made by the volume and particularly by the grain boundaries. The corresponding diffusion coefficients have been calculated with the WHIPPLE and LE CLAIRE solution. The presence of tetragonal zirconium oxide, its relation with the kinetic transition, and the evolution of the diffusion coefficients with the oxidation time, are discussed in terms of internal stresses in the oxide layer and of the oxide layer

  2. Monocarboxylate transporters in the brain and in cancer.

    Science.gov (United States)

    Pérez-Escuredo, Jhudit; Van Hée, Vincent F; Sboarina, Martina; Falces, Jorge; Payen, Valéry L; Pellerin, Luc; Sonveaux, Pierre

    2016-10-01

    Monocarboxylate transporters (MCTs) constitute a family of 14 members among which MCT1-4 facilitate the passive transport of monocarboxylates such as lactate, pyruvate and ketone bodies together with protons across cell membranes. Their anchorage and activity at the plasma membrane requires interaction with chaperon protein such as basigin/CD147 and embigin/gp70. MCT1-4 are expressed in different tissues where they play important roles in physiological and pathological processes. This review focuses on the brain and on cancer. In the brain, MCTs control the delivery of lactate, produced by astrocytes, to neurons, where it is used as an oxidative fuel. Consequently, MCT dysfunctions are associated with pathologies of the central nervous system encompassing neurodegeneration and cognitive defects, epilepsy and metabolic disorders. In tumors, MCTs control the exchange of lactate and other monocarboxylates between glycolytic and oxidative cancer cells, between stromal and cancer cells and between glycolytic cells and endothelial cells. Lactate is not only a metabolic waste for glycolytic cells and a metabolic fuel for oxidative cells, but it also behaves as a signaling agent that promotes angiogenesis and as an immunosuppressive metabolite. Because MCTs gate the activities of lactate, drugs targeting these transporters have been developed that could constitute new anticancer treatments. This article is part of a Special Issue entitled: Mitochondrial Channels edited by Pierre Sonveaux, Pierre Maechler and Jean-Claude Martinou. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  3. Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

    KAUST Repository

    Anneser, Markus R.

    2016-02-26

    The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(III) whereas in the latter case an oxide bridged Fe(III) dimer is formed. In acetone, an Fe(III)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(III)–O–Fe(III) dimer is formed from the Fe(III) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(II) complex in both solvents is a reversible process. For the regeneration of the initial Fe(II) complex both organic and inorganic reducing agents can be used.

  4. Intramyocardial oxygen transport by quantitative diffuse reflectance spectroscopy in calves

    Science.gov (United States)

    Lindbergh, Tobias; Larsson, Marcus; Szabó, Zoltán; Casimir-Ahn, Henrik; Strömberg, Tomas

    2010-03-01

    Intramyocardial oxygen transport was assessed during open-chest surgery in calves by diffuse reflectance spectroscopy using a small intramuscular fiber-optic probe. The sum of hemo- and myoglobin tissue fraction and oxygen saturation, the tissue fraction and oxidation of cytochrome aa3, and the tissue fraction of methemoglobin were estimated using a calibrated empirical light transport model. Increasing the oxygen content in the inhaled gas, 21%-50%-100%, in five calves (group A) gave an increasing oxygen saturation of 19+/-4%, 24+/-5%, and 28+/-8% (panimals increased with LVAD pump speed (p<0.001, ANOVA) and with oxygen content in inhaled gas (p<0.001, ANOVA). The cytochrome aa3 oxidation level was above 96% in both group A and group B calves, including the two cases involving cardiac arrest. In conclusion, the estimated tissue fractions and oxygenation/oxidation levels of the myocardial chromophores during respiratory and hemodynamic provocations were in agreement with previously presented results, demonstrating the potential of the method.

  5. Spin-dependent transport properties of a GaMnAs-based vertical spin metal-oxide-semiconductor field-effect transistor structure

    Energy Technology Data Exchange (ETDEWEB)

    Kanaki, Toshiki, E-mail: kanaki@cryst.t.u-tokyo.ac.jp; Asahara, Hirokatsu; Ohya, Shinobu, E-mail: ohya@cryst.t.u-tokyo.ac.jp; Tanaka, Masaaki, E-mail: masaaki@ee.t.u-tokyo.ac.jp [Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

    2015-12-14

    We fabricate a vertical spin metal-oxide-semiconductor field-effect transistor (spin-MOSFET) structure, which is composed of an epitaxial single-crystal heterostructure with a ferromagnetic-semiconductor GaMnAs source/drain, and investigate its spin-dependent transport properties. We modulate the drain-source current I{sub DS} by ∼±0.5% with a gate-source voltage of ±10.8 V and also modulate I{sub DS} by up to 60% with changing the magnetization configuration of the GaMnAs source/drain at 3.5 K. The magnetoresistance ratio is more than two orders of magnitude higher than that obtained in the previous studies on spin MOSFETs. Our result shows that a vertical structure is one of the hopeful candidates for spin MOSFET when the device size is reduced to a sub-micron or nanometer scale.

  6. Spin-dependent transport properties of a GaMnAs-based vertical spin metal-oxide-semiconductor field-effect transistor structure

    International Nuclear Information System (INIS)

    Kanaki, Toshiki; Asahara, Hirokatsu; Ohya, Shinobu; Tanaka, Masaaki

    2015-01-01

    We fabricate a vertical spin metal-oxide-semiconductor field-effect transistor (spin-MOSFET) structure, which is composed of an epitaxial single-crystal heterostructure with a ferromagnetic-semiconductor GaMnAs source/drain, and investigate its spin-dependent transport properties. We modulate the drain-source current I DS by ∼±0.5% with a gate-source voltage of ±10.8 V and also modulate I DS by up to 60% with changing the magnetization configuration of the GaMnAs source/drain at 3.5 K. The magnetoresistance ratio is more than two orders of magnitude higher than that obtained in the previous studies on spin MOSFETs. Our result shows that a vertical structure is one of the hopeful candidates for spin MOSFET when the device size is reduced to a sub-micron or nanometer scale

  7. Uncontrolled transport of nuclear materials

    International Nuclear Information System (INIS)

    Wassermann, U.

    1985-01-01

    An account is given of international transport of plutonium, uranium oxides, uranium hexafluoride, enriched uranium and irradiated fuel for reprocessing. Referring to the sinking of the 'Mont Louis', it is stated that the International Maritime Organization has been asked by the National Union of Seamen and 'Greenpeace' to bar shipment of radioactive material until stricter international safety regulations are introduced. (U.K.)

  8. Novel exchange mechanisms in the surface diffusion of oxides

    International Nuclear Information System (INIS)

    Harris, Duncan J; Lavrentiev, Mikhail Yu; Harding, John H; Allan, Neil L; Purton, John A

    2004-01-01

    We use temperature-accelerated dynamics to show the importance of exchange mechanisms in surface diffusion and growth of simple oxides. Such mechanisms can dominate transport processes both on terraces and steps for both homoepitaxial and heteroepitaxial growth. We suggest that the mixing inevitable when an exchange mechanism is present must be considered when attempts are made to grow sharp interfaces in oxide nanostructures. (letter to the editor)

  9. Significantly improved photovoltaic performance in polymer bulk heterojunction solar cells with graphene oxide /PEDOT:PSS double decked hole transport layer

    Science.gov (United States)

    Rafique, Saqib; Abdullah, Shahino Mah; Shahid, Muhammad Mehmood; Ansari, Mohammad Omaish; Sulaiman, Khaulah

    2017-01-01

    This work demonstrates the high performance graphene oxide (GO)/PEDOT:PSS doubled decked hole transport layer (HTL) in the PCDTBT:PC71BM based bulk heterojunction organic photovoltaic device. The devices were tested on merits of their power conversion efficiency (PCE), reproducibility, stability and further compared with the devices with individual GO or PEDOT:PSS HTLs. Solar cells employing GO/PEDOT:PSS HTL yielded a PCE of 4.28% as compared to either of individual GO or PEDOT:PSS HTLs where they demonstrated PCEs of 2.77 and 3.57%, respectively. In case of single GO HTL, an inhomogeneous coating of ITO caused the poor performance whereas PEDOT:PSS is known to be hygroscopic and acidic which upon direct contact with ITO reduced the device performance. The improvement in the photovoltaic performance is mainly ascribed to the increased charge carriers mobility, short circuit current, open circuit voltage, fill factor, and decreased series resistance. The well matched work function of GO and PEDOT:PSS is likely to facilitate the charge transportation and an overall reduction in the series resistance. Moreover, GO could effectively block the electrons due to its large band-gap of ~3.6 eV, leading to an increased shunt resistance. In addition, we also observed the improvement in the reproducibility and stability.

  10. Significantly improved photovoltaic performance in polymer bulk heterojunction solar cells with graphene oxide /PEDOT:PSS double decked hole transport layer.

    Science.gov (United States)

    Rafique, Saqib; Abdullah, Shahino Mah; Shahid, Muhammad Mehmood; Ansari, Mohammad Omaish; Sulaiman, Khaulah

    2017-01-13

    This work demonstrates the high performance graphene oxide (GO)/PEDOT:PSS doubled decked hole transport layer (HTL) in the PCDTBT:PC 71 BM based bulk heterojunction organic photovoltaic device. The devices were tested on merits of their power conversion efficiency (PCE), reproducibility, stability and further compared with the devices with individual GO or PEDOT:PSS HTLs. Solar cells employing GO/PEDOT:PSS HTL yielded a PCE of 4.28% as compared to either of individual GO or PEDOT:PSS HTLs where they demonstrated PCEs of 2.77 and 3.57%, respectively. In case of single GO HTL, an inhomogeneous coating of ITO caused the poor performance whereas PEDOT:PSS is known to be hygroscopic and acidic which upon direct contact with ITO reduced the device performance. The improvement in the photovoltaic performance is mainly ascribed to the increased charge carriers mobility, short circuit current, open circuit voltage, fill factor, and decreased series resistance. The well matched work function of GO and PEDOT:PSS is likely to facilitate the charge transportation and an overall reduction in the series resistance. Moreover, GO could effectively block the electrons due to its large band-gap of ~3.6 eV, leading to an increased shunt resistance. In addition, we also observed the improvement in the reproducibility and stability.

  11. Oxidative release of chromium from Archean ultramafic rocks, its transport and environmental impact – A Cr isotope perspective on the Sukinda valley ore district (Orissa, India)

    International Nuclear Information System (INIS)

    Paulukat, Cora; Døssing, Lasse N.; Mondal, Sisir K.; Voegelin, Andrea R.; Frei, Robert

    2015-01-01

    Highlights: • Cr in lateritic soil profiles in Sukinda valley are partly highly negatively fractionated. • Oxidative weathering and mining operations affect the Cr isotope composition of the local surface water. • Isotopically heavy Cr from land is probably preserved during its transport to the sea. • The environmental impact of toxic Cr(VI) can potentially be diminished by microbial mats. - Abstract: This study investigates Cr isotope fractionation during soil formation from Archean (3.1–3.3 Ga) ultramafic rocks in a chromite mining area in the southern Singhbhum Craton (Orissa, India). The Cr-isotope signatures of two studied weathering profiles, range from non-fractionated mantle values to negatively fractionated values as low as δ 53 Cr = −1.29 ± 0.04‰. Local surface waters are isotopically heavy relative to the soils. This supports the hypothesis that during oxidative weathering isotopically heavy Cr(VI) is leached from the soils to runoff. The impact of mining pollution is observed downstream from the mine where surface water Cr concentrations are significantly increased, accompanied by a shift to less positive δ 53 Cr values relative to upstream unpolluted surface water. A microbial mat sample indicates that microbes have the potential to reduce and immobilize Cr(VI), which could be a factor in controlling the hazardous impact of Cr(VI) on health and environment. The positive Cr isotope signatures of the Brahmani estuary and coastal seawater collected from the Bay of Bengal further indicate that the positively fractionated Cr isotope signal from the catchment area is preserved during its transport to the sea. Isotopically lighter Cr(VI) downstream from the mine is probably back-reduced to Cr(III) during riverine transport leading to similar Cr-isotope values in the estuary as observed upstream from the mine

  12. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] (A) is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"- (1), it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Combined evaluation. Plutonium transports in France. Problems of safety and reliability of transport container FS47

    International Nuclear Information System (INIS)

    Marignac, Y.; Coeytaux, X.; Large, J.H.

    2004-09-01

    This report concerns the safety and the protection of plutonium dioxide transported from Cogema La Hague to the mixed oxide fuel plant of Marcoule and Cadarache. The French approach of the transport safety is based on the combining of two essential principles: the first one affirms that the performances of the FS47 container in regard of containment (norms TS-R-1 from IAEA for the accidental conditions) is conceived to resist in any situation even terrorism or sabotage. In fact, the IAEA norm follows a probabilistic study without a voluntary attack such a terrorist one. The second principle rests on the ability to prevent the treat of terrorism acts, because of a secrecy policy on the plutonium transport. It appeared that the Green peace association has succeeded several times to know exactly the hours, the trips of the plutonium transport and this simple thing raises more questions than it solves. (N.C.)

  14. Modulating Hole Transport in Multilayered Photocathodes with Derivatized p-Type Nickel Oxide and Molecular Assemblies for Solar-Driven Water Splitting

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Bing [Department; Sherman, Benjamin D. [Department; Klug, Christina M. [Center; Nayak, Animesh [Department; Marquard, Seth L. [Department; Liu, Qing [Department; Bullock, R. Morris [Center; Meyer, Thomas J. [Department

    2017-08-31

    We report here a new photocathode composed of a bi-layered doped NiO film topped by a macro-mesoporous ITO (ioITO) layer with molecular assemblies attached to the ioITO surface. The NiO film containing a 2% K+ doped NiO inner layer and a 2% Cu2+ doped NiO outer layer provides sufficient driving force for hole transport after injection to NiO by the molecular assembly. The tri-layered oxide, NiK0.02O | NiCu0.02O | ioITO, sensitized by a ruthenium polypyridyl dye and functionalized with a nickel-based hydrogen evolution catalyst, outperforms its counterpart, NiO | NiO | ioITO, in photocatalytic hydrogen evolution from water over a period of several hours with a Faradaic yield of ~90%.

  15. Regulation and control of nitric oxide (NO) in macrophages

    DEFF Research Database (Denmark)

    Kovacevic, Zaklina; Sahni, Sumit; Lok, K.H.

    2017-01-01

    We recently demonstrated that a novel storage and transport mechanism for nitric oxide (NO) mediated by glutathione-S-transferase P1 (GSTP1) and multidrug resistance protein 1 (MRP1/ABCC1), protects M1-macrophage (M1-MØ) models from large quantities of endogenous NO. This system stores and transp......We recently demonstrated that a novel storage and transport mechanism for nitric oxide (NO) mediated by glutathione-S-transferase P1 (GSTP1) and multidrug resistance protein 1 (MRP1/ABCC1), protects M1-macrophage (M1-MØ) models from large quantities of endogenous NO. This system stores...... be responsible for delivering cytotoxic NO as DNICs via MRP1 from M1-MØs, to tumor cell targets....

  16. Alternative photosynthetic electron transport pathways during anaerobiosis in the green alga Chlamydomonas reinhardtii.

    Science.gov (United States)

    Hemschemeier, Anja; Happe, Thomas

    2011-08-01

    Oxygenic photosynthesis uses light as energy source to generate an oxidant powerful enough to oxidize water into oxygen, electrons and protons. Upon linear electron transport, electrons extracted from water are used to reduce NADP(+) to NADPH. The oxygen molecule has been integrated into the cellular metabolism, both as the most efficient electron acceptor during respiratory electron transport and as oxidant and/or "substrate" in a number of biosynthetic pathways. Though photosynthesis of higher plants, algae and cyanobacteria produces oxygen, there are conditions under which this type of photosynthesis operates under hypoxic or anaerobic conditions. In the unicellular green alga Chlamydomonas reinhardtii, this condition is induced by sulfur deficiency, and it results in the production of molecular hydrogen. Research on this biotechnologically relevant phenomenon has contributed largely to new insights into additional pathways of photosynthetic electron transport, which extend the former concept of linear electron flow by far. This review summarizes the recent knowledge about various electron sources and sinks of oxygenic photosynthesis besides water and NADP(+) in the context of their contribution to hydrogen photoproduction by C. reinhardtii. This article is part of a Special Issue entitled: Regulation of Electron Transport in Chloroplasts. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Modifying zirconia solid electrolyte surface property to enhance oxide transport

    Energy Technology Data Exchange (ETDEWEB)

    Liaw, B.Y.; Song, S.Y. [Univ. of Hawaii, Honolulu, HI (United States)

    1996-12-31

    Bismuth-strontium-calcium-copper oxide (Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}, BSCCO) is known for its high T{sub c} superconducting behavior and mixed conducting property. The applicability of similar high T{sub c} cuprates for intermediate-temperature solid oxide fuel cell (SOFC) application has been studied recently. We investigated the electrochemical behavior of several Ag{vert_bar}BSCCO{vert_bar}10 mol% yttria-stabilized zirconia (YSZ){vert_bar}Ag and Ag{vert_bar}YSZ{vert_bar}Ag cells using complex impedance spectroscopy. A highly uniform and porous microstructure was observed at the interface of the YSZ and BSCCO. The ionic conductivity determined from the Nyquest plots in the temperature range of 200-700{degrees}C agrees with the values reported in the literature. The specific resistance of the BSCCO{vert_bar}YSZ interface was also determined to be lower than those of the conventional manganite electrode, suggesting that BSCCO seems attractive for cathode applications in SOFC.

  18. Pressurization of Containment Vessels from Plutonium Oxide Contents

    International Nuclear Information System (INIS)

    Hensel, S.

    2012-01-01

    Transportation and storage of plutonium oxide is typically done using a convenience container to hold the oxide powder which is then placed inside a containment vessel. Intermediate containers which act as uncredited confinement barriers may also be used. The containment vessel is subject to an internal pressure due to several sources including; (1) plutonium oxide provides a heat source which raises the temperature of the gas space, (2) helium generation due to alpha decay of the plutonium, (3) hydrogen generation due to radiolysis of the water which has been adsorbed onto the plutonium oxide, and (4) degradation of plastic bags which may be used to bag out the convenience can from a glove box. The contributions of these sources are evaluated in a reasonably conservative manner.

