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Sample records for oxidation state

  1. Oxidation state in chondrites

    NASA Technical Reports Server (NTRS)

    Rubin, Alan E.; Fegley, Bruce; Brett, Robin

    1988-01-01

    An evaluation is made of extant data on chondrite oxidation states and intrinsic O fugacities. A variety of oxidation states are exhibited by the chondritic meteorites; petrologic and chemical data may be used to arrange the major chondrite groups in order of oxidation state. The intrinsic O fugacity measurements on chondrite whole-rock samples are noted to display a corresponding ordering of oxidation states. Metamorphosed chondrites and igneous meteorites that were substantially altered by metamorphic reactions, outgassing, and igneous processes may preserve information on the oxidation state and size of their parent bodies.

  2. Experiments with Unusual Oxidation States

    ERIC Educational Resources Information Center

    Kauffman, G. B.

    1975-01-01

    Describes four synthesis experiments, adapted for the general chemistry laboratory, in which compounds in unusual oxidation are prepared. The abnormal oxidation states involved in the synthesis products are: silver (II), chromium (II), lead (IV), and bromine (I). (MLH)

  3. Experiments with Unusual Oxidation States

    ERIC Educational Resources Information Center

    Kauffman, G. B.

    1975-01-01

    Describes four synthesis experiments, adapted for the general chemistry laboratory, in which compounds in unusual oxidation are prepared. The abnormal oxidation states involved in the synthesis products are: silver (II), chromium (II), lead (IV), and bromine (I). (MLH)

  4. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

    Mixed valence RhIII/RhIV oxides have been proposed as a promising class of candidate compounds for superconductivity. Unfortunately, it is difficult to stabilize rhodates with a formal oxidation state approaching RhIV, as other techniques used for the synthesis of rhodium. oxides favor the most commonly observed formal oxidation state, RhIII. One technique which has been used to stabilize metal oxides in high formal oxidation states is crystallization from molten hydroxides. This thesis explores the use of molten hydroxides to enhance the reactivity of rhodium oxides in order to synthesize rhodates with high formal oxidation states. K0.5RhO2, Rb0.2RhO2, and CsxRhO2 were synthesized from pure alkali metal hydroxides. All crystallized with a previously unobserved polytype in the alkali metal rhodate system. Due to the low activity of dissolved oxygen species in LiOH and NaOH, LiRhO2 and NaRhO2 cannot be crystallized. The formal oxidation state of rhodium in AxRhO2 (A = K, Rb, Cs) is a function of the alkali metal hydroxide used to synthesize these oxides. These materials exhibit remarkable stability for layered metal oxides containing the heavier alkali metals, but all phases are susceptible to intercalation by water. The synthesis, structural characterization, magnetic susceptibility, and reactivity of these oxides are reported. Sr2RhO4 and a new rhodate were crystallized from a KOH-Sr(OH)2 flux. The synthesis and characterization of these materials is reported. Efforts to substitute platinum for rhodium in Sr 2RhO4 are also discussed. Mixed alkali metal-alkaline earth metal hydroxide fluxes were used to crystallize LiSr3RhO6, and NaSr3RhO 6. The synthesis of LiSr3RhO6 and NaSr3RhO 6 represents the first example of the stabilization of a rhodium oxide with a formal oxidation state approaching RhV. X-ray diffraction, electron beam microprobe analysis, thermogravimetric analysis, potentiometric titrations, X-ray photoelectron spectroscopy, and magnetic susceptibility

  5. Semiconductor Oxide Interface States.

    DTIC Science & Technology

    1981-05-01

    essentially coincides. The density of state curves of the interface states based on the Terman method are shown in Fig. 7 for the three conditions: (i...terrestrial applications. A visit was made at the NASA Lewis Research Center with Dr. Brandhorst on August 31, 1979. The PI has attended DOE meetings on

  6. XPS Determination of Uranium Oxidations States

    SciTech Connect

    Ilton, Eugene S.; Bagus, Paul S.

    2011-12-01

    This contribution is both a review of different aspects of the XPS spectra that can help one determine U oxidation states and a personal perspective on how to effectively model the XPS of complicated mixed valence U phases. After a discussion of the valence band, the focus lingers on the U4f region, where the use of binding energies, satellite structures, and peak shapes is discussed in some detail. Binding energies were shown to be very dependent on composition/structure and consequently unreliable guides to oxidation state, particularly where assignment of composition is difficult. Likewise, the spin orbit split 4f7/2 and 4f5/2 peak shapes do not carry significant information on oxidation states. In contrast, both satellite-primary peak binding energy separations, as well as intensities too lesser extent, are relatively insensitive to composition/structure within the oxide-hydroxide-hydrate system and can be used to both identify and help quantify U oxidation states in mixed valence phases. An example of the usefulness of the satellite structure in constraining the interpretation of a complex multivalence U compound is given.

  7. Manganese Oxidation State Assignment for Manganese Catalase.

    PubMed

    Beal, Nathan J; O'Malley, Patrick J

    2016-04-06

    The oxidation state assignment of the manganese ions present in the superoxidized manganese (III/IV) catalase active site is determined by comparing experimental and broken symmetry density functional theory calculated (14)N, (17)O, and (1)H hyperfine couplings. Experimental results have been interpreted to indicate that the substrate water is coordinated to the Mn(III) ion. However, by calculating hyperfine couplings for both scenarios we show that water is coordinated to the Mn(IV) ion and that the assigned oxidation states of the two manganese ions present in the site are the opposite of that previously proposed based on experimental measurements alone.

  8. Oxidation state of the mantle

    SciTech Connect

    Saxena, S.K. Graduate Center, New York, NY )

    1989-01-01

    Phase equilibrium relations are established in a system Mg-Fe-Si-H-O, with and without C, at high pressures and temperatures. High pressure-temperature equations of state for the fluids including non-ideal mixing are used in the calculations. The computed equilibrium data show that an olivine of appropriate mantle composition is stable over a wide range of temperature and oxygen fugacities in the carbon-free system. If C is introduced, such that the equilibrium assemblage may contain graphite or diamond, the fluid phase in the peridotite + water system consists mostly of H{sub 2}O and little CO{sub 2} and CH{sub 4}. However, the fluid composition is strongly affected by the Fe content of the system. If Fe is increased from undersaturation to that of saturation the CH{sub 4} content of the fluid changes from a low of 1% to a high of 89%. The calculated results show a fluid with as much as 75% methane could be in equilibrium with olivine without metallic Fe as a coexisting phase. The fO{sub 2} of the primitive mantle with such a fluid composition would be several log units below that of the quartz-fayalite-magnetite buffer.

  9. Average oxidation state of carbon in proteins.

    PubMed

    Dick, Jeffrey M

    2014-11-06

    The formal oxidation state of carbon atoms in organic molecules depends on the covalent structure. In proteins, the average oxidation state of carbon (Z(C)) can be calculated as an elemental ratio from the chemical formula. To investigate oxidation-reduction (redox) patterns, groups of proteins from different subcellular locations and phylogenetic groups were selected for comparison. Extracellular proteins of yeast have a relatively high oxidation state of carbon, corresponding with oxidizing conditions outside of the cell. However, an inverse relationship between Z(C) and redox potential occurs between the endoplasmic reticulum and cytoplasm. This trend provides support for the hypothesis that protein transport and turnover are ultimately coupled to the maintenance of different glutathione redox potentials in subcellular compartments. There are broad changes in Z(C) in whole-genome protein compositions in microbes from different environments, and in Rubisco homologues, lower Z(C) tends to occur in organisms with higher optimal growth temperature. Energetic costs calculated from thermodynamic models are consistent with the notion that thermophilic organisms exhibit molecular adaptation to not only high temperature but also the reducing nature of many hydrothermal fluids. Further characterization of the material requirements of protein metabolism in terms of the chemical conditions of cells and environments may help to reveal other linkages among biochemical processes with implications for changes on evolutionary time scales.