  19. A Novel Sugar Transporter from Dianthus spiculifolius, DsSWEET12, Affects Sugar Metabolism and Confers Osmotic and Oxidative Stress Tolerance in Arabidopsis.

    Science.gov (United States)

    Zhou, Aimin; Ma, Hongping; Feng, Shuang; Gong, Shufang; Wang, Jingang

    2018-02-07

    Plant SWEETs (sugars will eventually be exported transporters) play a role in plant growth and plant response to biotic and abiotic stresses. In the present study, DsSWEET12 from Dianthus spiculifolius was identified and characterized. Real-time quantitative PCR analysis revealed that DsSWEET12 expression was induced by sucrose starvation, mannitol, and hydrogen peroxide. Colocalization experiment showed that the DsSWEET12-GFP fusion protein was localized to the plasma membrane, which was labeled with FM4-64 dye, in Arabidopsis and suspension cells of D. spiculifolius . Compared to wild type plants, transgenic Arabidopsis seedlings overexpressing DsSWEET12 have longer roots and have a greater fresh weight, which depends on sucrose content. Furthermore, a relative root length analysis showed that transgenic Arabidopsis showed higher tolerance to osmotic and oxidative stresses. Finally, a sugar content analysis showed that the sucrose content in transgenic Arabidopsis was less than that in the wild type, while fructose and glucose contents were higher than those in the wild type. Taken together, our results suggest that DsSWEET12 plays an important role in seedling growth and plant response to osmotic and oxidative stress in Arabidopsis by influencing sugar metabolism.

  20. Role of MRP transporters in regulating antimicrobial drug inefficacy and oxidative stress-induced pathogenesis during HIV-1 and TB infections.

    Science.gov (United States)

    Roy, Upal; Barber, Paul; Tse-Dinh, Yuk-Ching; Batrakova, Elena V; Mondal, Debasis; Nair, Madhavan

    2015-01-01

    Multi-Drug Resistance Proteins (MRPs) are members of the ATP binding cassette (ABC) drug-efflux transporter superfamily. MRPs are known to regulate the efficacy of a broad range of anti-retroviral drugs (ARV) used in highly active antiretroviral therapy (HAART) and antibacterial agents used in Tuberculus Bacilli (TB) therapy. Due to their role in efflux of glutathione (GSH) conjugated drugs, MRPs can also regulate cellular oxidative stress, which may contribute to both HIV and/or TB pathogenesis. This review focuses on the characteristics, functional expression, and modulation of known members of the MRP family in HIV infected cells exposed to ARV drugs and discusses their known role in drug-inefficacy in HIV/TB-induced dysfunctions. Currently, nine members of the MRP family (MRP1-MRP9) have been identified, with MRP1 and MRP2 being the most extensively studied. Details of the other members of this family have not been known until recently, but differential expression has been documented in inflammatory tissues. Researchers have found that the distribution, function, and reactivity of members of MRP family vary in different types of lymphocytes and macrophages, and are differentially expressed at the basal and apical surfaces of both endothelial and epithelial cells. Therefore, the prime objective of this review is to delineate the role of MRP transporters in HAART and TB therapy and their potential in precipitating cellular dysfunctions manifested in these chronic infectious diseases. We also provide an overview of different available options and novel experimental strategies that are being utilized to overcome the drug resistance and disease pathogenesis mediated by these membrane transporters.

  1. Role of MRP Transporters in Regulating Antimicrobial Drug Inefficacy and Oxidative Stress-induced Pathogenesis during HIV-1 and TB Infections

    Directory of Open Access Journals (Sweden)

    Upal eRoy

    2015-09-01

    Full Text Available Multi-Drug Resistance Proteins (MRPs are members of the ATP binding cassette (ABC drug-efflux transporter superfamily. MRPs are known to regulate the efficacy of a broad range of anti-retroviral drugs (ARV used in highly active antiretroviral therapy (HAART and antibacterial agents used in Tuberculus Bacilli (TB therapy. Due to their role in efflux of glutathione (GSH conjugated drugs, MRPs can also regulate cellular oxidative stress, which may contribute to both HIV and/or TB pathogenesis. This review focuses on the characteristics, functional expression, and modulation of known members of the MRP family in HIV infected cells exposed to ARV drugs and discusses their known role in drug-inefficacy in HIV/TB-induced dysfunctions. Currently, nine members of the MRP family (MRP1-MRP9 have been identified, with MRP1 and MRP2 being the most extensively studied. Details of the other members of this family have not been known until recently, but differential expression has been documented in inflammatory tissues. Researchers have found that the distribution, function and reactivity of members of MRP family vary in different types of lymphocytes and macrophages, and are differentially expressed at the basal and apical surfaces of both endothelial and epithelial cells. Therefore, the prime objective of this review is to delineate the role of MRP transporters in HAART and TB therapy and their potential in precipitating cellular dysfunctions manifested in these chronic infectious diseases. We also provide an overview of different available options and novel experimental strategies that are being utilized to overcome the drug resistance and disease pathogenesis mediated by these membrane transporters.

  2. Irradiated nuclear fuel transport from Japan to Europe

    International Nuclear Information System (INIS)

    Kavanagh, M.T.; Shimoyama, S.

    1976-01-01

    Irradiated nuclear fuel has been transported from Japan to Europe since 1969, although U.K. experience goes back almost two decades. Both magnox and oxide fuel have been transported, and the technical requirements associated with each type of fuel are outlined. The specialized ships used by British Nuclear Fuels Limited (BNFL) for this transport are described, as well as the ships being developed for future use in the Japan trade. The ship requirements are related to the regulatory position both in the United Kingdom and internationally, and the Japanese regulatory requirements are described. Finally, specific operational experience of a Japanese reactor operator is described

  3. Proton and oxide ion conductivity of doped LaScO3

    DEFF Research Database (Denmark)

    Lybye, D.; Bonanos, N.

    1999-01-01

    . At temperatures below 800 degrees C and low partial pressure of oxygen, proton conduction was dominant. Above this temperature, the ionic conductivity is dominated by oxide ion transport. The protonic transport number was estimated from the conductivities measured in dry and in water-moisturised gas. An isotope......The conductivity of La0.9Sr0.1Sc0.9Mg0.1O3 has been studied by impedance spectroscopy in controlled atmospheres. The material was found to be a mixed conductor with p-type conduction at high oxygen partial pressures and a combined proton and oxide ion conductor at low oxygen partial pressures...

  4. The ascorbate carrier of higher plant plasma membranes preferentially translocates the fully oxidized (dehydroascorbate) molecule

    International Nuclear Information System (INIS)

    Horemans, N.; Asard, H.; Caubergs, R.J.

    1997-01-01

    Recently, the uptake of 14C-labeled ascorbate (ASC) into highly purified bean (Phaseolus vulgaris L.) plasma membrane vesicles was demonstrated in our laboratory. However, the question of the redox status of the transported molecule (ASC or dehydroascorbate [DHA]) remained unanswered. In this paper we present evidence that DHA is transported through the plasma membrane. High-performance liquid chromatography analysis of the redox status of ASC demonstrated that freshly purified plasma membranes exhibit a high ASC oxidation activity. Although it is not yet clear whether this activity is enzymatic it complicates the interpretation of ASC-transport experiments in vitro and in vivo. In an attempt to correlate the ASC redox status to transport of the molecule, the ability of different compounds to reduce DHA was analyzed and their effect on ASC-transport activity tested. Administering of various reductants resulted in different levels of inhibition of ASC uptake (dithiothreitol dithioerythritol beta-mercaptoethanol beta-mercaptopropanol). Glutathione, cysteine, dithionite, and thiourea did not significantly affect ASC transport. Statistical analysis indicated a strong correlation of the Spearman rank correlation coefficient (Rs) of 0.919 (P = 0.0005, n = 9) between the level of ASC oxidation and the amount of transported molecules into the vesicles. The administering of ASC oxidants such as ferricyanide and ASC oxidase resulted in a stimulated ASC uptake into the plasma membrane vesicles. Together, our results demonstrate that a vitamin C carrier in purified bean plasma membranes translocates DHA from the apoplast to the cytosol

  5. Role of solution chemistry in the retention and release of graphene oxide nanomaterials in uncoated and iron oxide-coated sand

    Science.gov (United States)

    Upon increasing production and use of graphene oxide nanoparticles (GONPs), concerns agitate over their potential impacts and risks to the environment, ecosystem, and human health. An improved understanding of the fate and transport including remobilization of GONPs in the subsur...

  6. Carrier transport and electronic structure in amorphous oxide semiconductor, a-InGaZnO4

    International Nuclear Information System (INIS)

    Takagi, Akihiro; Nomura, Kenji; Ohta, Hiromichi; Yanagi, Hiroshi; Kamiya, Toshio; Hirano, Masahiro; Hosono, Hideo

    2005-01-01

    Carrier transport properties in amorphous oxide semiconductor InGaZnO 4 (a-IGZO) thin films were investigated in detail using temperature dependence of Hall measurements. It was found that Hall mobility increased distinctly as carrier concentration increased. Unlikely conventional amorphous semiconductors such as a-Si/H, definite normal Hall voltage signals were observed on the films with carrier concentrations (N e )>10 16 cm -3 , and Hall mobilities as large as 15 cm 2 (Vs) -1 were attained in the films with N e >10 20 cm -3 . When N e was less than 10 19 cm -3 , the temperature dependence of Hall mobility showed thermally-activated behavior in spite that carrier concentration was independent of temperature. While, it changed to almost degenerate conduction at N e >10 18 cm -3 . These behaviors are similar to those observed in single-crystalline IGZO, and are explained by percolation conduction through distributed potential barriers which are formed in the vicinity of the conduction band bottom due to the randomness of the amorphous structure. The effective mass of a-IGZO was estimated to be ∼0.34 m e (m e is the mass of free electron) from optical data, which is almost the same as that of crystalline IGZO (∼0.32 m e )

  7. The occurrence and control of nitric oxide generation by the plant mitochondrial electron transport chain.

    Science.gov (United States)

    Alber, Nicole A; Sivanesan, Hampavi; Vanlerberghe, Greg C

    2017-07-01

    The plant mitochondrial electron transport chain (ETC) is bifurcated such that electrons from ubiquinol are passed to oxygen via the usual cytochrome path or through alternative oxidase (AOX). We previously showed that knockdown of AOX in transgenic tobacco increased leaf concentrations of nitric oxide (NO), implying that an activity capable of generating NO had been effected. Here, we identify the potential source of this NO. Treatment of leaves with antimycin A (AA, Q i -site inhibitor of Complex III) increased NO amount more than treatment with myxothiazol (Myxo, Q o -site inhibitor) despite both being equally effective at inhibiting respiration. Comparison of nitrate-grown wild-type with AOX knockdown and overexpression plants showed a negative correlation between AOX amount and NO amount following AA. Further, Myxo fully negated the ability of AA to increase NO amount. With ammonium-grown plants, neither AA nor Myxo strongly increased NO amount in any plant line. When these leaves were supplied with nitrite alongside the AA or Myxo, then the inhibitor effects across lines mirrored that of nitrate-grown plants. Hence the ETC, likely the Q-cycle of Complex III generates NO from nitrite, and AOX reduces this activity by acting as a non-energy-conserving electron sink upstream of Complex III. © 2016 John Wiley & Sons Ltd.

  8. Quantifying Ion Transport in Polymers Using Electrochemical Quartz Crystal Microbalance with Dissipation

    Science.gov (United States)

    Lutkenhaus, Jodie; Wang, Shaoyang

    For polymers in energy systems, one of the most common means of quantifying ion transport is that of electrochemical impedance spectroscopy, in which an alternating electric field is applied and the resultant impedance response is recorded. While useful, this approach misses subtle details in transient film swelling, effects of hydration or solvent shells around the transporting ion, and changes in mechanical properties of the polymer. Here we present electrochemical quartz crystal microbalance with dissipation (EQCMD) monitoring as a means to quantify ion transport, dynamic swelling, and mechanical properties of polymers during electrochemical interrogation. We focus upon EQCMD characterization of the redox-active nitroxide radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA). Upon oxidation, PTMA becomes positively charged, which requires the transport of a complementary anion into the polymer for electroneutrality. By EQCMD, we quantify anion transport and resultant swelling upon oxidation, as well as decoupling of contributions attributed to the ion and the solvent. We explore the effect of different lithium electrolyte salts in which each salt gives different charge storage and mass transport behavior. This is attributed to varied polymer-dopant and dopant-solvent interactions. The work was supported by the Grant DE-SC0014006 funded by the U.S. Department of Energy, Office of Science.

  9. A Systematic Transport and Thermodynamic Study of Heavy Transition Metal Oxides with Hexagonal Structure

    Science.gov (United States)

    Butrouna, Kamal

    There is no apparent, dominant interaction in heavy transition metal oxides (TMO), especially in 5d-TMO, where all relevant interactions are of comparable energy scales, and therefore strongly compete. In particular, the spin-orbit interaction (SOI) strongly competes with the electron-lattice and on-site Coulomb interaction (U). Therefore, any tool that allows one to tune the relative strengths of SOI and U is expected to offer an opportunity for the discovery and study of novel materials. BaIrO3 is a magnetic insulator driven by SOI, whereas the isostructural BaRuO3 is a paramagnetic metal. The contrasting ground states have been shown to result from the critical role of SOI in the iridate. This dissertation thoroughly examines a wide array of newly observed novel phenomena induced by adjusting the relative strengths of SOI and U via a systematic chemical substitution of the Ru4+(4d 4) ions for Ir4+(5d5) ions in BaIrO3, i.e., in high quality single crystals of BaIr1--x RuxO3(0.0 ≤ x ≤ 1.0). Our investigation of structural, magnetic, transport and thermal properties reveals that Ru substitution directly rebalances the competing energies so profoundly that it generates a rich phase diagram for BaIr 1--xRuxO 3 featuring two major effects: (1) Light Ru doping (0 ≤ x ≤ 0.15) prompts a simultaneous and precipitous drop in both the magnetic ordering temperature TC and the electrical resistivity, which exhibits metal-insulator transition at around TC. (2) Heavier Ru doping (0.41 ≤ x ≤ 0.82) induces a robust metallic and spin frustration state. For comparison and contrast, we also substituted Rh4+(4d 5) ions for Ir4+(5d5) ions in BaIrO3, i.e. in BaIr1--xRhxO 3(0.0 ≤ x ≤ 0.1), where Rh only reduces the SOI, but without altering the band filling. Hence, this system remains tuned at the Mott instability and is very susceptible to disorder scattering which gives rise to Anderson localization. KEYWORDS: spin-orbit interaction, heavy transition metal oxides

  10. Toxicity of Graphene Shells, Graphene Oxide, and Graphene Oxide Paper Evaluated with Escherichia coli Biotests.

    Science.gov (United States)

    Efremova, Ludmila V; Vasilchenko, Alexey S; Rakov, Eduard G; Deryabin, Dmitry G

    2015-01-01

    The plate-like graphene shells (GS) produced by an original methane pyrolysis method and their derivatives graphene oxide (GO) and graphene oxide paper (GO-P) were evaluated with luminescent Escherichia coli biotests and additional bacterial-based assays which together revealed the graphene-family nanomaterials' toxicity and bioactivity mechanisms. Bioluminescence inhibition assay, fluorescent two-component staining to evaluate cell membrane permeability, and atomic force microscopy data showed GO expressed bioactivity in aqueous suspension, whereas GS suspensions and the GO-P surface were assessed as nontoxic materials. The mechanism of toxicity of GO was shown not to be associated with oxidative stress in the targeted soxS::lux and katG::lux reporter cells; also, GO did not lead to significant mechanical disruption of treated bacteria with the release of intracellular DNA contents into the environment. The well-coordinated time- and dose-dependent surface charge neutralization and transport and energetic disorders in the Escherichia coli cells suggest direct membrane interaction, internalization, and perturbation (i.e., "membrane stress") as a clue to graphene oxide's mechanism of toxicity.

  11. Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex.

    Science.gov (United States)

    Wasser, Ian M; Fry, H Christopher; Hoertz, Paul G; Meyer, Gerald J; Karlin, Kenneth D

    2004-12-27

    Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief

  12. Pulsed Magnetic Field Improves the Transport of Iron Oxide Nanoparticles through Cell Barriers

    Science.gov (United States)

    Min, Kyoung Ah; Shin, Meong Cheol; Yu, Faquan; Yang, Meizhu; David, Allan E.; Yang, Victor C.; Rosania, Gus R.

    2013-01-01

    Understanding how a magnetic field affects the interaction of magnetic nanoparticles (MNPs) with cells is fundamental to any potential downstream applications of MNPs as gene and drug delivery vehicles. Here, we present a quantitative analysis of how a pulsed magnetic field influences the manner in which MNPs interact with, and penetrate across a cell monolayer. Relative to a constant magnetic field, the rate of MNP uptake and transport across cell monolayers was enhanced by a pulsed magnetic field. MNP transport across cells was significantly inhibited at low temperature under both constant and pulsed magnetic field conditions, consistent with an active mechanism (i.e. endocytosis) mediating MNP transport. Microscopic observations and biochemical analysis indicated that, in a constant magnetic field, transport of MNPs across the cells was inhibited due to the formation of large (>2 μm) magnetically-induced MNP aggregates, which exceeded the size of endocytic vesicles. Thus, a pulsed magnetic field enhances the cellular uptake and transport of MNPs across cell barriers relative to a constant magnetic field by promoting accumulation while minimizing magnetically-induced MNP aggregates at the cell surface. PMID:23373613

  13. Bacterial Electrocatalysis of K4[Fe(CN)6] Oxidation

    DEFF Research Database (Denmark)

    Zheng, Zhiyong; Xiao, Yong; Wu, Ranran

    Shewanella oneidensis MR-1 (MR-1), a model strain of electrochemically active bacteria, can transfer electrons from cell to extracellular electron acceptors including Fe(III) (hydro)oxides. It has been reported that several redox species such as cytochromes in membranes and flavins assist...... in the electron transport (ET) processes. However, the oxidization of metal compounds was barely described. Here we report electrocatalysis of K4[Fe(CN)6] oxidation by MR-1. K4[Fe(CN)6] is a redox inorganic compound and shows a reversible redox process on bare glassy carbon (GCE). This is reflected by a pair...