  10. Expanded Definition of the Oxidation State

    ERIC Educational Resources Information Center

    Loock, Hans-Peter

    2011-01-01

    A proposal to define the oxidation state of an atom in a compound as the hypothetical charge of the corresponding atomic ion that is obtained by heterolytically cleaving its bonds such that the atom with the higher electronegativity in a bond is allocated all electrons in the bond. Bonds between like atoms are cleaved homolytically. This…

  11. Expanded Definition of the Oxidation State

    ERIC Educational Resources Information Center

    Loock, Hans-Peter

    2011-01-01

    A proposal to define the oxidation state of an atom in a compound as the hypothetical charge of the corresponding atomic ion that is obtained by heterolytically cleaving its bonds such that the atom with the higher electronegativity in a bond is allocated all electrons in the bond. Bonds between like atoms are cleaved homolytically. This…

  12. Higher Americium Oxidation State Research Roadmap

    SciTech Connect

    Mincher, Bruce J.; Law, Jack D.; Goff, George S.; Moyer, Bruce A.; Burns, Jon D.; Lumetta, Gregg J.; Sinkov, Sergey I.; Shehee, Thomas C.; Hobbs, David T.

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  13. Average oxidation state of carbon in proteins

    PubMed Central

    Dick, Jeffrey M.

    2014-01-01

    The formal oxidation state of carbon atoms in organic molecules depends on the covalent structure. In proteins, the average oxidation state of carbon (ZC) can be calculated as an elemental ratio from the chemical formula. To investigate oxidation–reduction (redox) patterns, groups of proteins from different subcellular locations and phylogenetic groups were selected for comparison. Extracellular proteins of yeast have a relatively high oxidation state of carbon, corresponding with oxidizing conditions outside of the cell. However, an inverse relationship between ZC and redox potential occurs between the endoplasmic reticulum and cytoplasm. This trend provides support for the hypothesis that protein transport and turnover are ultimately coupled to the maintenance of different glutathione redox potentials in subcellular compartments. There are broad changes in ZC in whole-genome protein compositions in microbes from different environments, and in Rubisco homologues, lower ZC tends to occur in organisms with higher optimal growth temperature. Energetic costs calculated from thermodynamic models are consistent with the notion that thermophilic organisms exhibit molecular adaptation to not only high temperature but also the reducing nature of many hydrothermal fluids. Further characterization of the material requirements of protein metabolism in terms of the chemical conditions of cells and environments may help to reveal other linkages among biochemical processes with implications for changes on evolutionary time scales. PMID:25165594

  14. Oxidation state of BZ reaction mixtures.

    PubMed

    Sobel, Sabrina G; Hastings, Harold M; Field, Richard J

    2006-01-12

    The unstirred, ferroin (Fe(phen)(3)2+)-catalyzed Belousov-Zhabotinsky (BZ) reaction1-4 is the prototype oscillatory chemical system. After an induction period of several minutes, one sees "spontaneous" formation of "pacemaker" sites, which oscillate between a blue, oxidized state (high [Fe(phen)3(3+)]) and a red, reduced state (low [Fe(phen)(3)3+]). The reaction medium appears red (reduced) during the induction phase, and the pacemaker sites generate target patterns of concentric, outwardly moving waves of oxidation (blue). Auto-oscillatory behavior is also seen in the Oregonator model of Field, Korös, and Noyes (FKN), a robust, reduced model which captures qualitative BZ kinetics in the auto-oscillatory regime. However, the Oregonator model predicts a blue (oxidized) induction phase. Here, we show that including reaction R8 of the FKN mechanism, not incorporated in the original Oregonator, accounts for bromide release during the induction phase, thus producing the observed red oxidation state.

  15. Oxidation state of marine manganese nodules

    USGS Publications Warehouse

    Piper, D.Z.; Basler, J.R.; Bischoff, J.L.

    1984-01-01

    Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba).33(Mg, Cu, Ni).76Mn5O22(H2O)3.2. ?? 1984.

  16. Photochemical oxidants: state of the science.

    PubMed

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  17. Chromium oxidation state mapping in human cells

    NASA Astrophysics Data System (ADS)

    Ortega, R.; Fayard, B.; Salomé, M.; Devès, G.; Susini, J.

    2003-03-01

    The widespread use of chromium in industrial applications such as chemical production of pigments, refractory brick production, tanning, metallurgy, electroplating, and combustion of fuels has lead to human occupational exposure and to its increased introduction into the environment. Hexavalent chromium compounds are established carcinogens but their mechanism of cell transformation is not known. Up to now, no microanalytical technique was sensitive enough to allow the observation of chromium distribution, and oxidation state identification, within isolated cells at carcinogenic concentrations. In this experiment, we used successfully the ID-21 X-ray microscope to map Cr(VI) and total Cr distributions in cells exposed in vitro to soluble, and insoluble, Cr(VI) compounds. Exposure to soluble compounds, weak carcinogens, resulted in a homogeneous intracellular distribution of Cr, confirming by in situ measurement that Cr is present in the cell nucleus. Cr(VI) was never detected in cells which suggests a mechanism of rapid intracellular reducticn. On the other hand, exposure to insoluble compounds, strong carcinogens, also resulted in a homogeneous distribution of reduced forms of Cr in cells, and their nucleus. However, in this case, Cr(VI)-rich structures were observed into the cells suggesting that carcinogenicity is enhanced when oxidation reactions due to Cr(VI) chronic exposure are associated to Cr-DNA alterations.

  18. On the Extreme Oxidation States of Iridium.

    PubMed

    Pyykkö, Pekka; Xu, Wen-Hua

    2015-06-22

    It has recently been suggested that the oxidation states of Ir run from the putative -III in the synthesized solid Na3 [Ir(CO)3 ] to the well-documented +IX in the species IrO4 (+) . Furthermore, [Ir(CO)3 ](3-) was identified as an 18-electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18 e leave the orbital symmetries unchanged. The isoelectronic systems from Os(-IV) to Au(-I) behave similarly, suggesting further possible species. To paraphrase Richard P. Feynmann "there is plenty of room at the bottom".

  19. Synthesis of nanoscale silicon oxide oxidation state distributions: The transformation from hydrophilicity to hydrophobicity

    NASA Astrophysics Data System (ADS)

    Laminack, William; Gole, James L.; White, Mark G.; Ozdemir, Serdar; Ogden, Andrew G.; Martin, Holly J.; Fang, Zongtang; Wang, Tsang-Hsiu; Dixon, David A.

    2016-06-01

    Silicon oxide nanostructures which span the range from hydrophilic to hydrophobic have been synthesized. The surface chemistry of these silicon-based nanostructures was analyzed using a combination of X-ray photoelectron spectroscopy, reflectance infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The dominant oxidation state for the nanostructured oxides shifts from an average oxidation state of +III to a combination of +II and +III oxidation states. A correlation of the ability to adsorb water with variations in the surface Si:O ratios was observed showing a transition from hydrophilic to hydrophobic character.

  20. Equation of state of uranium oxide

    NASA Astrophysics Data System (ADS)

    Ohse, R. W.; Babelot, J.-F.; Cercignani, C.; Hiernaut, J.-P.; Hoch, M.; Hyland, G. J.; Magill, J.

    1985-02-01

    The total and partial pressures over liquid UO 2 have been measured and calculated up to 5000K. A review of previous work is given. The equation of state of UO 2 as the main constituent of the fast breeder oxide fuel is required up to at least 5000K in order to estimate the energy release in a loss of flow (LOF) driven hypothetical core disruptive accident (HCDA) of the liquid metal fast breeder reactor (LMFBR). Two models, a macroscopic "mixture" model and a microscopic "defect" model have been developed to determine the oxygen potential of UO 200 up to 5000 K. A combination of mass spectrometric, Langmuir probe and high tension diode studies, applied for the first time to the laser vaporization process, revealed large quantities of ions emitted directly from the surface, and resolved previous discrepancies between measured and calculated vapour pressures by an enhanced rate of evaporation due to ion emission. As shown theoretically intrinsic ion emission can contribute to the net evaporation rate only if the resulting positive space charge can be neutralised. It is proposed that this can be accomplished by the presence of "hot" electrons in the plasma. The recommended equilibrium total pressure over liquid UO 2.00, valid between the melting point and 5000K, is log p (MPa) = - 2.717 - 20131/T + 1.925 log T.

  1. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    SciTech Connect

    Jernigan, Glenn Geoffrey

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  2. Ion Exchange Separation of the Oxidation State of Vanadium.