  14. Conductive oxide cantilever for cryogenic nano-potentiometry

    International Nuclear Information System (INIS)

    Hiroya, Tsutomu; Inagaki, Katsuhiko; Tanda, Satoshi; Tsuneta, Taku; Yamaya, Kazuhiko

    2003-01-01

    Nanoscale electrical transport properties have attracted attentions because of new phenomena such as ballistic transport, quantized resistance, and Coulomb blockade. For measurement of nanoscale resistance, we have been developing a cryogenic atomic force microscope that can operate at 1.8 K. To use it as an electrode, we coated the cantilever with conductive oxides of TiO and indium tin oxide (ITO). We verified that TiO and ITO thin films remain conductive even at 4.2 K. Also we measured I-V characteristics of the tip-sample contact with a standard sample of NbSe 2 single crystal, and found that the conductive coats were not lost under large stresses due to the tip-sample contact. Moreover, we succeeded in obtaining a room temperature nano-potentiometry of a gold thin film with the ITO coated cantilever. In conclusion, the TiO and ITO coated cantilevers are applicable to cryogenic nano-potentiometry

  15. Electronic properties of hafnium oxide: A contribution from defects and traps

    Energy Technology Data Exchange (ETDEWEB)

    Gritsenko, Vladimir A., E-mail: grits@isp.nsc.ru; Perevalov, Timofey V.; Islamov, Damir R., E-mail: damir@isp.nsc.ru

    2016-02-15

    In the present article, we give a review of modern data and latest achievements pertaining to the study of electronic properties of oxygen vacancies in hafnium oxide. Hafnium oxide is a key dielectric for use in many advanced silicon devices. Oxygen vacancies in hafnium oxide largely determine the electronic properties of the material. We show that the electronic transitions between the states due to oxygen vacancies largely determine the optical absorption and luminescent properties of hafnium oxide. We discuss the role of oxygen vacancies as traps that facilitate charge transport in hafnium oxide films. Also, we demonstrate the fact that the electrical conductivity in hafnium oxide is controlled by the phonon-assisted tunnelling of charge carriers between traps that were identified as oxygen vacancies.

  16. Enhanced photovoltaic performance of inverted hybrid bulk-heterojunction solar cells using TiO2/reduced graphene oxide films as electron transport layers

    Science.gov (United States)

    Morais, Andreia; Alves, João Paulo C.; Lima, Francisco Anderson S.; Lira-Cantu, Monica; Nogueira, Ana Flavia

    2015-01-01

    In this study, we investigated inverted hybrid bulk-heterojunction solar cells with the following configuration: fluorine-doped tin oxide (FTO) |TiO2/RGO|P3HT:PC61BM|V2O5 or PEDOT:PSS|Ag. The TiO2/GO dispersions were prepared by sol-gel method, employing titanium isopropoxide and graphene oxide (GO) as starting materials. The GO concentration was varied from 0.1 to 4.0 wt%. The corresponding dispersions were spin-coated onto FTO substrates and a thermal treatment was performed to remove organic materials and to reduce GO to reduced graphene oxide (RGO). The TiO2/RGO films were characterized by x-ray diffraction, Raman spectroscopy, and microscopy techniques. Atomic force microscopy (AFM) images showed that the addition of RGO significantly changes the morphology of the TiO2 films, with loss of uniformity and increase in surface roughness. Independent of the use of V2O5 or PEDOT: PSS films as the hole transport layer, the incorporation of 2.0 wt% of RGO into TiO2 films was the optimal concentration for the best organic photovoltaic performance. The solar cells based on TiO2/RGO (2.0 wt%) electrode exhibited a ˜22.3% and ˜28.9% short circuit current density (Jsc) and a power conversion efficiency enhancement, respectively, if compared with the devices based on pure TiO2 films. Kelvin probe force microscopy images suggest that the incorporation of RGO into TiO2 films can promote the appearance of regions with different charge dissipation capacities.

  17. Sulfhydryl oxidation of mutants with cysteine in place of acidic residues in the lactose permease.

    Science.gov (United States)

    Voss, J; Sun, J; Venkatesan, P; Kaback, H R

    1998-06-02

    To examine further the role of charge-pair interactions in the structure and function of lactose permease, Asp237 (helix VII), Asp240 (helix VII), Glu126 (cytoplasmic loop IV/V), Glu269 (helix VIII), and Glu325 (helix X) were replaced individually with Cys in a functional mutant devoid of Cys residues. Each mutant was then oxidized with H2O2 in order to generate a sulfinic and/or sulfonic acid at these positions. Due to the isosteric relationship between aspartate and sulfinate, in particular, and the lower pKa of the sulfinic and sulfonic acid side chains, oxidized derivatives of Cys are useful probes for examining the role of carboxylates. Asp237-->Cys or Asp240-->Cys permease is inactive, as shown previously, but H2O2 oxidation restores activity to an extent similar to that observed when a negative charge is reintroduced by other means. Glu126-->Cys, Glu269-->Cys, or Glu325-->Cys permease is inactive, but oxidation does not restore active lactose transport. The data are consistent with previous observations indicating that Asp237 and Asp240 are not critical for active lactose transport, while Glu126, Glu269, and Glu325 are irreplaceable. Although Glu269-->Cys permease does not transport lactose, the oxidized mutant exhibits significant transport of beta,D-galactosylpyranosyl 1-thio-beta,D-galactopyranoside, a property observed with Glu269-->Asp permease. The observation supports the idea that an acidic residue at position 269 is important for substrate recognition. Finally, oxidized Glu325-->Cys permease catalyzes equilibrium exchange with an apparent pKa of about 6.5, more than a pH unit lower than that observed with Glu325-->Asp permease, thereby providing strong confirmatory evidence that a negative charge at position 325 determines the rate of translocation of the ternary complex between the permease, substrate, and H+.

  18. High-Temperature, Dual-Atmosphere Corrosion of Solid-Oxide Fuel Cell Interconnects

    Science.gov (United States)

    Gannon, Paul; Amendola, Roberta

    2012-12-01

    High-temperature corrosion of ferritic stainless steel (FSS) surfaces can be accelerated and anomalous when it is simultaneously subjected to different gaseous environments, e.g., when separating fuel (hydrogen) and oxidant (air) streams, in comparison with single-atmosphere exposures, e.g., air only. This so-called "dual-atmosphere" exposure is realized in many energy-conversion systems including turbines, boilers, gasifiers, heat exchangers, and particularly in intermediate temperature (600-800°C) planar solid-oxide fuel cell (SOFC) stacks. It is generally accepted that hydrogen transport through the FSS (plate or tube) and its subsequent integration into the growing air-side surface oxide layer can promote accelerated and anomalous corrosion—relative to single-atmosphere exposure—via defect chemistry changes, such as increased cation vacancy concentrations, decreased oxygen activity, and steam formation within the growing surface oxide layers. Establishment of a continuous and dense surface oxide layer on the fuel side of the FSS can inhibit hydrogen transport and the associated effects on the air side. Minor differences in FSS composition, microstructure, and surface conditions can all have dramatic influences on dual-atmosphere corrosion behaviors. This article reviews high-temperature, dual-atmosphere corrosion phenomena and discusses implications for SOFC stacks, related applications, and future research.

  19. The effect of yttrium addition on oxidation of a sputtered nanocrystalline coating with moderate amount of tantalum in composition

    International Nuclear Information System (INIS)

    Wang, Jinlong; Chen, Minghui; Yang, Lanlan; Liu, Li; Zhu, Shenglong; Wang, Fuhui; Meng, Guozhe

    2016-01-01

    Graphical abstract: - Highlights: • Effect of Y addition on oxidation of nanocrystalline coating is studied. • Y addition delays transformation of q-Al_2O_3 to a-Al_2O_3 during oxidation. • Y addition prevents scale rumpling. • Y segregates at grain boundaries of the nanocrystalline coating. • Y retards the transportation of Ta thus reduces its oxidation. - Abstract: The effect of yttrium addition on isothermal oxidation at 1050 °C of a sputtered nanocrystalline coating with moderate amount of tantalum in composition was investigated. Results indicate that yttrium addition delays transformation of metastable θ-Al_2O_3 to equilibrium α-Al_2O_3 grown on the nanocrystalline coatings. It prevents scale rumpling and promotes the formation of oxide pegs at interface between the oxide scale and the underlying coating. Besides, yttrium prefers to segregate at grain boundaries of the nanocrystalline coating and retards the outward transportation of tantalum from coating to oxide scale, thus reducing the excessive oxidation of tantalum.

  20. The transportation of PuO2 and MOX fuel and management of irradiated MOX fuel

    International Nuclear Information System (INIS)

    Dyck, H.P.; Rawl, R.; Durpel, L. van den

    2000-01-01

    Information is given on the transportation of PuO 2 and mixed-oxide (MOX) fuel, the regulatory requirements for transportation, the packages used and the security provisions for transports. The experience with and management of irradiated MOX fuel and the reprocessing of MOX fuel are described. Information on the amount of MOX fuel irradiated is provided. (author)

  1. A model of pyritic oxidation in waste rock dumps

    International Nuclear Information System (INIS)

    Davis, G.B.; Ritchie, A.I.M.

    1983-01-01

    The oxidation of pyrite can lead to high acid levels and high concentrations of trace metals in the water that runs off and percolates through pyritic material. This is the situation at the abandoned uranium mine at Rum Jungle in the Northern Territory of Australia, where pyritic oxidation in the waste rock dumps resulting from open cut mining of the uranium orebody has led to pollution of the nearby East Branch of the Finniss River, with trace metals such as copper, manganese and zinc. Mathematical equations are formulated which describe a model of pyritic oxidation within a waste rock dump, where it is assumed that oxygen transport is the rate limiting step in the oxidation process and that oxygen is transported by gaseous diffusion through the pore space of the dump, followed by diffusion into oxidation sites within the particles that comprise the dump. The equations have been solved numerically assuming values for such parameters as porosity, sulphur density and oxygen diffusion coefficients which are applicable to the waste rock dumps at Rum Jungle. An approximate solution to the equations is also presented. Calculations of the heat source distribution and the total SO 4 production rate are presented for both single size particles and for a range of particle sizes in the dump. The usefulness of the approximate solution, and of calculations based on single size particles in the dump in assessing the effectiveness of strategies to reduce pollution from such waste rock dumps are discussed

  2. Electronic transport behavior of diameter-graded Ag nanowires

    International Nuclear Information System (INIS)

    Wang Xuewei; Yuan Zhihao

    2010-01-01

    Ag nanowires with a graded diameter in anodic aluminum oxide (AAO) membranes were fabricated by the direct-current electrodeposition. The Ag nanowires have a graded-change in diameter from 8 to 32 nm, which is matched with the graded-change of the AAO pore diameter. Electronic transport measurements show that there is a transport behavior similar to that of a metal-semiconductor junction along the axial direction in the diameter-graded Ag nanowires. Such a novel homogeneous nanojunction will be of great fundamental and practical significance.

  3. Electronic transport behavior of diameter-graded Ag nanowires

    Science.gov (United States)

    Wang, Xue Wei; Yuan, Zhi Hao

    2010-05-01

    Ag nanowires with a graded diameter in anodic aluminum oxide (AAO) membranes were fabricated by the direct-current electrodeposition. The Ag nanowires have a graded-change in diameter from 8 to 32 nm, which is matched with the graded-change of the AAO pore diameter. Electronic transport measurements show that there is a transport behavior similar to that of a metal-semiconductor junction along the axial direction in the diameter-graded Ag nanowires. Such a novel homogeneous nanojunction will be of great fundamental and practical significance.

  4. Resonance Raman study on photoreduction of cytochrome c oxidase: distinction of cytochromes a and a3 in the intermediate oxidation states.

    Science.gov (United States)

    Ogura, T; Yoshikawa, S; Kitagawa, T

    1985-12-17

    Occurrence of photoreduction of bovine cytochrome c oxidase was confirmed with the difference absorption spectra and oxygen consumption measurements for the enzyme irradiated with laser light at 406.7, 441.6, and 590 nm. The resonance Raman spectra were obtained under the same experimental conditions as those adopted for the measurements of oxygen consumption and difference absorption spectra. The photoreduction was more effective upon irradiation at shorter wavelengths and was irreversible under anaerobic conditions. However, upon aeration into the cell, the original oxidized form was restored. It was found that aerobic laser irradiation produces a photo steady state of the catalytic dioxygen reduction and that the Raman scattering from this photo steady state probes cytochrome a2+ and cytochrome a3(3)+ separately upon excitations at 441.6 and 406.7 nm, respectively. The enzyme was apparently protected from the photoreduction in the spinning cell with the spinning speed between 1 and 1500 rpm. These results were explained satisfactorily with the reported rate constant for the electron transfer from cytochrome a to cytochrome a3 (0.58 s-1) and a comparable photoreduction rate of cytochrome a. The anaerobic photoreduction did give Raman lines at 1666 and 214 cm-1, which are characteristic of the ferrous high-spin cytochrome a3(2)+, but they were absent under aerobic photoreduction. The formyl CH = O stretching mode of the a3 heme was observed at 1671 cm-1 for a2+a3(2)+CO but at 1664 cm-1 for a2+a3(2)+CN-, indicating that the CH = O stretching frequency reflects the pi back-donation to the axial ligand similar to the oxidation state marker line (v4).

  5. Efficient electrochemical regeneration of nicotinamide cofactors using a cyclopentadienyl-rhodium complex on functionalized indium tin oxide electrodes

    International Nuclear Information System (INIS)

    Kim, Soojin; Lee, Ga Ye; Lee, Jungha; Rajkumar, Eswaran; Baeg, Jin-Ook; Kim, Jinheung

    2013-01-01

    Functionalized ITO electrodes are used to regenerate NADH using [Cp*Rh(bpy)(H 2 O)] 2+ (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridine) electrochemically in a buffer solution. Amino- and mercapto-functionalized electrodes featured higher activity and stability for electrocatalytic generation of NADH than a bare ITO electrode. Effect of metal nanoparticles was also studied on modified ITO electrodes and the addition of platinum nanoparticles even resulted in improved activity. The electrochemical regeneration was somewhat affected in the presence of dioxygen, but not significantly. In addition, a conversion of carbon dioxide was carried out utilizing the electrochemically generated NADH and formate dehydrogenase to produce formic acid

  6. Carbon Inputs From Riparian Vegetation Limit Oxidation of Physically Bound Organic Carbon Via Biochemical and Thermodynamic Processes: OC Oxidation Processes Across Vegetation

    Energy Technology Data Exchange (ETDEWEB)

    Graham, Emily B. [Pacific Northwest National Laboratory, Richland WA USA; Tfaily, Malak M. [Environmental Molecular Sciences Laboratory, Richland WA USA; Crump, Alex R. [Pacific Northwest National Laboratory, Richland WA USA; Goldman, Amy E. [Pacific Northwest National Laboratory, Richland WA USA; Bramer, Lisa M. [Pacific Northwest National Laboratory, Richland WA USA; Arntzen, Evan [Pacific Northwest National Laboratory, Richland WA USA; Romero, Elvira [Pacific Northwest National Laboratory, Richland WA USA; Resch, C. Tom [Pacific Northwest National Laboratory, Richland WA USA; Kennedy, David W. [Pacific Northwest National Laboratory, Richland WA USA; Stegen, James C. [Pacific Northwest National Laboratory, Richland WA USA

    2017-12-01

    In light of increasing terrestrial carbon (C) transport across aquatic boundaries, the mechanisms governing organic carbon (OC) oxidation along terrestrial-aquatic interfaces are crucial to future climate predictions. Here, we investigate biochemistry, metabolic pathways, and thermodynamics corresponding to OC oxidation in the Columbia River corridor. We leverage natural vegetative differences to encompass variation in terrestrial C inputs. Our results suggest that decreases in terrestrial C deposition associated with diminished riparian vegetation induce oxidation of physically-bound (i.e., mineral and microbial) OC at terrestrial-aquatic interfaces. We also find that contrasting metabolic pathways oxidize OC in the presence and absence of vegetation and—in direct conflict with the concept of ‘priming’—that inputs of water-soluble and thermodynamically-favorable terrestrial OC protects bound-OC from oxidation. Based on our results, we propose a mechanistic conceptualization of OC oxidation along terrestrial-aquatic interfaces that can be used to model heterogeneous patterns of OC loss under changing land cover distributions.

  7. Defect engineering of the electronic transport through cuprous oxide interlayers

    KAUST Repository

    Fadlallah, Mohamed M.; Eckern, Ulrich; Schwingenschlö gl, Udo

    2016-01-01

    The electronic transport through Au–(Cu2O)n–Au junctions is investigated using first-principles calculations and the nonequilibrium Green’s function method. The effect of varying the thickness (i.e., n) is studied as well as that of point defects

  8. Heterojunction PbS Nanocrystal Solar Cells with Oxide Charge-Transport Layers

    KAUST Repository

    Hyun, Byung-Ryool; Choi, Joshua J.; Seyler, Kyle L.; Hanrath, Tobias; Wise, Frank W.

    2013-01-01

    and characterized. Solution-processed devices were used to systematically study the dependence on nanocrystal size and achieve conversion efficiency as high as 2.5%. Optical modeling indicates that optimum performance should be obtained with thinner oxide layers

  9. Solute transport during the cyclic oxidation of Ni-Cr-Al alloys. M.S. Thesis

    Science.gov (United States)

    Nesbitt, J. A.

    1982-01-01

    Important requirements for protective coatings of Ni-Cr-Al alloys for gas turbine superalloys are resistance to oxidation accompanied by thermal cycling, resistance to thermal fatigue cracking. The resistance to oxidation accompanied by thermal cycling is discussed. The resistance to thermal fatigue cracking is also considered.

  10. Endoplasmic reticulum transport of glutathione by Sec61 is regulated by Ero1 and Bip

    DEFF Research Database (Denmark)

    Ponsero, Alise J.; Igbaria, Aeid; Darch, Maxwell A.