    ERIC Educational Resources Information Center

    Cornelius, Richard

    1980-01-01

    Describes an experiment that emphasizes the discrete nature of the different oxidation states of vanadium by the separation of ammonium metavanadate into all four species by ion exchange chromatography. (CS)

  3. Ion Exchange Separation of the Oxidation State of Vanadium.

    ERIC Educational Resources Information Center

    Cornelius, Richard

    1980-01-01

    Describes an experiment that emphasizes the discrete nature of the different oxidation states of vanadium by the separation of ammonium metavanadate into all four species by ion exchange chromatography. (CS)

  4. XPS determination of Mn oxidation states in Mn (hydr)oxides

    SciTech Connect

    Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

    2016-03-01

    Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a common layered structure that occurs readily in Nature but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and widths of each oxidation state, composed of a packet of correlated component peaks, were allowed vary. whereas widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated with close agreement between Mn3s and Mn3p, whereas Mn2p3/2 gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than Mn2p. Consequently, fitting the Mn3p and Mn3s lines yields robust quantification of oxidation states over a range of hydrous Mn oxide polytypes and compositions. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line is not appropriate for birnessites.

  5. XPS determination of Mn oxidation states in Mn (hydr)oxides

    NASA Astrophysics Data System (ADS)

    Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

    2016-03-01

    Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic and redox activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a layered structure that occurs commonly in soils but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and peak-widths of each oxidation state, composed of a packet of correlated component peaks, were allowed to vary. Peak-widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated, with close agreement between Mn3s and Mn3p analyses, whereas calculations based on the Mn2p3/2 spectra gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than that for Mn2p. Consequently, fitting the Mn3p and Mn3s lines yielded robust quantification of oxidation states over a range of Mn (hydr)oxide phases. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line was found to be not appropriate for birnessites.

  6. What are the oxidation states of manganese required to catalyze photosynthetic water oxidation?

    PubMed

    Kolling, Derrick R J; Cox, Nicholas; Ananyev, Gennady M; Pace, Ron J; Dismukes, G Charles

    2012-07-18

    Photosynthetic O(2) production from water is catalyzed by a cluster of four manganese ions and a tyrosine residue that comprise the redox-active components of the water-oxidizing complex (WOC) of photosystem II (PSII) in all known oxygenic phototrophs. Knowledge of the oxidation states is indispensable for understanding the fundamental principles of catalysis by PSII and the catalytic mechanism of the WOC. Previous spectroscopic studies and redox titrations predicted the net oxidation state of the S(0) state to be (Mn(III))(3)Mn(IV). We have refined a previously developed photoassembly procedure that directly determines the number of oxidizing equivalents needed to assemble the Mn(4)Ca core of WOC during photoassembly, starting from free Mn(II) and the Mn-depleted apo-WOC complex. This experiment entails counting the number of light flashes required to produce the first O(2) molecules during photoassembly. Unlike spectroscopic methods, this process does not require reference to synthetic model complexes. We find the number of photoassembly intermediates required to reach the lowest oxidation state of the WOC, S(0), to be three, indicating a net oxidation state three equivalents above four Mn(II), formally (Mn(III))(3)Mn(II), whereas the O(2) releasing state, S(4), corresponds formally to (Mn(IV))(3)Mn(III). The results from this study have major implications for proposed mechanisms of photosynthetic water oxidation.

  7. Growth control of the oxidation state in vanadium oxide thin films

    NASA Astrophysics Data System (ADS)

    Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung

    2014-12-01

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V2 + 3 O 3 , V + 4 O 2 , and V2 + 5 O 5 . A well pronounced MIT was only observed in VO2 films grown in a very narrow range of oxygen partial pressure P(O2). The films grown either in lower (<10 mTorr) or higher P(O2) (>25 mTorr) result in V2O3 and V2O5 phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO2 thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

  8. Growth control of the oxidation state in vanadium oxide thin films

    SciTech Connect

    Lee, Shinbuhm; Meyer, Tricia L.; Lee, Ho Nyung; Park, Sungkyun; Egami, Takeshi

    2014-12-01

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V{sub 2}{sup +3}O{sub 3}, V{sup +4}O{sub 2}, and V{sub 2}{sup +5}O{sub 5}. A well pronounced MIT was only observed in VO{sub 2} films grown in a very narrow range of oxygen partial pressure P(O{sub 2}). The films grown either in lower (<10 mTorr) or higher P(O{sub 2}) (>25 mTorr) result in V{sub 2}O{sub 3} and V{sub 2}O{sub 5} phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO{sub 2} thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