    2017-01-01

    In the endoplasmic reticulum (ER), Ero1 catalyzes disulfide bond formation and promotes glutathione (GSH) oxidation to GSSG. Since GSSG cannot be reduced in the ER, maintenance of the ER glutathione redox state and levels likely depends on ER glutathione import and GSSG export. We used quantitative...... oxidation through Ero1 reductive activation, which inhibits glutathione import in a negative regulatory loop. During ER stress, transport is activated by UPR-dependent Ero1 induction, and cytosolic glutathione levels increase. Thus, the ER redox poise is tuned by reciprocal control of glutathione import...... by reduction, causing Bip oxidation and inhibition of glutathione transport. Coupling of glutathione ER import to Ero1 activation provides a basis for glutathione ER redox poise maintenance....

  11. Synthesis and characterization of magnesium doped cerium oxide for the fuel cell application

    International Nuclear Information System (INIS)

    Kumar, Amit; Kumari, Monika; Kumar, Mintu; Kumar, Sacheen; Kumar, Dinesh

    2016-01-01

    Cerium oxide has attained much attentions in global nanotechnology market due to valuable application for catalytic, fuel additive, and widely as electrolyte in solid oxide fuel cell. Doped cerium oxide has large oxygen vacancies that allow for greater reactivity and faster ion transport. These properties make cerium oxide suitable material for SOFCs application. Cerium oxide electrolyte requires lower operation temperature which shows improvement in processing and the fabrication technique. In our work, we synthesized magnesium doped cerium oxide by the co-precipitation method. With the magnesium doping catalytic reactivity of CeO_2 was increased. Synthesized nanoparticle were characterized by the XRD and UV absorption techniques.

  12. Extraction of plutonium from lean residues by room-temperature fluoride volatility

    International Nuclear Information System (INIS)

    Campbell, G.M.; Foropoulos, J.; Kennedy, R.C.; Dye, B.A.; Behrens, R.G.

    1990-01-01

    The use of dioxygen difluoride and krypton difluoride for the recovery of plutonium from lean residues by conversion to gaseous plutonium hexa-fluoride is being investigated. The synthesis of dioxygen difluoride in practical quantity has been demonstrated. Fluorination of plutonium compounds under ideal conditions supports the contention that a viable process can be developed. Application of the method to lean plutonium residues is in the early stage of development

  13. Inhaled nitric oxide augments nitric oxide transport on sickle cell hemoglobin without affecting oxygen affinity

    OpenAIRE

    Gladwin, Mark T.; Schechter, Alan N.; Shelhamer, James H.; Pannell, Lewis K.; Conway, Deirdre A.; Hrinczenko, Borys W.; Nichols, James S.; Pease-Fye, Margaret E.; Noguchi, Constance T.; Rodgers, Griffin P.; Ognibene, Frederick P.

    1999-01-01

    Nitric oxide (NO) inhalation has been reported to increase the oxygen affinity of sickle cell erythrocytes. Also, proposed allosteric mechanisms for hemoglobin, based on S-nitrosation of β-chain cysteine 93, raise the possibilty of altering the pathophysiology of sickle cell disease by inhibiting polymerization or by increasing NO delivery to the tissue. We studied the effects of a 2-hour treatment, using varying concentrations of inhaled NO. Oxygen affinity, as measured by P50, did not respo...

  14. Cost and Performance Assessment of In-situ Chemical Oxidation for Intermittent and Continuous Oxidant Injection

    Science.gov (United States)

    Kim, U.; Parker, J.; Borden, R. C.

    2015-12-01

    In situ chemical oxidation (ISCO) is a popular remediation technology that involves injection of chemical oxidant into groundwater to destroy dissolved and non-aqueous liquid phase contaminants. Depending on site conditions, oxidant can be injected into the contaminated subsurface periodically (intermittently) or continuously. A common approach is to intermittently inject oxidant into a network of wells over a period long enough to emplace oxidant over a target treatment volume (referred to ISCO-int). The injection phase is followed by a passive phase when the oxidant is allowed to react with contaminants and natural oxygen demand (NOD) and to migrate under natural hydraulic gradients. This process may be repeated multiple times until termination criteria are met. Recently, some practitioners have adopted an alternative approach in which oxidant is injected continuously with extraction wells recovering unreacted oxidant to recycle with additional makeup oxidant to maintain its constant concentration (referred to ISCO-cont). Each method has certain advantages and disadvantages. This study numerically evaluates those two ISCO practices in terms of remediation costs and performance based on multiple equi-probable parameter sets. Stochastic cost optimization toolbox (SCOToolkit) is used for this purpose. SCOToolkit is an integrated semi-analytical model for contaminant transport and remediation (e.g., thermal source treatment, ISCO, electron donor injections, permeable reactive barriers) enabling inverse solution and Monte Carlo simulations. Four different aquifer settings, slow and fast Darcy velocities combined with low and high NOD conditions, are used for the evaluation. Preliminary results showed that ISCO-cont is effective for a full scale application without large investment while ISCO-int is more efficient to utilize oxidant in well-characterized sites. Pros and cons of each approach are discussed for the practical use of ISCO for various site conditions.

  15. Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

    Science.gov (United States)

    Fitzpatrick, Jessica; Kim, Eunsuk

    2015-08-18

    Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen

  16. CHMTRNS, Non-Equilibrium Chemical Transport Code

    International Nuclear Information System (INIS)

    Noorishad, J.; Carnahan, C.L.; Benson, L.V.

    1998-01-01

    1 - Description of program or function: CHMTRNS simulates solute transport for steady one-dimensional fluid flow by convection and diffusion or dispersion in a saturated porous medium based on the assumption of local chemical equilibrium. The chemical interactions included in the model are aqueous-phase complexation, solid-phase ion exchange of bare ions and complexes using the surface complexation model, and precipitation or dissolution of solids. The program can simulate the kinetic dissolution or precipitation for calcite and silica as well as irreversible dissolution of glass. Thermodynamic parameters are temperature dependent and are coupled to a companion heat transport simulator; thus, the effects of transient temperature conditions can be considered. Options for oxidation-reduction (redox) and C-13 fractionation as well as non-isothermal conditions are included. 2 - Method of solution: The governing equations for both reactive chemical and heat transport are discretized in time and space. For heat transport, the Crank-Nicolson approximation is used in conjunction with a LU decomposition and backward substitution solution procedure. To deal with the strong nonlinearity of the chemical transport equations, a generalized Newton-Raphson method is used

  17. Advanced methods of solid oxide fuel cell modeling

    CERN Document Server

    Milewski, Jaroslaw; Santarelli, Massimo; Leone, Pierluigi

    2011-01-01

    Fuel cells are widely regarded as the future of the power and transportation industries. Intensive research in this area now requires new methods of fuel cell operation modeling and cell design. Typical mathematical models are based on the physical process description of fuel cells and require a detailed knowledge of the microscopic properties that govern both chemical and electrochemical reactions. ""Advanced Methods of Solid Oxide Fuel Cell Modeling"" proposes the alternative methodology of generalized artificial neural networks (ANN) solid oxide fuel cell (SOFC) modeling. ""Advanced Methods

  18. Orphan drugs in development for long-chain fatty acid oxidation disorders: challenges and progress

    OpenAIRE

    Merritt II, J Lawrence; Sun,Angela

    2015-01-01

    Angela Sun, J Lawrence Merritt II Department of Pediatrics, University of Washington, Seattle, WA, USA Abstract: Fatty acid oxidation disorders are inborn errors of metabolism resulting in failure of ß-oxidation within or transport of fatty acids into the mitochondria. The long-chain fatty acid oxidation disorders are characterized by variable presentations ranging from newborn cardiomyopathy, to infantile hypoketotic hypoglycemia resulting from liver involvement, to skeletal myopa...

  19. PREFACE: Semiconducting oxides Semiconducting oxides

    Science.gov (United States)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    their help in producing this special section. We hope that it conveys some of the excitement and significance of the field. Semiconducting oxides contents Chemical bonding in copper-based transparent conducting oxides: CuMO2 (M = In, Ga, Sc) K G Godinho, B J Morgan, J P Allen, D O Scanlon and G W Watson Electrical properties of (Ba, Sr)TiO3 thin films with Pt and ITO electrodes: dielectric and rectifying behaviourShunyi Li, Cosmina Ghinea, Thorsten J M Bayer, Markus Motzko, Robert Schafranek and Andreas Klein Orientation dependent ionization potential of In2O3: a natural source for inhomogeneous barrier formation at electrode interfaces in organic electronicsMareike V Hohmann, Péter Ágoston, André Wachau, Thorsten J M Bayer, Joachim Brötz, Karsten Albe and Andreas Klein Cathodoluminescence studies of electron irradiation effects in n-type ZnOCasey Schwarz, Yuqing Lin, Max Shathkin, Elena Flitsiyan and Leonid Chernyak Resonant Raman scattering in ZnO:Mn and ZnO:Mn:Al thin films grown by RF sputteringM F Cerqueira, M I Vasilevskiy, F Oliveira, A G Rolo, T Viseu, J Ayres de Campos, E Alves and R Correia Structure and electrical properties of nanoparticulate tungsten oxide prepared by microwave plasma synthesisM Sagmeister, M Postl, U Brossmann, E J W List, A Klug, I Letofsky-Papst, D V Szabó and R Würschum Charge compensation in trivalent cation doped bulk rutile TiO2Anna Iwaszuk and Michael Nolan Deep level transient spectroscopy studies of n-type ZnO single crystals grown by different techniquesL Scheffler, Vl Kolkovsky, E V Lavrov and J Weber Microstructural and conductivity changes induced by annealing of ZnO:B thin films deposited by chemical vapour depositionC David, T Girardeau, F Paumier, D Eyidi, B Lacroix, N Papathanasiou, B P Tinkham, P Guérin and M Marteau Multi-component transparent conducting oxides: progress in materials modellingAron Walsh, Juarez L F Da Silva and Su-Huai Wei Thickness dependence of the strain, band gap and transport properties of

  20. Manganese oxide-based materials as electrochemical supercapacitor electrodes.

    Science.gov (United States)

    Wei, Weifeng; Cui, Xinwei; Chen, Weixing; Ivey, Douglas G

    2011-03-01

    Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high energy densities, have become a versatile solution to various emerging energy applications. This critical review describes some materials science aspects on manganese oxide-based materials for these applications, primarily including the strategic design and fabrication of these electrode materials. Nanostructurization, chemical modification and incorporation with high surface area, conductive nanoarchitectures are the three major strategies in the development of high-performance manganese oxide-based electrodes for EC applications. Numerous works reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based electrode materials. However, many fundamental questions remain unanswered, particularly with respect to characterization and understanding of electron transfer and atomic transport of the electrochemical interface processes within the manganese oxide-based electrodes. In order to fully exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation of these basic questions and optimization of synthesis parameters and material properties are critical for the further development of EC devices (233 references).

  1. Increased oxidative metabolism and neurotransmitter cycling in the brain of mice lacking the thyroid hormone transporter SLC16A2 (MCT8).

    Science.gov (United States)

    Rodrigues, Tiago B; Ceballos, Ainhoa; Grijota-Martínez, Carmen; Nuñez, Barbara; Refetoff, Samuel; Cerdán, Sebastian; Morte, Beatriz; Bernal, Juan

    2013-01-01

    Mutations of the monocarboxylate transporter 8 (MCT8) cause a severe X-linked intellectual deficit and neurological impairment. MCT8 is a specific thyroid hormone (T4 and T3) transporter and the patients also present unusual abnormalities in the serum profile of thyroid hormone concentrations due to altered secretion and metabolism of T4 and T3. Given the role of thyroid hormones in brain development, it is thought that the neurological impairment is due to restricted transport of thyroid hormones to the target neurons. In this work we have investigated cerebral metabolism in mice with Mct8 deficiency. Adult male mice were infused for 30 minutes with (1-(13)C) glucose and brain extracts prepared and analyzed by (13)C nuclear magnetic resonance spectroscopy. Genetic inactivation of Mct8 resulted in increased oxidative metabolism as reflected by increased glutamate C4 enrichment, and of glutamatergic and GABAergic neurotransmissions as observed by the increases in glutamine C4 and GABA C2 enrichments, respectively. These changes were distinct to those produced by hypothyroidism or hyperthyroidism. Similar increments in glutamate C4 enrichment and GABAergic neurotransmission were observed in the combined inactivation of Mct8 and D2, indicating that the increased neurotransmission and metabolic activity were not due to increased production of cerebral T3 by the D2-encoded type 2 deiodinase. In conclusion, Mct8 deficiency has important metabolic consequences in the brain that could not be correlated with deficiency or excess of thyroid hormone supply to the brain during adulthood.

  2. Increased oxidative metabolism and neurotransmitter cycling in the brain of mice lacking the thyroid hormone transporter SLC16A2 (MCT8.

    Directory of Open Access Journals (Sweden)

    Tiago B Rodrigues

    Full Text Available Mutations of the monocarboxylate transporter 8 (MCT8 cause a severe X-linked intellectual deficit and neurological impairment. MCT8 is a specific thyroid hormone (T4 and T3 transporter and the patients also present unusual abnormalities in the serum profile of thyroid hormone concentrations due to altered secretion and metabolism of T4 and T3. Given the role of thyroid hormones in brain development, it is thought that the neurological impairment is due to restricted transport of thyroid hormones to the target neurons. In this work we have investigated cerebral metabolism in mice with Mct8 deficiency. Adult male mice were infused for 30 minutes with (1-(13C glucose and brain extracts prepared and analyzed by (13C nuclear magnetic resonance spectroscopy. Genetic inactivation of Mct8 resulted in increased oxidative metabolism as reflected by increased glutamate C4 enrichment, and of glutamatergic and GABAergic neurotransmissions as observed by the increases in glutamine C4 and GABA C2 enrichments, respectively. These changes were distinct to those produced by hypothyroidism or hyperthyroidism. Similar increments in glutamate C4 enrichment and GABAergic neurotransmission were observed in the combined inactivation of Mct8 and D2, indicating that the increased neurotransmission and metabolic activity were not due to increased production of cerebral T3 by the D2-encoded type 2 deiodinase. In conclusion, Mct8 deficiency has important metabolic consequences in the brain that could not be correlated with deficiency or excess of thyroid hormone supply to the brain during adulthood.

  3. Liquid-fueled SOFC power sources for transportation

    Science.gov (United States)

    Myles, K. M.; Doshi, R.; Kumar, R.; Krumpelt, M.

    Traditionally, fuel cells have been developed for space or stationary terrestrial applications. As the first commercial 200-kW systems were being introduced by ONSI and Fuji Electric, the potentially much larger, but also more challenging, application in transportation was beginning to be addressed. As a result, fuel cell-powered buses have been designed and built, and R&D programs for fuel cell-powered passenger cars have been initiated. The engineering challenge of eventually replacing the internal combustion engine in buses, trucks, and passenger cars with fuel cell systems is to achieve much higher power densities and much lower costs than obtainable in systems designed for stationary applications. At present, the leading fuel cell candidate for transportation applications is, without question, the polymer electrolyte fuel cell (PEFC). Offering ambient temperature start-up and the potential for a relatively high power density, the polymer technology has attracted the interest of automotive manufacturers worldwide. But the difficulties of fuel handling for the PEFC have led to a growing interest in exploring the prospects for solid oxide fuel cells (SOFCs) operating on liquid fuels for transportation applications. Solid oxide fuel cells are much more compatible with liquid fuels (methanol or other hydrocarbons) and are potentially capable of power densities high enough for vehicular use. Two SOFC options for such use are discussed in this report.

  4. Graphite Oxidation Simulation in HTR Accident Conditions

    Energy Technology Data Exchange (ETDEWEB)

    El-Genk, Mohamed

    2012-10-19

    Massive air and water ingress, following a pipe break or leak in steam-generator tubes, is a design-basis accident for high-temperature reactors (HTRs). Analysis of these accidents in both prismatic and pebble bed HTRs requires state-of-the-art capability for predictions of: 1) oxidation kinetics, 2) air helium gas mixture stratification and diffusion into the core following the depressurization, 3) transport of multi-species gas mixture, and 4) graphite corrosion. This project will develop a multi-dimensional, comprehensive oxidation kinetics model of graphite in HTRs, with diverse capabilities for handling different flow regimes. The chemical kinetics/multi-species transport model for graphite burning and oxidation will account for temperature-related changes in the properties of graphite, oxidants (O2, H2O, CO), reaction products (CO, CO2, H2, CH4) and other gases in the mixture (He and N2). The model will treat the oxidation and corrosion of graphite in geometries representative of HTR core component at temperatures of 900°C or higher. The developed chemical reaction kinetics model will be user-friendly for coupling to full core analysis codes such as MELCOR and RELAP, as well as computational fluid dynamics (CFD) codes such as CD-adapco. The research team will solve governing equations for the multi-dimensional flow and the chemical reactions and kinetics using Simulink, an extension of the MATLAB solver, and will validate and benchmark the model's predictions using reported experimental data. Researchers will develop an interface to couple the validated model to a commercially available CFD fluid flow and thermal-hydraulic model of the reactor , and will perform a simulation of a pipe break in a prismatic core HTR, with the potential for future application to a pebble-bed type HTR.

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

    Science.gov (United States)

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

    2015-06-03

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

  6. Biological Superoxide In Manganese Oxide Formation

    Science.gov (United States)

    Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

    2011-12-01

    Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

  7. A Novel Sugar Transporter from Dianthus spiculifolius, DsSWEET12, Affects Sugar Metabolism and Confers Osmotic and Oxidative Stress Tolerance in Arabidopsis

    Directory of Open Access Journals (Sweden)

    Aimin Zhou

    2018-02-01

    Full Text Available Plant SWEETs (sugars will eventually be exported transporters play a role in plant growth and plant response to biotic and abiotic stresses. In the present study, DsSWEET12 from Dianthus spiculifolius was identified and characterized. Real-time quantitative PCR analysis revealed that DsSWEET12 expression was induced by sucrose starvation, mannitol, and hydrogen peroxide. Colocalization experiment showed that the DsSWEET12-GFP fusion protein was localized to the plasma membrane, which was labeled with FM4-64 dye, in Arabidopsis and suspension cells of D. spiculifolius. Compared to wild type plants, transgenic Arabidopsis seedlings overexpressing DsSWEET12 have longer roots and have a greater fresh weight, which depends on sucrose content. Furthermore, a relative root length analysis showed that transgenic Arabidopsis showed higher tolerance to osmotic and oxidative stresses. Finally, a sugar content analysis showed that the sucrose content in transgenic Arabidopsis was less than that in the wild type, while fructose and glucose contents were higher than those in the wild type. Taken together, our results suggest that DsSWEET12 plays an important role in seedling growth and plant response to osmotic and oxidative stress in Arabidopsis by influencing sugar metabolism.

  8. Purple perilla extracts with α-asarone enhance cholesterol efflux from oxidized LDL-exposed macrophages.

    Science.gov (United States)

    Park, Sin-Hye; Paek, Ji Hun; Shin, Daekeun; Lee, Jae-Yong; Lim, Soon Sung; Kang, Young-Hee

    2015-04-01

    The cellular accumulation of cholesterol is critical in the development and progression of atherosclerosis. ATP-binding cassette (ABC) transporters play an essential role in mediating the efflux of excess cholesterol. In the current study, we investigated whether purple Perilla frutescens extracts (PPE) at a non-toxic concentration of 1-10 µg/ml stimulate the induction of the ABC transporters, ABCA1 and ABCG1, and cholesterol efflux from lipid-laden J774A.1 murine macrophages exposed to 50 ng/ml oxidized low-density lipoprotein (LDL). Purple perilla, an annual herb in the mint family and its constituents, have been reported to exhibit antioxidant and cytostatic activity, as well as to exert anti-allergic effects. Our results revealed that treatment with oxidized LDL for 24 h led to the accumulation of lipid droplets in the macrophages. PPE suppressed the oxidized LDL-induced foam cell formation by blocking the induction of scavenger receptor B1. However, PPE promoted the induction of the ABC transporters, ABCA1 and ABCG1, and subsequently accelerated cholesterol efflux from the lipid-loaded macrophages. The liver X receptor (LXR) agonist, TO-091317, and the peroxisome proliferator-activated receptor (PPAR) agonist, pioglitazone, increased ABCA1 expression and treatment with 10 µg/ml PPE further enhanced this effect. PPE did not induce LXRα and PPARγ expression per se, but enhanced their expression in the macrophages exposed to oxidized LDL. α-asarone was isolated from PPE and characterized as a major component enhancing the induction of ABCA1 and ABCG1 in macrophages exposed to oxidized LDL. α-asarone, but not β-asarone was effective in attenuating foam cell formation and enhancing cholesterol efflux, revealing an isomeric difference in their activity. The results from the present study demonstrate that PPE promotes cholesterol efflux from macrophages by activating the interaction of PPARγ-LXRα-ABC transporters.

  9. Emissions of greenhouse gases from the use of transportation fuels and electricity

    International Nuclear Information System (INIS)

    DeLuchi, M.A.

    1991-11-01

    This report presents estimates of full fuel-cycle emissions of greenhouse gases from using transportation fuels and electricity. The data cover emissions of carbon dioxide (CO 2 ), methane, carbon monoxide, nitrous oxide, nitrogen oxides, and nonmethane organic compounds resulting from the end use of fuels, compression or liquefaction of gaseous transportation fuels, fuel distribution, fuel production, feedstock transport, feedstock recovery, manufacture of motor vehicles, maintenance of transportation systems, manufacture of materials used in major energy facilities, and changes in land use that result from using biomass-derived fuels. The results for electricity use are in grams of CO 2 -equivalent emissions per kilowatt-hour of electricity delivered to end users and cover generating plants powered by coal, oil, natural gas, methanol, biomass, and nuclear energy. The transportation analysis compares CO 2 -equivalent emissions, in grams per mile, from base-case gasoline and diesel fuel cycles with emissions from these alternative- fuel cycles: methanol from coal, natural gas, or wood; compressed or liquefied natural gas; synthetic natural gas from wood; ethanol from corn or wood; liquefied petroleum gas from oil or natural gas; hydrogen from nuclear or solar power; electricity from coal, uranium, oil, natural gas, biomass, or solar energy, used in battery-powered electric vehicles; and hydrogen and methanol used in fuel-cell vehicles

  10. Long-range transport of air pollution under light gradient wind conditions

    International Nuclear Information System (INIS)

    Kurita, H.; Sasaki, K.; Muroga, H.; Ueda, H.; Wakamatsu, S.

    1985-01-01

    The long-range transport of air pollution on clear days under light gradient wind conditions is investigated from an analysis of all days with high oxidant concentrations in 1979 at locations in central Japan that are far from pollutant sources. Surface-level wind and pressure distributions over a 300 x 300 km area were analyzed, together with concentration isopleths of oxidants and suspended particles produced by photochemical reactions

  11. Feed gas contaminant control in ion transport membrane systems

    Science.gov (United States)

    Carolan, Michael Francis [Allentown, PA; Minford, Eric [Laurys Station, PA; Waldron, William Emil [Whitehall, PA

    2009-07-07

    Ion transport membrane oxidation system comprising an enclosure having an interior and an interior surface, inlet piping having an internal surface and adapted to introduce a heated feed gas into the interior of the enclosure, and outlet piping adapted to withdraw a product gas from the interior of the enclosure; one or more planar ion transport membrane modules disposed in the interior of the enclosure, each membrane module comprising mixed metal oxide material; and a preheater adapted to heat a feed gas to provide the heated feed gas to the inlet piping, wherein the preheater comprises an interior surface. Any of the interior surfaces of the enclosure, the inlet piping, and the preheater may be lined with a copper-containing metal lining. Alternatively, any of the interior surfaces of the inlet piping and the preheater may be lined with a copper-containing metal lining and the enclosure may comprise copper.

  12. Long-distance electron transport by cable bacteria in mangrove sediments

    NARCIS (Netherlands)

    Burdorf, L.D.; Hidalgo-Martinez, S.; Cook, P.L.M.C.; Meysman, F.

    2016-01-01

    Cable bacteria are long, filamentoussulphur-oxidizing bacteria that induce long-distanceelectron transport in aquatic sediments. They turnthe seafloor into an electro-active environment, characterizedby currents and electrical fields, and whenpresent, they exert a strong impact on the

  13. Synthesis, Characterization and Applications of One-Dimensional Metal Oxide Nanostructures

    Science.gov (United States)

    Santulli, Alexander

    Nanomaterials have been of keen research interest, owing to their exciting and unique properties (e.g. optical, magnetic, electronic, and mechanical). These properties allow nanomaterials to have many applications in areas of medicine, alternative energy, catalysis, and information storage. In particular, one-dimensional (1D) nanomaterials are highly advantageous, owing to the inherent anisotropic nature, which allows for effective transport and study of properties on the nanoscale. More specifically, 1D metal oxide nanomaterials are of particular interest, owing to their high thermal and chemical stability, as well as their intriguing optical, electronic, and magnetic properties. Herein, we will investigate the synthesis and characterization of vanadium oxide, lithium niobate and chromium oxide. We will explore the methodologies utilized for the synthesis of these materials, as well as the overall properties of these unique nanomaterials. Furthermore, we will explore the application of titanium dioxide nanomaterials as the electron transport layer in dye sensitized solar cells (DSSCs), with an emphasis on the effect of the nanoscale morphology on the overall device efficiency.

  14. Coupled transport/reaction model of the properties of bentonite buffer in a repository

    International Nuclear Information System (INIS)

    Liu, Jinsong; Neretnieks, I.

    1996-11-01

    Two mechanisms that can affect the long-term properties of the bentonite buffer surrounding the canister in a final repository of spent nuclear fuel are studied. The two mechanisms are the oxidation of reducing minerals in the buffer by radiolytically generated oxidant, and the low-temperature alteration of Na-montmorillonite in the bentonite buffer to illite. A coupled mass transport with geochemical reaction model is used. Four cases have been considered, which differ in the assumptions of whether the radiolytically generated oxidant first oxidizes uraninite in the spent fuel, or it is directly transported to the bentonite to oxidize the pyrite. The cases also differ in the assumptions of varying initial concentrations of pyrite in the bentonite buffer. The modelling results show that, at low temperatures, the sodium montmorillonite in the bentonite buffer is chemically stable with respect to the chemical conditions of the near field. Alteration to illite and thus an increase in hydraulic conductivity and loss of swelling ability is not likely to occur. The radiolytically generated oxidant can possibly oxidize the reducing minerals in the bentonite buffer. A redox front can be generated. In all the cases considered in this study, the modelling results indicate that slightly less than 1% by weight of pyrite in the bentonite buffer will be able to ensure that the redox front does not penetrate through the bentonite buffer within 1 million years. 31 refs

  15. Influence of titanium and vanadium on the hydrogen transport through amorphous alumina films

    Energy Technology Data Exchange (ETDEWEB)

    Palsson, G.K. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Wang, Y.T. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Azofeifa, D. [Centro de Investigacion en Ciencia e Ingenieria de Materiales and Escuela de Fisica, Universidad de Costa Rica, San Jose (Costa Rica); Raanaei, H. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden); Department of Physics, Persian Gulf University, Bushehr 75168 (Iran, Islamic Republic of); Sahlberg, M. [Department of Materials Chemistry, Uppsala University, Box 538, S-751 21 Uppsala (Sweden); Hjoervarsson, B. [Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala (Sweden)

    2010-04-02

    The influence of titanium and vanadium on the hydrogen transport rate through thin amorphous alumina films is addressed. Only small changes in the transport rate are observed when the Al{sub 2}O{sub 3} are covered with titanium or vanadium. This is in stark contrast to results with a Pd overlayer, which enhances the transport by an order of magnitude. Similarly, when titanium is embedded into the alumina the transport rate is faster than for the covered case but still slower than the undoped reference. Embedding vanadium in the alumina does not yield an increase in uptake rate compared to the vanadium covered oxide layers. These results add to the understanding of the hydrogen uptake of oxidized metals, especially the alanates, where the addition of titanium has been found to significantly enhance the rate of hydrogen uptake. The current findings eliminate two possible routes for the catalysis of alanates by Ti, namely dissociation and effective diffusion short-cuts formed by Ti. Finally, no photocatalytic enhancement was noticed on the titanium covered samples.

  16. Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2016-02-28

    Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

  17. Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

    Energy Technology Data Exchange (ETDEWEB)

    Krajčí, Marian [Institute of Physics, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84511 Bratislava (Slovakia); Kameoka, Satoshi; Tsai, An-Pang [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577 (Japan)

    2016-08-28

    We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al{sub 2}Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped (211) surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir–Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO–OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.

  18. Inkjet printed ambipolar transistors and inverters based on carbon nanotube/zinc tin oxide heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Bongjun; Jang, Seonpil; Dodabalapur, Ananth, E-mail: ananth.dodabalapur@engr.utexas.edu [Microelectronics Research Center, The University of Texas at Austin, Austin, Texas 78758 (United States); Department of Electrical and Computer Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Geier, Michael L.; Prabhumirashi, Pradyumna L. [Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (United States); Hersam, Mark C. [Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (United States); Department of Chemistry, Northwestern University, Evanston, Illinois 60208 (United States); Department of Medicine, Northwestern University, Evanston, Illinois 60208 (United States)

    2014-02-10

    We report ambipolar field-effect transistors (FETs) consisting of inkjet printed semiconductor bilayer heterostructures utilizing semiconducting single-walled carbon nanotubes (SWCNTs) and amorphous zinc tin oxide (ZTO). The bilayer structure allows for electron transport to occur principally in the amorphous oxide layer and hole transport to occur exclusively in the SWCNT layer. This results in balanced electron and hole mobilities exceeding 2 cm{sup 2} V{sup −1} s{sup −1} at low operating voltages (<5 V) in air. We further show that the SWCNT-ZTO hybrid ambipolar FETs can be integrated into functional inverter circuits that display high peak gain (>10). This work provides a pathway for realizing solution processable, inkjet printable, large area electronic devices, and systems based on SWCNT-amorphous oxide heterostructures.

  19. Broadband dielectric spectroscopy of oxidized porous silicon

    International Nuclear Information System (INIS)

    Axelrod, Ekaterina; Urbach, Benayahu; Sa'ar, Amir; Feldman, Yuri

    2006-01-01

    Dielectric measurements accompanied by infrared absorption and photoluminescence (PL) spectroscopy were used to investigate the electrical and optical properties of oxidized porous silicon (PS). As opposed to non-oxidized PS, only high temperature relaxation processes could be resolved for oxidized PS. Two relaxation processes have been observed. The first process is related to dc-conductivity that dominates at high temperatures and low frequencies. After subtraction of dc-conductivity we could analyse a second high-temperature relaxation process that is related to interface polarization induced by charge carriers trapped at the host matrix-pore interfaces. We found that, while the main effect of the oxidation on the PL appears to be a size reduction in the silicon nanocrystals that gives rise to a blue shift of the PL spectrum, its main contribution to the dielectric properties turns out to be blocking of transport channels in the host tissue and activation of hopping conductivity between silicon nanocrystals

  20. Broadband dielectric spectroscopy of oxidized porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Axelrod, Ekaterina [Department of Applied Physics, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel); Urbach, Benayahu [Racah Institute of Physics and the Center for Nanoscience and Nanotechnology, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel); Sa' ar, Amir [Racah Institute of Physics and the Center for Nanoscience and Nanotechnology, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel); Feldman, Yuri [Department of Applied Physics, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel)

    2006-04-07

    Dielectric measurements accompanied by infrared absorption and photoluminescence (PL) spectroscopy were used to investigate the electrical and optical properties of oxidized porous silicon (PS). As opposed to non-oxidized PS, only high temperature relaxation processes could be resolved for oxidized PS. Two relaxation processes have been observed. The first process is related to dc-conductivity that dominates at high temperatures and low frequencies. After subtraction of dc-conductivity we could analyse a second high-temperature relaxation process that is related to interface polarization induced by charge carriers trapped at the host matrix-pore interfaces. We found that, while the main effect of the oxidation on the PL appears to be a size reduction in the silicon nanocrystals that gives rise to a blue shift of the PL spectrum, its main contribution to the dielectric properties turns out to be blocking of transport channels in the host tissue and activation of hopping conductivity between silicon nanocrystals.

  1. Influence of natural convection and diluent inerting on H2 and CO oxidation in the reactor cavity

    International Nuclear Information System (INIS)

    Wong, C.C.

    1988-01-01

    The question of complete in-cavity oxidation of combustible gases produced by core-concrete interactions following vessel breach has been investigated. It is overly optimistic to assume a complete oxidation because a variety of phenomena, such as steam inerting and oxygen transport by natural convection, may influence the degree of in-cavity oxidation that takes place. HECTR analyses of an ice-condenser containment during an S2HF drain-closed accident show that the in-cavity oxidation process is limited by the rate at which oxygen is transported into the reactor cavity region. Accumulation and subsequent combustion of hydrogen and carbon monoxide in the upper and lower compartments generate a peak pressure of 384 kPa (56 psig) at 7.4 h, that an earlier IDCOR analysis did not predict. (orig.)

  2. Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

    DEFF Research Database (Denmark)

    Farver, Ole; Kroneck, Peter M H; Zumft, Walter G

    2003-01-01

    Cytochrome cd1 nitrite reductase is a bifunctional multiheme enzyme catalyzing the one-electron reduction of nitrite to nitric oxide and the four-electron reduction of dioxygen to water. Kinetics and thermodynamics of the internal electron transfer process in the Pseudomonas stutzeri enzyme have...... been studied and found to be dominated by pronounced interactions between the c and the d1 hemes. The interactions are expressed both in dramatic changes in the internal electron-transfer rates between these sites and in marked cooperativity in their electron affinity. The results constitute a prime...... example of intraprotein control of the electron-transfer rates by allosteric interactions....

  3. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2012-12-07

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1), it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Low-temperature thermal reduction of graphene oxide: In situ correlative structural, thermal desorption, and electrical transport measurements

    Science.gov (United States)

    Lipatov, Alexey; Guinel, Maxime J.-F.; Muratov, Dmitry S.; Vanyushin, Vladislav O.; Wilson, Peter M.; Kolmakov, Andrei; Sinitskii, Alexander

    2018-01-01

    Elucidation of the structural transformations in graphene oxide (GO) upon reduction remains an active and important area of research. We report the results of in situ heating experiments, during which electrical, mass spectrometry, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) measurements were carried out correlatively. The simultaneous electrical and temperature programmed desorption measurements allowed us to correlate the onset of the increase in the electrical conductivity of GO by five orders of magnitude at about 150 °C with the maxima of the rates of desorption of H2O, CO, and CO2. Interestingly, this large conductivity change happens at an intermediate level of the reduction of GO, which likely corresponds to the point when the graphitic domains become large enough to enable percolative electronic transport. We demonstrate that the gas desorption is intimately related to (i) the changes in the chemical structure of GO detected by XPS and Raman spectroscopy and (ii) the formation of nanoscopic holes in GO sheets revealed by TEM. These in situ observations provide a better understanding of the mechanism of the GO thermal reduction.

  5. Environmentally sustainable transport in Germany

    International Nuclear Information System (INIS)

    Verron, H.; Friedrich, A.

    2004-01-01

    The study reported in this paper is part of an OECD project with several case studies in different countries. The purpose of the project was to look for possible ways to reduce the environmental impact of transport to a level which is compatible with sustainability. The participants in the case studies agreed upon quantifying criteria for carbon dioxide, nitrogen oxides and volatile organic compounds, which should describe environmentally sustainable transport (EST), and each case study constructed a business-as-usual scenario and three EST scenarios, considering the period from 1990 to 2030. Each EST scenario should meet the criteria in a backcasting effort, EST1 looking for solely technical solutions, EST2 restricting and shifting transport volumes while ignoring technological progress, and EST3 combining components of both strategies. In the German case study criteria were additionally quantified for particulate matter, noise and land-take for transport purposes. The German EST1 scenario is based on hybrid electric hypercars, hydrogen for public transport, freight and aviation, and electricity from renewable sources. In the EST2 scenario total transport activity for passenger and freight transport had to be reduced by 40% and 25% respectively, compared to 1990 in order to meet the criteria. In the EST3 scenario, while highly energy efficient conventional propulsion systems and engines were used, total passenger transport decreased only slightly and freight transport even increased. Implementation measures were then defined on the basis of the EST3 scenario. Emission regulation, fuel tax, and road pricing for heavy duty vehicles were the key features in order to achieve EST in this case study. They were complemented by additional sets of measures, designed to prevent urban sprawl, diminish freight traffic growth, increase liveability of towns, improve the infrastructure and service conditions of alternative modes as well as provide energy supply by regenerative

  6. High temperature oxidation behavior of AISI 304L stainless steel—Effect of surface working operations

    International Nuclear Information System (INIS)

    Ghosh, Swati; Kumar, M. Kiran; Kain, Vivekanand

    2013-01-01

    Highlights: ► Surface working resulted in thinner oxide on the surface. ► Oxides on machined/ground surfaces richer in Cr, higher in specific resistivity. ► Additional ionic transport process at the metal-oxide for ground sample established. ► Presence of fragmented grains and martensite influenced oxide nature/morphology. - Abstract: The oxidation behavior of grade 304L stainless steel (SS) subjected to different surface finishing (machining and grinding) operations was followed in situ by contact electric resistance (CER) and electrochemical impedance spectroscopy (EIS) measurements using controlled distance electrochemistry (CDE) technique in high purity water (conductivity −1 ) at 300 °C and 10 MPa in an autoclave connected to a recirculation loop system. The results highlight the distinct differences in the oxidation behavior of surface worked material as compared to solution annealed material in terms of specific resistivity and low frequency Warburg impedance. The resultant oxide layer was characterized for (a) elemental analyses by glow discharge optical emission spectroscopy (GDOES) and (b) morphology by scanning electron microscopy (SEM). Oxide layers with higher specific resistivity and chromium content were formed in case of machined and ground conditions. Presence of an additional ionic transport process has also been identified for the ground condition at the metal/oxide interface. These differences in electrochemical properties and distinct morphological features of the oxide layer as a result of surface working were attributed to the prevalence of heavily fragmented grain structure and presence of martensite.

  7. Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

    Science.gov (United States)

    Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

    2013-12-17

    This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

  8. Enhanced bulk conductivity and bipolar transport in mixtures of MoOx and organic hole transport materials

    International Nuclear Information System (INIS)

    Tian, Baolin; Ban, Dayan; Aziz, Hany

    2013-01-01

    We study the conductivity of thin films of molybdenum oxide (MoO x ) mixed with an organic hole transport material, such as N,N′-bis(naphthalen-1-yl)-N,N′-bis (phenyl)benzidine or 4′,4″-tri(N-carbazolyl)triphenylamine, in lateral test devices. Contrary to previous reports, the conductivity of the mixture is found to exceed that of neat MoO x , exhibiting ∼ 5 orders of magnitude higher conductivity in comparison to the neat films. Studies also show that the mixing enhances both hole and electron transport. The higher conductivity may be attributed to a higher concentration of “free” carriers in the mixture, as a result of the formation of a charge transfer complex between the MoO x and the hole transport material. The findings shed light on the potential of hybrid composites of inorganic and organic materials in realizing enhanced conductivity. - Highlights: • We investigate the conductivity of mixtures of MoO x and hole transport material (HTM). • Materials are studied in lateral devices instead of conventional vertical devices. • Mixing MoO x with HTM brings > 5 orders of magnitude increase in bulk conductivity. • The mixture of MoO x and HTM enhances both hole and electron transport

  9. Mesoscale modeling of the production and the three-dimensional transport of nitrogen oxides in thunderstorms; Mesoskalige Modellierung der Produktion und des dreidimensionalen Transports von Stickoxiden durch Gewitter

    Energy Technology Data Exchange (ETDEWEB)

    Fehr, T.

    2000-07-01

    Nitrogen oxides, NO{sub x} = NO + NO{sub 2}, play a fundamental role in tropospheric chemistry. Compared to other sources, the contribution of lightning induced NO{sub x} (LNO{sub x}) is known with considerable uncertainties and difficult to determine experimentally. The distribution of nitrogen oxides in an isolated thunderstorm is investigated using a modified version of the Penn State/NCAR Mesoscale Model (MM5) with cloud-scale resolution. A Lagrangian particle model has been developed to represent the NO{sub x} released by individual flashes. The position of the flash, the flash type, the geometrical properties of the channel, and the amount of emitted NO{sub x} are introduced to the MM5 in a parameterized form. On July 21, 1998, during the European lightning nitrogen oxides project (EULINOX) field campaign, a supercell development was observed in the German alpine foreland. Anvil penetrations by the DLR Falcon aircraft contributed high resolution profiles of NO{sub x}. DLR radar observation covered the complete life cycle of the thunderstorm. The lightning activity was recorded with a lightning positioning and tracking system (LPATS) run by local power suppliers, while radiosonde and aircraft measurements supplied detailed information on the atmospheric stratification ahead of the thunderstorm. This meteorological information was used to initalize a cloud-scale MM5 simulation. The modeled thunderstorm reproduces many observed properties, e.g. cell splitting, propagation speed and direction, anvil and overshooting top height, and WER (weak echo region). The number of simulated cloud-to-ground flashes, as well as the temporal evolution of the lightning activity are comparable to the LPAT observations. The general transport properties of the model thunderstorm are investigated using an inert PBL-tracer, as well as trajectory analysis. The simulated lightning activity leads to the release of approximately 1 000 000 NO{sub x}-particles. The thunderstorm produces 28

  10. 78 FR 47253 - Approval and Promulgation of Air Quality Implementation Plans; Maine; Oxides of Nitrogen...

    Science.gov (United States)

    2013-08-05

    ... Promulgation of Air Quality Implementation Plans; Maine; Oxides of Nitrogen Exemption and Ozone Transport... is proposing to approve Maine's October 13, 2012, request for an exemption from the nitrogen oxides... from Stephen D. Page, Director, OAQPS, dated January 14, 2005, entitled ``Guidance on Limiting Nitrogen...

  11. A conceptual and calculational model for gas formation from impure calcined plutonium oxides

    International Nuclear Information System (INIS)

    Lyman, John L.; Eller, P. Gary

    2000-01-01

    Safe transport and storage of pure and impure plutonium oxides requires an understanding of processes that may generate or consume gases in a confined storage vessel. We have formulated conceptual and calculational models for gas formation from calcined materials. The conceptual model for impure calcined plutonium oxides is based on the data collected to date

  12. Electroactive mesoporous yttria stabilized zirconia containing platinum or nickel oxide nanoclusters: a new class of solid oxide fuel cell electrode materials

    Energy Technology Data Exchange (ETDEWEB)

    Mamak, M.; Coombs, N.; Ozin, G.A. [Toronto Univ., ON (Canada). Dept. of Chemistry

    2001-02-01

    The electroactivity of surfactant-templated mesoporous yttria stabilized zirconia, containing nanoclusters of platinum or nickel oxide, is explored by alternating current (AC) complex impedance spectroscopy. The observed oxygen ion and mixed oxygen ion-electron charge-transport behavior for these materials, compared to the sintered-densified non-porous crystalline versions, is ascribed to the unique integration of mesoporosity and nanocrystallinity within the binary and ternary solid solution microstructure. These attributes inspire interest in this new class of materials as candidates for the development of improved performance solid oxide fuel cell electrodes. (orig.)

  13. Ultrathin reduced graphene oxide films as transparent top-contacts for light switchable solid-state molecular junctions

    DEFF Research Database (Denmark)

    Li, Tao; Jevric, Martyn; Hauptmann, Jonas Rahlf

    2013-01-01

    A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules. The electr......A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules...

  14. Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

    DEFF Research Database (Denmark)

    Postma, Diederik Jan; Appelo, C. A. J.

    2000-01-01

    Cl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe21 reacts with MnO2 producing Fe......The reduction of Mn-oxide by Fe21 was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement...... of adsorbed Ca21 with Mg21. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the Fe...

  15. Surface characterization of low-temperature grown yttrium oxide

    Science.gov (United States)

    Krawczyk, Mirosław; Lisowski, Wojciech; Pisarek, Marcin; Nikiforow, Kostiantyn; Jablonski, Aleksander

    2018-04-01

    The step-by-step growth of yttrium oxide layer was controlled in situ using X-ray photoelectron spectroscopy (XPS). The O/Y atomic concentration (AC) ratio in the surface layer of finally oxidized Y substrate was found to be equal to 1.48. The as-grown yttrium oxide layers were then analyzed ex situ using combination of Auger electron spectroscopy (AES), elastic-peak electron spectroscopy (EPES) and scanning electron microscopy (SEM) in order to characterize their surface chemical composition, electron transport phenomena and surface morphology. Prior to EPES measurements, the Y oxide surface was pre-sputtered by 3 kV argon ions, and the resulting AES-derived composition was found to be Y0.383O0.465C0.152 (O/Y AC ratio of 1.21). The SEM images revealed different surface morphology of sample before and after Ar sputtering. The oxide precipitates were observed on the top of un-sputtered Y oxide layer, whereas the oxide growth at the Ar ion-sputtered surface proceeded along defects lines normal to the layer plane. The inelastic mean free path (IMFP) characterizing electron transport was evaluated as a function of energy in the range of 0.5-2 keV from the EPES method. Two reference materials (Ni and Au) were used in these measurements. Experimental IMFPs determined for the Y0.383O0.465C0.152 and Y2O3 surface compositions, λ, were uncorrected for surface excitations and approximated by the simple function λ = kEp at electron energies E between 500 eV and 2000 eV, where k and p were fitted parameters. These values were also compared with IMFPs resulting from the TPP-2 M predictive equation for both oxide compositions. The fitted functions were found to be reasonably consistent with the measured and predicted IMFPs. In both cases, the average value of the mean percentage deviation from the fits varied between 5% and 37%. The IMFPs measured for Y0.383O0.465C0.152 surface composition were found to be similar to the IMFPs for Y2O3.

  16. SITE-94. CAMEO: A model of mass-transport limited general corrosion of copper canisters

    International Nuclear Information System (INIS)

    Worgan, K.J.; Apted, M.J.

    1996-12-01

    This report describes the technical basis for the CAMEO code, which models the general, uniform corrosion of a copper canister either by transport of corrodants to the canister, or by transport of corrosion products away from the canister. According to the current Swedish concept for final disposal of spent nuclear fuels, extremely long containment times are achieved by thick (60-100 mm) copper canisters. Each canister is surrounded by a compacted bentonite buffer, located in a saturated, crystalline rock at a depth of around 500 m below ground level. Three diffusive transport-limited cases are identified for general, uniform corrosion of copper: General corrosion rate-limited by diffusive mass-transport of sulphide to the canister surface under reducing conditions; General corrosion rate-limited by diffusive mass-transport of oxygen to the canister surface under mildly oxidizing conditions; General corrosion rate-limited by diffusive mass-transport of copper chloride away from the canister surface under highly oxidizing conditions. The CAMEO code includes general corrosion models for each of the above three processes. CAMEO is based on the well-tested CALIBRE code previously developed as a finite-difference, mass-transfer analysis code for the SKI to evaluate long-term radionuclide release and transport in the near-field. A series of scoping calculations for the general, uniform corrosion of a reference copper canister are presented

  17. Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

    Science.gov (United States)

    Opila, Elizabeth J.

    1994-01-01

    The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

  18. Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

    Directory of Open Access Journals (Sweden)

    K. Yu

    2016-04-01

    Full Text Available Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2. We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5° to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 % than at coarser resolution (59 %. The cumulative probability distribution functions (CDFs of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy changing little across model resolutions. Model concentrations in the

  19. Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review

    Science.gov (United States)

    Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

    2012-12-01

    This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

  20. Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review.

    Science.gov (United States)

    Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

    2013-01-07

    This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

  1. Analysis on groundwater evolution and interlayer oxidation zone position at the southern margin of Yilin basin

    International Nuclear Information System (INIS)

    Zhang Guanghui

    2007-01-01

    This paper discusses the development and evolution history of groundwater and its reworking to the interlayer oxidation zone, hydrogeochemical zonation of interlayer oxidation zone, mechanism of water-rock interaction and transportation pattern of uranium in the water in Yili Basin. It is suggested that groundwater is one of the important factors to control the development of interlayer oxidation zone and uranium mineralization. (authors)

  2. Storage capacity and oxygen mobility in mixed oxides from transition metals promoted by cerium

    Energy Technology Data Exchange (ETDEWEB)

    Perdomo, Camilo [Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 45-03, Bogotá (Colombia); Pérez, Alejandro [Grupo de Investigación Fitoquímica (GIFUJ), Departamento de Química, Facultad de Ciencias, Pontificia Universidad Javeriana, Carrera 7 No. 43-82, Bogotá D.C (Colombia); Molina, Rafael [Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 45-03, Bogotá (Colombia); Moreno, Sonia, E-mail: smorenog@unal.edu.co [Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 45-03, Bogotá (Colombia)

    2016-10-15

    Highlights: • Ce addition to the catalysts improves the availability of oxygen in the materials. • Mixed oxide with Co and Cu exhibits the best oxygen transport properties. • Co presence improves O{sub 2} mobility in the catalysts. • The presence of Cu in the solids improves redox properties. - Abstract: The oxygen mobility and storage capacity of Ce-Co/Cu-MgAl or Ce–MgAl mixed oxides, obtained by hydrotalcite precursors, were evaluated using Toluene-temperature-programmed-reaction, {sup 18}O{sub 2} isotopic exchange and O{sub 2}-H{sub 2} titration. The presence of oxygen vacancies-related species was evaluated by means of Electron Paramagnetic Resonance. A correlation was found between the studied properties and the catalytic activity of the oxides in total oxidation processes. It was evidenced that catalytic activity depends on two related processes: the facility with which the solid can be reduced and its ability to regenerate itself in the presence of molecular oxygen in the gas phase. These processes are enhanced by Cu-Co cooperative effect in the mixed oxides. Additionally, the incorporation of Ce in the Co-Cu catalysts improved their oxygen transport properties.

  3. Storage capacity and oxygen mobility in mixed oxides from transition metals promoted by cerium

    International Nuclear Information System (INIS)

    Perdomo, Camilo; Pérez, Alejandro; Molina, Rafael; Moreno, Sonia

    2016-01-01

    Highlights: • Ce addition to the catalysts improves the availability of oxygen in the materials. • Mixed oxide with Co and Cu exhibits the best oxygen transport properties. • Co presence improves O 2 mobility in the catalysts. • The presence of Cu in the solids improves redox properties. - Abstract: The oxygen mobility and storage capacity of Ce-Co/Cu-MgAl or Ce–MgAl mixed oxides, obtained by hydrotalcite precursors, were evaluated using Toluene-temperature-programmed-reaction, 18 O 2 isotopic exchange and O 2 -H 2 titration. The presence of oxygen vacancies-related species was evaluated by means of Electron Paramagnetic Resonance. A correlation was found between the studied properties and the catalytic activity of the oxides in total oxidation processes. It was evidenced that catalytic activity depends on two related processes: the facility with which the solid can be reduced and its ability to regenerate itself in the presence of molecular oxygen in the gas phase. These processes are enhanced by Cu-Co cooperative effect in the mixed oxides. Additionally, the incorporation of Ce in the Co-Cu catalysts improved their oxygen transport properties.

  4. Lanthanum Manganate Based Cathodes for Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Jørgensen, Mette Juhl

    Composite cathodes for solid oxide fuel cells were investigated using electrochemical impedance spectroscopy and scanning electron microscopy. The aim was to study the oxygen reduction process in the electrode in order to minimise the voltage drop in the cathode. The electrodes contained...... five processes were found to affect the impedance of LSM/YSZ composite electrodes. Two high frequency processes were ascribed to transport of oxide ions/oxygen intermediates across LSM/YSZ interfaces and through YSZ in the composite. Several competitive elementary reaction steps, which appear as one...

  5. Single-Step Electrophoretic Deposition of Non-noble Metal Catalyst Layer with Low Onset Voltage for Ethanol Electro-oxidation.

    Science.gov (United States)

    Ahmadi Daryakenari, Ahmad; Hosseini, Davood; Ho, Ya-Lun; Saito, Takumi; Apostoluk, Aleksandra; Müller, Christoph R; Delaunay, Jean-Jacques

    2016-06-29

    A single-step electrophoretic deposition (EPD) process is used to fabricate catalyst layers which consist of nickel oxide nanoparticles attached on the surface of nanographitic flakes. Magnesium ions present in the colloid charge positively the flake's surface as they attach on it and are also used to bind nanographitic flakes together. The fabricated catalyst layers showed a very low onset voltage (-0.2 V vs Ag/AgCl) in the electro-oxidation of ethanol. To clarify the occurring catalytic mechanism, we performed annealing treatment to produce samples having a different electrochemical behavior with a large onset voltage. Temperature dependence measurements of the layer conductivity pointed toward a charge transport mechanism based on hopping for the nonannealed layers, while the drift transport is observed in the annealed layers. The hopping charge transport is responsible for the appearance of the low onset voltage in ethanol electro-oxidation.

  6. Changes in ion transport in inflammatory disease

    Directory of Open Access Journals (Sweden)

    Eisenhut Michael

    2006-03-01

    Full Text Available Abstract Ion transport is essential for maintenance of transmembranous and transcellular electric potential, fluid transport and cellular volume. Disturbance of ion transport has been associated with cellular dysfunction, intra and extracellular edema and abnormalities of epithelial surface liquid volume. There is increasing evidence that conditions characterized by an intense local or systemic inflammatory response are associated with abnormal ion transport. This abnormal ion transport has been involved in the pathogenesis of conditions like hypovolemia due to fluid losses, hyponatremia and hypokalemia in diarrhoeal diseases, electrolyte abnormalites in pyelonephritis of early infancy, septicemia induced pulmonary edema, and in hypersecretion and edema induced by inflammatory reactions of the mucosa of the upper respiratory tract. Components of membranous ion transport systems, which have been shown to undergo a change in function during an inflammatory response include the sodium potassium ATPase, the epithelial sodium channel, the Cystic Fibrosis Transmembrane Conductance Regulator and calcium activated chloride channels and the sodium potassium chloride co-transporter. Inflammatory mediators, which influence ion transport are tumor necrosis factor, gamma interferon, interleukins, transforming growth factor, leukotrienes and bradykinin. They trigger the release of specific messengers like prostaglandins, nitric oxide and histamine which alter ion transport system function through specific receptors, intracellular second messengers and protein kinases. This review summarizes data on in vivo measurements of changes in ion transport in acute inflammatory conditions and in vitro studies, which have explored the underlying mechanisms. Potential interventions directed at a correction of the observed abnormalities are discussed.

  7. Modeling low-dose-rate effects in irradiated bipolar-base oxides

    International Nuclear Information System (INIS)

    Graves, R.J.; Cirba, C.R.; Schrimpf, R.D.; Milanowski, R.J.; Saigne, F.; Michez, A.; Fleetwood, D.M.; Witczak, S.C.

    1997-02-01

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in BJTs. Simulations show that space charge limited transport is partially responsible for the low-dose-rate enhancement

  8. CFD analysis of a solid oxide fuel cell with internal reforming: Coupled interactions of transport, heterogeneous catalysis and electrochemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Janardhanan, Vinod M.; Deutschmann, Olaf [Institute for Chemical Technology and Polymer Chemistry, Engesserstr. 20, D-76131 Karlsruhe, University of Karlsruhe (TH) (Germany)

    2006-11-22

    Direct internal reforming in solid oxide fuel cell (SOFC) results in increased overall efficiency of the system. Present study focus on the chemical and electrochemical process in an internally reforming anode supported SOFC button cell running on humidified CH{sub 4} (3% H{sub 2} O). The computational approach employs a detailed multi-step model for heterogeneous chemistry in the anode, modified Butler-Volmer formalism for the electrochemistry and Dusty Gas Model (DGM) for the porous media transport. Two-dimensional elliptic model equations are solved for a button cell configuration. The electrochemical model assumes hydrogen as the only electrochemically active species. The predicted cell performances are compared with experimental reports. The results show that model predictions are in good agreement with experimental observation except the open circuit potentials. Furthermore, the steam content in the anode feed stream is found to have remarkable effect on the resulting overpotential losses and surface coverages of various species at the three-phase boundary. (author)

  9. CFD analysis of a solid oxide fuel cell with internal reforming: Coupled interactions of transport, heterogeneous catalysis and electrochemical processes

    Science.gov (United States)

    Janardhanan, Vinod M.; Deutschmann, Olaf

    Direct internal reforming in solid oxide fuel cell (SOFC) results in increased overall efficiency of the system. Present study focus on the chemical and electrochemical process in an internally reforming anode supported SOFC button cell running on humidified CH 4 (3% H 2 O). The computational approach employs a detailed multi-step model for heterogeneous chemistry in the anode, modified Butler-Volmer formalism for the electrochemistry and Dusty Gas Model (DGM) for the porous media transport. Two-dimensional elliptic model equations are solved for a button cell configuration. The electrochemical model assumes hydrogen as the only electrochemically active species. The predicted cell performances are compared with experimental reports. The results show that model predictions are in good agreement with experimental observation except the open circuit potentials. Furthermore, the steam content in the anode feed stream is found to have remarkable effect on the resulting overpotential losses and surface coverages of various species at the three-phase boundary.

  10. The Type VI Secretion System Engages a Redox-Regulated Dual-Functional Heme Transporter for Zinc Acquisition.

    Science.gov (United States)

    Si, Meiru; Wang, Yao; Zhang, Bing; Zhao, Chao; Kang, Yiwen; Bai, Haonan; Wei, Dawei; Zhu, Lingfang; Zhang, Lei; Dong, Tao G; Shen, Xihui

    2017-07-25

    The type VI secretion system was recently reported to be involved in zinc acquisition, but the underlying mechanism remains unclear. Here, we report that Burkholderia thailandensis T6SS4 is involved in zinc acquisition via secretion of a zinc-scavenging protein, TseZ, that interacts with the outer membrane heme transporter HmuR. We find that HmuR is a redox-regulated dual-functional transporter that transports heme iron under normal conditions but zinc upon sensing extracellular oxidative stress, triggered by formation of an intramolecular disulfide bond. Acting as the first line of defense against oxidative stress, HmuR not only guarantees an immediate response to the changing environment but also provides a fine-tuned mechanism that allows a gradual response to perceived stress. The T6SS/HmuR-mediated active zinc transport system is also involved in bacterial virulence and contact-independent bacterial competition. We describe a sophisticated bacterial zinc acquisition mechanism affording insights into the role of metal ion transport systems. Copyright © 2017 The Author(s). Published by Elsevier Inc. All rights reserved.

  11. Anisotropic amplification of proton transport in proton exchange membrane fuel cells

    Science.gov (United States)

    Thimmappa, Ravikumar; Fawaz, Mohammed; Devendrachari, Mruthyunjayachari Chattanahalli; Gautam, Manu; Kottaichamy, Alagar Raja; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

    2017-07-01

    Though graphene oxide (GO) membrane shuttles protons under humid conditions, it suffer severe disintegration and anhydrous conditions lead to abysmal ionic conductivity. The trade-off between mechanical integrity and ionic conductivity challenge the amplification of GO's ionic transport under anhydrous conditions. We show anisotropic amplification of GO's ionic transport with a selective amplification of in plane contribution under anhydrous conditions by doping it with a plant extract, phytic acid (PA). The hygroscopic nature of PA stabilized interlayer water molecules and peculiar geometry of sbnd OH functionalities around saturated hydrocarbon ring anisotropically enhanced ionic transport amplifying the fuel cell performance metrics.

  12. Lactate transport and signaling in the brain

    DEFF Research Database (Denmark)

    Bergersen, Linda Hildegard

    2015-01-01

    AMP. The localization and function of HCAR1 and the three MCTs (MCT1, MCT2, and MCT4) expressed in brain constitute the focus of this review. They are possible targets for new therapeutic drugs and interventions. The author proposes that lactate actions in the brain through MCTs and the lactate receptor underlie part......Lactate acts as a ‘buffer’ between glycolysis and oxidative metabolism. In addition to being exchanged as a fuel by the monocarboxylate transporters (MCTs) between cells and tissues with different glycolytic and oxidative rates, lactate may be a ‘volume transmitter’ of brain signals. According...... to some, lactate is a preferred fuel for brain metabolism. Immediately after brain activation, the rate of glycolysis exceeds oxidation, leading to net production of lactate. At physical rest, there is a net efflux of lactate from the brain into the blood stream. But when blood lactate levels rise...

  13. Fuel Production from Seawater and Fuel Cells Using Seawater.

    Science.gov (United States)

    Fukuzumi, Shunichi; Lee, Yong-Min; Nam, Wonwoo

    2017-11-23

    Seawater is the most abundant resource on our planet and fuel production from seawater has the notable advantage that it would not compete with growing demands for pure water. This Review focuses on the production of fuels from seawater and their direct use in fuel cells. Electrolysis of seawater under appropriate conditions affords hydrogen and dioxygen with 100 % faradaic efficiency without oxidation of chloride. Photoelectrocatalytic production of hydrogen from seawater provides a promising way to produce hydrogen with low cost and high efficiency. Microbial solar cells (MSCs) that use biofilms produced in seawater can generate electricity from sunlight without additional fuel because the products of photosynthesis can be utilized as electrode reactants, whereas the electrode products can be utilized as photosynthetic reactants. Another important source for hydrogen is hydrogen sulfide, which is abundantly found in Black Sea deep water. Hydrogen produced by electrolysis of Black Sea deep water can also be used in hydrogen fuel cells. Production of a fuel and its direct use in a fuel cell has been made possible for the first time by a combination of photocatalytic production of hydrogen peroxide from seawater and dioxygen in the air and its direct use in one-compartment hydrogen peroxide fuel cells to obtain electric power. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products

    Science.gov (United States)

    Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.

    2017-07-01

    Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.

  15. Atomic-scale Studies of Uranium Oxidation and Corrosion by Water Vapour.

    Science.gov (United States)

    Martin, T L; Coe, C; Bagot, P A J; Morrall, P; Smith, G D W; Scott, T; Moody, M P

    2016-07-12

    Understanding the corrosion of uranium is important for its safe, long-term storage. Uranium metal corrodes rapidly in air, but the exact mechanism remains subject to debate. Atom Probe Tomography was used to investigate the surface microstructure of metallic depleted uranium specimens following polishing and exposure to moist air. A complex, corrugated metal-oxide interface was observed, with approximately 60 at.% oxygen content within the oxide. Interestingly, a very thin (~5 nm) interfacial layer of uranium hydride was observed at the oxide-metal interface. Exposure to deuterated water vapour produced an equivalent deuteride signal at the metal-oxide interface, confirming the hydride as originating via the water vapour oxidation mechanism. Hydroxide ions were detected uniformly throughout the oxide, yet showed reduced prominence at the metal interface. These results support a proposed mechanism for the oxidation of uranium in water vapour environments where the transport of hydroxyl species and the formation of hydride are key to understanding the observed behaviour.

  16. Atomic-scale Studies of Uranium Oxidation and Corrosion by Water Vapour

    Science.gov (United States)

    Martin, T. L.; Coe, C.; Bagot, P. A. J.; Morrall, P.; Smith, G. D. W.; Scott, T.; Moody, M. P.

    2016-07-01

    Understanding the corrosion of uranium is important for its safe, long-term storage. Uranium metal corrodes rapidly in air, but the exact mechanism remains subject to debate. Atom Probe Tomography was used to investigate the surface microstructure of metallic depleted uranium specimens following polishing and exposure to moist air. A complex, corrugated metal-oxide interface was observed, with approximately 60 at.% oxygen content within the oxide. Interestingly, a very thin (~5 nm) interfacial layer of uranium hydride was observed at the oxide-metal interface. Exposure to deuterated water vapour produced an equivalent deuteride signal at the metal-oxide interface, confirming the hydride as originating via the water vapour oxidation mechanism. Hydroxide ions were detected uniformly throughout the oxide, yet showed reduced prominence at the metal interface. These results support a proposed mechanism for the oxidation of uranium in water vapour environments where the transport of hydroxyl species and the formation of hydride are key to understanding the observed behaviour.

  17. TYPE AF CERTIFICATE FOR TRANSPORTATION OF LOW ENRICHED URANIUM OXIDE (LEUO) FOR DISPOSAL

    International Nuclear Information System (INIS)

    Opperman, E; Kenneth Yates, K

    2007-01-01

    Washington Savannah River Company (WSRC) operates the Savannah River Site (SRS) in Aiken, SC under contract with the U.S. Department of Energy (DOE). SRS had the need to ship 227 drums of low enriched uranium oxide (LEUO) to a disposal site. The LEUO had been packaged nearly 25 years ago in U.S. Department of Transportation (DOT) 17C 55-gallon drums and stored in a warehouse. Since the 235U enrichment was just above 1 percent by weight (wt%) the material did not qualify for the fissile material exceptions in 49 CFR 173.453, and therefore was categorized as 'fissile material' for shipping purposes. WSRC evaluated all existing Type AF packages and did not identify any feasible packaging. Applying for a new Type AF certificate of compliance was considered too costly for a one-time/one-way shipment for disposal. Down-blending the material with depleted uranium (to reduce enrichment below 1 wt% and enable shipment as low specific activity (LSA) radioactive material) was considered, but appropriate blending facilities do not exist at SRS. After reviewing all options, WSRC concluded that seeking a DOT Special Permit was the best option to enable shipment of the material for permanent disposal. WSRC submitted the Special Permit application to the DOT, and after one request-for-additional-information (RAI) the permit was considered acceptable. However, in an interesting development that resulted from the DOT Special Permit application process, it was determined that it was more appropriate for the DOE to issue a Type AF certificate [Ref. 1] for this shipping campaign. This paper will outline the DOT Special Permit application and Type AF considerations, and will discuss the issuance of the new DOE Type AF certificate of compliance

  18. Virtual transportation as a solution to urban transportation problems: a critical analysis of the potential of telecommuting as a work trip reduction strategy

    Energy Technology Data Exchange (ETDEWEB)

    Buczynski, J.A.

    1997-10-01

    Recent advancements in technology have made virtual transportation a potential solution to the urban transportation crisis. Virtual transportation (also called telecommuting or teleworking) was defined as `a philosophy of allowing an employee to perform required tasks full-time or part-time from his or her choice of location by using information technology`. Virtual transportation would help ease peak travel demands during rush hours. The exhaust gases from automobiles with internal combustion engines emit pollutants such as carbon monoxide, carbon dioxide, volatile organic compounds and nitrous oxides into the atmosphere, thus virtual transportation could contribute significantly to the improvement of air quality. Telecommuting also offers other advantages, for example, geographic constraints of time and space are removed and employees are able to locate anywhere with telecommunications networks. It was suggested that road pricing could be used to generate revenue to build networks of telecommunication centres. Road pricing could be an incentive for commuters to substitute physical travel with virtual travel. 23 refs., 2 tabs.

  19. Anticipated development in radioactive materials packaging and transport systems

    International Nuclear Information System (INIS)

    Williams, L.D.; Rhoads, R.E.; Hall, R.J.

    1976-07-01

    Closing the light water reactor fuel cycle and the use of mixed oxide fuels will produce materials such as solidified high level waste, cladding hulls and plutonium from Pu recycle fuel that have not been transported extensively in the past. Changes in allowable gaseous emissions from fuel cycle facilities may require the collection and transportation of radioactive noble gases and tritium. Although all of these materials could be transported in existing radioactive material packaging, economic considerations will make it desirable to develop new packaging specifically designed for each material. Conceptual package designs for these materials are reviewed. Special Nuclear Material transportation safeguards are expected to have a significant impact on future fuel cycle transportation. This subject is reviewed briefly. Other factors that could affect fuel cycle transportation are also discussed. Development of new packaging for radioactive materials is not believed to require the development of new technologies. New package designs will be primarily an adaptation of existing technology to fit the changing needs of a growing nuclear power industry. 23 references

  20. Reaction and Transport Processes Controlling In Situ Chemical Oxidation of DNAPLs

    Science.gov (United States)

    2006-11-01

    Contact Areas. Ground Water, 36(4):495-502. Atlas , R.M., and R. Bartha (1987). Microbial Ecology , Benjamin/Cummings Publishing Company, Menlo Park...relatively few species ( Atlas and Bartha 1987). If selection for bioremediation processes following oxidation does occur, competition for substrates...Experiments.....................................................................3-23 3.6.3. Microbial Culture Preparation for Evaluation of Coupling

  1. Stability and transport of commercial metal oxide nanoparticles in aquatic systems

    Science.gov (United States)

    The use of nano-technology and the application of products containing nano-scale particles have been increasing. When nano-scale particles are released to the environment, their stability, transport properties and interaction with other pollutants and natural organic matter play ...

  2. Low-temperature, solution-processed aluminum-doped zinc oxide as electron transport layer for stable efficient polymer solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Qianqian [College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Bao, Xichang, E-mail: baoxc@qibebt.ac.cn [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Yu, Jianhua [College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Zhu, Dangqiang [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Zhang, Qian [College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Gu, Chuantao [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Dong, Hongzhou [College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Yang, Renqiang [Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Dong, Lifeng, E-mail: DongLifeng@qust.edu.cn [College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Department of Physics, Hamline University, St. Paul, MN 55104 (United States)

    2016-04-30

    A simple low-temperature solution-processed zinc oxide (ZnO) and aluminum-doped ZnO (AZO) were synthesized and investigated as an electron transport layer (ETL) for inverted polymer solar cells. A solar cell with a blend of poly(4,8-bis-alkyloxy-benzo[1,2-b:4,5-b′] dithiophene-alt-alkylcarbonyl-thieno [3,4-b] thiophene) and (6,6)-phenyl-C71-butyric acid methyl ester as an active layer and AZO as ETL demonstrates a high power conversion efficiency (PCE) of 7.36% under the illumination of AM 1.5G, 100 mW/cm{sup 2}. Compared to the cells with ZnO ETL (PCE of 6.85%), the PCE is improved by 7.45% with the introduction of an AZO layer. The improved PCE is ascribed to the enhanced short circuit current density, which results from the electron transport property of the AZO layer. Moreover, AZO is a more stable interfacial layer than ZnO. The PCE of the solar cells with AZO as ETL retain 85% of their original value after storage for 120 days, superior to the 39% of cells with ZnO ETL. The results above indicate that a simple low-temperature solution-processed AZO film is an efficient and economical ETL for high-performance inverted polymer solar cells. Due to its environmental friendliness, good electrical properties, and simple preparation approach, AZO has the potential to be applied in high-performance, large-scale industrialization of solar cells and other electronic devices. - Highlights: • ZnO and AZO were synthesized by a simple low-temperature solution-processed method. • AZO films show high transmittance and conductivity. • The photovoltaic performance can be improved with AZO as ETL. • AZO-based devices demonstrate excellent stability, with 85% retained after 120 days.

  3. Transport of Water in Semicrystalline Block Copolymer Membranes

    Science.gov (United States)

    Hallinan, Daniel; Oparaji, Onyekachi

    Poly(styrene)-block-poly(ethylene oxide) (PS- b-PEO) is a semicrystalline block copolymer (BCP) with interesting properties. It is mechanically tough, amphiphilic, and has a polar phase. The mechanical toughness is due to the crystallinity of PEO and the high glass transition temperature of PS, as well as the morphological structure of the BCP. The polymer has high CO2, water, and salt solubility that derive from the polar PEO component. Potential applications include CO2 separation, water purification, and lithium air batteries. In all of the aforementioned applications, water transport is an important parameter. The presence of water can also affect thermal and mechanical properties. Water transport and thermal and mechanical properties of a lamellar PS- b-PEO copolymer have been measured as a function of water activity. Water transport can be affected by the heterogeneous nature of a semicrystalline BCP. Therefore, Fourier transform infrared - attenuated total reflectance (FTIR-ATR) spectroscopy has been employed, because water transport and polymer swelling can be measured simultaneously. The effect of BCP structure on transport has been investigated by comparing water transport in PS- b-PEO to a PEO homopolymer. The crystalline content of the PEO and the presence of glassy PS lamellae will be used to explain the transport results.

  4. GREET 1.5 - transportation fuel-cycle model - Vol. 1 : methodology, development, use, and results

    International Nuclear Information System (INIS)

    Wang, M. Q.

    1999-01-01

    This report documents the development and use of the most recent version (Version 1.5) of the Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model. The model, developed in a spreadsheet format, estimates the full fuel-cycle emissions and energy associated with various transportation fuels and advanced vehicle technologies for light-duty vehicles. The model calculates fuel-cycle emissions of five criteria pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter with diameters of 10 micrometers or less, and sulfur oxides) and three greenhouse gases (carbon dioxide, methane, and nitrous oxide). The model also calculates total energy consumption, fossil fuel consumption, and petroleum consumption when various transportation fuels are used. The GREET model includes the following cycles: petroleum to conventional gasoline, reformulated gasoline, conventional diesel, reformulated diesel, liquefied petroleum gas, and electricity via residual oil; natural gas to compressed natural gas, liquefied natural gas, liquefied petroleum gas, methanol, Fischer-Tropsch diesel, dimethyl ether, hydrogen, and electricity; coal to electricity; uranium to electricity; renewable energy (hydropower, solar energy, and wind) to electricity; corn, woody biomass, and herbaceous biomass to ethanol; soybeans to biodiesel; flared gas to methanol, dimethyl ether, and Fischer-Tropsch diesel; and landfill gases to methanol. This report also presents the results of the analysis of fuel-cycle energy use and emissions associated with alternative transportation fuels and advanced vehicle technologies to be applied to passenger cars and light-duty trucks

  5. Analysis of time-of-flight experiment on lithium-oxide assemblies by a two-dimensional transport code DOT3.5

    International Nuclear Information System (INIS)

    Oyama, Yukio; Yamaguchi, Seiya; Maekawa, Hiroshi

    1985-03-01

    Calculational analyses were made on the time-of-flight experiment of neutron leakage spectra from lithium-oxide slabs. The uncertainties in the calculation due to modelling were examined and it was estimated to be 1-2 %. The calculational results were compared with the experimental ones. The calculations were carried out by a two-dimensional transport code DOT3.5 using ENDF/B-4 nuclear data file. The comparison of energy-integrated fluxes in C/E from made it clear that the tendency of discrepancy between both results depended on the thickness of assembly and leaking angle. The discrepancy of C/E was about 40 % at the maximum. The effect due to the cross section change to a new data of 7 Li(n,n't) 4 He was also examined. This type of comparison is useful for the systematic assesments. From the comparison, it was suggested that the angular distribution of secondary neutron should be improved in the calculation, and the correct differential data of cross section are required. (author)

  6. Control of intracellular heme levels: Heme transporters and Heme oxygenases

    Science.gov (United States)

    Khan, Anwar A.; Quigley, John G.

    2011-01-01

    Heme serves as a co-factor in proteins involved in fundamental biological processes including oxidative metabolism, oxygen storage and transport, signal transduction and drug metabolism. In addition, heme is important for systemic iron homeostasis in mammals. Heme has important regulatory roles in cell biology, yet excessive levels of intracellular heme are toxic; thus, mechanisms have evolved to control the acquisition, synthesis, catabolism and expulsion of cellular heme. Recently, a number of transporters of heme and heme synthesis intermediates have been described. Here we review aspects of heme metabolism and discuss our current understanding of heme transporters, with emphasis on the function of the cell-surface heme exporter, FLVCR. Knockdown of Flvcr in mice leads to both defective erythropoiesis and disturbed systemic iron homeostasis, underscoring the critical role of heme transporters in mammalian physiology. PMID:21238504

  7. Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

    Science.gov (United States)

    Kletzin, Arnulf; Urich, Tim; Müller, Fabian; Bandeiras, Tiago M; Gomes, Cláudio M

    2004-02-01

    The oxidation and reduction of elemental sulfur and reduced inorganic sulfur species are some of the most important energy-yielding reactions for microorganisms living in volcanic hot springs, solfataras, and submarine hydrothermal vents, including both heterotrophic, mixotrophic, and chemolithoautotrophic, carbon dioxide-fixing species. Elemental sulfur is the electron donor in aerobic archaea like Acidianus and Sulfolobus. It is oxidized via sulfite and thiosulfate in a pathway involving both soluble and membrane-bound enzymes. This pathway was recently found to be coupled to the aerobic respiratory chain, eliciting a link between sulfur oxidation and oxygen reduction at the level of the respiratory heme copper oxidase. In contrast, elemental sulfur is the electron acceptor in a short electron transport chain consisting of a membrane-bound hydrogenase and a sulfur reductase in (facultatively) anaerobic chemolithotrophic archaea Acidianus and Pyrodictium species. It is also the electron acceptor in organoheterotrophic anaerobic species like Pyrococcus and Thermococcus, however, an electron transport chain has not been described as yet. The current knowledge on the composition and properties of the aerobic and anaerobic pathways of dissimilatory elemental sulfur metabolism in thermophilic archaea is summarized in this contribution.

  8. Oxidative stress negatively affects human sperm mitochondrial respiration.

    Science.gov (United States)

    Ferramosca, Alessandra; Pinto Provenzano, Sara; Montagna, Daniela Domenica; Coppola, Lamberto; Zara, Vincenzo

    2013-07-01

    To correlate the level of oxidative stress in serum and seminal fluid and the level of sperm deoxyribonucleic acid (DNA) fragmentation with sperm mitochondrial respiratory efficiency. Sperm mitochondrial respiratory activity was evaluated with a polarographic assay of oxygen consumption carried out in hypotonically treated sperm cells. A possible relationship between sperm mitochondrial respiratory efficiency, the level of oxidative stress, and the level of sperm DNA fragmentation was investigated. Sperm motility was positively correlated with mitochondrial respiration but negatively correlated with oxidative stress and DNA fragmentation. Interestingly, sperm mitochondrial respiratory activity was negatively affected by oxidative stress and DNA fragmentation. Our data indicate that sperm mitochondrial respiration is decreased in patients with high levels of reactive oxygen species by an uncoupling between electron transport and adenosine triphosphate synthesis. This reduction in mitochondrial functionality might be 1 of the reasons responsible for the decrease in spermatozoa motility. Copyright © 2013 Elsevier Inc. All rights reserved.

  9. On direct and indirect methanol fuel cells for transportation applications

    Energy Technology Data Exchange (ETDEWEB)

    Gottesfield, S.

    1996-04-01

    Research on direct oxidation methanol fuel cells (DMFCs) and polymer electrolyte fuel cells (PEFCs) is discussed. Systems considered for transportation applications are addressed. The use of platinum/ruthenium anode electrocatalysts and platinum cathode electrocatalysts in polymer electrolyte DMFCs has resulted in significant performance enhancements.

  10. Toxicity of Graphene Shells, Graphene Oxide, and Graphene Oxide Paper Evaluated with Escherichia coli Biotests

    Directory of Open Access Journals (Sweden)

    Ludmila V. Efremova

    2015-01-01

    Full Text Available The plate-like graphene shells (GS produced by an original methane pyrolysis method and their derivatives graphene oxide (GO and graphene oxide paper (GO-P were evaluated with luminescent Escherichia coli biotests and additional bacterial-based assays which together revealed the graphene-family nanomaterials’ toxicity and bioactivity mechanisms. Bioluminescence inhibition assay, fluorescent two-component staining to evaluate cell membrane permeability, and atomic force microscopy data showed GO expressed bioactivity in aqueous suspension, whereas GS suspensions and the GO-P surface were assessed as nontoxic materials. The mechanism of toxicity of GO was shown not to be associated with oxidative stress in the targeted soxS::lux and katG::lux reporter cells; also, GO did not lead to significant mechanical disruption of treated bacteria with the release of intracellular DNA contents into the environment. The well-coordinated time- and dose-dependent surface charge neutralization and transport and energetic disorders in the Escherichia coli cells suggest direct membrane interaction, internalization, and perturbation (i.e., “membrane stress” as a clue to graphene oxide’s mechanism of toxicity.

  11. Weld oxide formation on lean duplex stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Westin, E.M. [Outokumpu Stainless, Avesta Research Centre, P.O. Box 74, SE-774 22 Avesta (Sweden)], E-mail: elin.westin@outokumpu.com; Olsson, C.-O.A. [Outokumpu Stainless, Avesta Research Centre, P.O. Box 74, SE-774 22 Avesta (Sweden); Hertzman, S. [Outokumpu Stainless Research Foundation, Brinellvaegen 23, SE-100 44 Stockholm (Sweden)

    2008-09-15

    Weld oxides have a strong influence on corrosion resistance, but have hitherto only been studied to a limited extent for duplex stainless steels. X-ray photoelectron spectroscopy (XPS) has here been used to study heat tint formed on gas tungsten arc (GTA) welds on the commercial duplex grades LDX 2101 (EN 1.4162/UNS S32101) and 2304 (EN 1.4362/UNS S32304) welded with and without nitrogen additions to the shielding gas. The process of heat tint formation is discussed in terms of transport phenomena to explain the effect of atmosphere, temperature and composition. The oxides formed were found to be enriched in manganese and corrosion testing shows that nitrogen has a strong influence on the weld oxide. A mechanism is proposed including evaporation from the weld pool and subsequent redeposition.

  12. Weld oxide formation on lean duplex stainless steel

    International Nuclear Information System (INIS)

    Westin, E.M.; Olsson, C.-O.A.; Hertzman, S.

    2008-01-01

    Weld oxides have a strong influence on corrosion resistance, but have hitherto only been studied to a limited extent for duplex stainless steels. X-ray photoelectron spectroscopy (XPS) has here been used to study heat tint formed on gas tungsten arc (GTA) welds on the commercial duplex grades LDX 2101 (EN 1.4162/UNS S32101) and 2304 (EN 1.4362/UNS S32304) welded with and without nitrogen additions to the shielding gas. The process of heat tint formation is discussed in terms of transport phenomena to explain the effect of atmosphere, temperature and composition. The oxides formed were found to be enriched in manganese and corrosion testing shows that nitrogen has a strong influence on the weld oxide. A mechanism is proposed including evaporation from the weld pool and subsequent redeposition

  13. Non-oxidative conversion of methane into higher hydrocarbons over ...

    Indian Academy of Sciences (India)

    SOURABH MISHRA

    2017-09-27

    Sep 27, 2017 ... ... in the Design and Development of Catalysts and their Applications ... of methane (natural gas) into transportable chemicals ... molybdenum (Mo) catalyst under non-oxidative condi- ... Micromeritics ASAP 2010 apparatus at liquid nitrogen tem- ... fixed-bed tubular reactor (500 mm length & 15 mm ID) at.

  14. Evaluation of a self-guided transport vehicle for remote transportation of transuranic and other hazardous waste

    Energy Technology Data Exchange (ETDEWEB)

    Rice, P.M.; Moody, S.J.; Peterson, R. [and others

    1997-04-01

    Between 1952 and 1970, over two million cubic ft of transuranic mixed waste was buried in shallow pits and trenches in the Subsurface Disposal Area at the Idaho National Engineering Laboratory`s Radioactive Waste Management Complex. Commingled with this two million cubic ft of waste is up to 10 million cubic ft of fill soil. The pits and trenches were constructed similarly to municipal landfills with both stacked and random dump waste forms such as barrels and boxes. The main contaminants are micron-sized particles of plutonium and americium oxides, chlorides, and hydroxides. Retrieval, treatment, and disposal is one of the options being considered for the waste. This report describes the results of a field demonstration conducted to evaluate a technology for transporting exhumed transuranic wastes at the Idaho National Engineering and Environmental Laboratory (INEEL) and at other hazardous or radioactive waste sites through the U.S. Department of Energy complex. The full-scale demonstration, conducted at the INEEL Robotics Center in the summer of 1995, evaluated equipment performance and techniques for remote transport of exhumed buried waste. The technology consisted of a Self-Guided Transport Vehicle designed to remotely convey retrieved waste from the retrieval digface and transport it to a receiving/processing area with minimal human intervention. Data were gathered and analyzed to evaluate performance parameters such as precision and accuracy of navigation and transportation rates.

  15. Evaluation of a self-guided transport vehicle for remote transportation of transuranic and other hazardous waste

    International Nuclear Information System (INIS)

    Rice, P.M.; Moody, S.J.; Peterson, R.

    1997-04-01

    Between 1952 and 1970, over two million cubic ft of transuranic mixed waste was buried in shallow pits and trenches in the Subsurface Disposal Area at the Idaho National Engineering Laboratory's Radioactive Waste Management Complex. Commingled with this two million cubic ft of waste is up to 10 million cubic ft of fill soil. The pits and trenches were constructed similarly to municipal landfills with both stacked and random dump waste forms such as barrels and boxes. The main contaminants are micron-sized particles of plutonium and americium oxides, chlorides, and hydroxides. Retrieval, treatment, and disposal is one of the options being considered for the waste. This report describes the results of a field demonstration conducted to evaluate a technology for transporting exhumed transuranic wastes at the Idaho National Engineering and Environmental Laboratory (INEEL) and at other hazardous or radioactive waste sites through the U.S. Department of Energy complex. The full-scale demonstration, conducted at the INEEL Robotics Center in the summer of 1995, evaluated equipment performance and techniques for remote transport of exhumed buried waste. The technology consisted of a Self-Guided Transport Vehicle designed to remotely convey retrieved waste from the retrieval digface and transport it to a receiving/processing area with minimal human intervention. Data were gathered and analyzed to evaluate performance parameters such as precision and accuracy of navigation and transportation rates

  16. Oxidative release of chromium from Archean ultramafic rocks, its transport and environmental impact – A Cr isotope perspective on the Sukinda valley ore district (Orissa, India)

    DEFF Research Database (Denmark)

    Paulukat, Cora Stefanie; Døssing, Lasse Nørbye; Mondal, Sisir K.

    2015-01-01

    to negatively fractionated values as low as δ53Cr = −1.29 ± 0.04‰. Local surface waters are isotopically heavy relative to the soils. This supports the hypothesis that during oxidative weathering isotopically heavy Cr(VI) is leached from the soils to runoff. The impact of mining pollution is observed downstream...... in controlling the hazardous impact of Cr(VI) on health and environment. The positive Cr isotope signatures of the Brahmani estuary and coastal seawater collected from the Bay of Bengal further indicate that the positively fractionated Cr isotope signal from the catchment area is preserved during its transport...

  17. Transportation Sector Model of the National Energy Modeling System. Volume 1

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-01-01

    This report documents the objectives, analytical approach and development of the National Energy Modeling System (NEMS) Transportation Model (TRAN). The report catalogues and describes the model assumptions, computational methodology, parameter estimation techniques, model source code, and forecast results generated by the model. The NEMS Transportation Model comprises a series of semi-independent models which address different aspects of the transportation sector. The primary purpose of this model is to provide mid-term forecasts of transportation energy demand by fuel type including, but not limited to, motor gasoline, distillate, jet fuel, and alternative fuels (such as CNG) not commonly associated with transportation. The current NEMS forecast horizon extends to the year 2010 and uses 1990 as the base year. Forecasts are generated through the separate consideration of energy consumption within the various modes of transport, including: private and fleet light-duty vehicles; aircraft; marine, rail, and truck freight; and various modes with minor overall impacts, such as mass transit and recreational boating. This approach is useful in assessing the impacts of policy initiatives, legislative mandates which affect individual modes of travel, and technological developments. The model also provides forecasts of selected intermediate values which are generated in order to determine energy consumption. These elements include estimates of passenger travel demand by automobile, air, or mass transit; estimates of the efficiency with which that demand is met; projections of vehicle stocks and the penetration of new technologies; and estimates of the demand for freight transport which are linked to forecasts of industrial output. Following the estimation of energy demand, TRAN produces forecasts of vehicular emissions of the following pollutants by source: oxides of sulfur, oxides of nitrogen, total carbon, carbon dioxide, carbon monoxide, and volatile organic compounds.

  18. Evolution of pollutants emissions by transports in france from 1970 to 2010; Evolution des emissions de polluants par les transports en France de 1970 a 2010

    Energy Technology Data Exchange (ETDEWEB)

    Joumard, R; Lambert, J

    1996-07-01

    Fuel consumption and CO, CO{sub 2}, HC, NOx, particulates and PAH amounts released by all transport modes from 1970 to 2010 are calculated. A thorough analysis, using parc and pollen softwares, was performed for road traffic. Three scenarios of transport development from 1989 are simulated. Results show that there will not be any problem with CO and HC emissions for the following 20 years, but emissions of nitrogen oxides and carbon dioxide will be significantly increased. Motorcycles and air transport are significantly polluting too, while duty vehicles, specifically diesel-engined cars, are the main polluting mode. Average unit emissions are analysed according to road type and vehicle type. (author)

  19. Comparison of reduction products from graphite oxide and graphene oxide for anode applications in lithium-ion batteries and sodium-ion batteries.

    Science.gov (United States)

    Sun, Yige; Tang, Jie; Zhang, Kun; Yuan, Jinshi; Li, Jing; Zhu, Da-Ming; Ozawa, Kiyoshi; Qin, Lu-Chang

    2017-02-16

    Hydrazine-reduced graphite oxide and graphene oxide were synthesized to compare their performances as anode materials in lithium-ion batteries and sodium-ion batteries. Reduced graphite oxide inherits the layer structure of graphite, with an average spacing between neighboring layers (d-spacing) of 0.374 nm; this exceeds the d-spacing of graphite (0.335 nm). The larger d-spacing provides wider channels for transporting lithium ions and sodium ions in the material. We showed that reduced graphite oxide as an anode in lithium-ion batteries can reach a specific capacity of 917 mA h g -1 , which is about three times of 372 mA h g -1 , the value expected for the LiC 6 structures on the electrode. This increase is consistent with the wider d-spacing, which enhances lithium intercalation and de-intercalation on the electrodes. The electrochemical performance of the lithium-ion batteries and sodium-ion batteries with reduced graphite oxide anodes show a noticeable improvement compared to those with reduced graphene oxide anodes. This improvement indicates that reduced graphite oxide, with larger interlayer spacing, has fewer defects and is thus more stable. In summary, we found that reduced graphite oxide may be a more favorable form of graphene for the fabrication of electrodes for lithium-ion and sodium-ion batteries and other energy storage devices.

  20. Fuel cell water transport

    Science.gov (United States)

    Vanderborgh, Nicholas E.; Hedstrom, James C.

    1990-01-01

    The moisture content and temperature of hydrogen and oxygen gases is regulated throughout traverse of the gases in a fuel cell incorporating a solid polymer membrane. At least one of the gases traverses a first flow field adjacent the solid polymer membrane, where chemical reactions occur to generate an electrical current. A second flow field is located sequential with the first flow field and incorporates a membrane for effective water transport. A control fluid is then circulated adjacent the second membrane on the face opposite the fuel cell gas wherein moisture is either transported from the control fluid to humidify a fuel gas, e.g., hydrogen, or to the control fluid to prevent excess water buildup in the oxidizer gas, e.g., oxygen. Evaporation of water into the control gas and the control gas temperature act to control the fuel cell gas temperatures throughout the traverse of the fuel cell by the gases.