  9. Growth control of the oxidation state in vanadium oxide thin films

    SciTech Connect

    Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Lee, Ho Nyung

    2014-12-05

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metalinsulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V₂⁺²O₃, V⁺⁴O₂, and V₂⁺⁵O₅. A well pronounced MIT was only observed in VO₂ films grown in a very narrow range of oxygen partial pressure P(O₂). The films grown either in lower (< 10 mTorr) or higher P(O₂) (> 25 mTorr) result in V₂O₃ and V₂O₅ phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO₂ thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an 3 improved MIT behavior.

  10. Growth control of the oxidation state in vanadium oxide thin films

    DOE PAGES

    Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; ...

    2014-12-05

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metalinsulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V₂⁺²O₃, V⁺⁴O₂, and V₂⁺⁵O₅. A well pronounced MIT was only observed in VO₂ films grown in a very narrow range of oxygen partial pressure P(O₂). The films grown either in lower (< 10 mTorr) or higher P(O₂) (> 25 mTorr) result in V₂O₃ and V₂O₅ phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO₂ thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an 3 improved MIT behavior.« less

  11. Solid state tungsten oxide hydrate/tin oxide hydrate electrochromic device prepared by electrochemical reactions

    NASA Astrophysics Data System (ADS)

    Nishiyama, Kentaro; Matsuo, Ryo; Sasano, Junji; Yokoyama, Seiji; Izaki, Masanobu

    2017-03-01

    The solid state electrochromic device composed of tungsten oxide hydrate (WO3(H2O)0.33) and tin oxide hydrate (Sn(O,OH)) has been constructed by anodic deposition of WO3(H2O)0.33 and Sn(O,OH) layers and showed the color change from clear to blue by applying voltage through an Au electrode.

  12. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    SciTech Connect

    Ma, Wen; Yildiz, Bilge; Herbert, F. William; Senanayake, Sanjaya D.

    2015-03-09

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr{sup 1+}, Zr{sup 2+}, and Zr{sup 3+} as non-equilibrium oxidation states, in addition to Zr{sup 4+} in the stoichiometric ZrO{sub 2}. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr{sup 0} and Zr{sup 4+} at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.

  13. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    DOE PAGES

    Ma, Wen; Senanayake, Sanjaya D.; Herbert, F. William; ...

    2015-03-11

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr1+, Zr2+, and Zr3+ as non-equilibrium oxidation states, in addition to Zr4+ in the stoichiometric ZrO2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr0 and Zr4+ at the metal-oxide interface. As a result, the presence of local strong electric fields andmore » the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.« less

  14. Theoretical Equation of State for Beryllium Oxide

    NASA Astrophysics Data System (ADS)

    Boettger, Jonathan C.; Honnell, Kevin G.; Mori, Yoshihisa; Niiya, Naoto; Mizuno, Takafumi

    2006-07-01

    A new, tabular (SESAME format) equation of state for BeO is developed. The new equation of state combines LGA and GGA density-functional predictions for the 0 K isotherm, the Johnson ionic model (which transitions smoothly from Debye behavior in the solid to ideal-gas behavior at high temperatures), and the Thomas-Fermi-Dirac model for thermal electronic contributions. Results for the compressibility, shock Hugoniots, thermal expansion, and heat capacity are in very good agreement with experimental measurements. At room temperature, the theory predicts a wurtzite-to-rock-salt transition at a pressure of 105 GPa, consistent with new XRD diamond-anvil results.

  15. The global oxidation state of the upper oceanic crust

    NASA Astrophysics Data System (ADS)

    Rutter, J.; Harris, M.; Coggon, R. M.; Alt, J.; Smith-Duque, C. E.; Teagle, D. A.

    2012-12-01

    The oxidation state of the oceanic crust is an important component of the Earth system. The widespread oxidation of the crust is a major contributor to the redox state of the mantle due to the subduction of hydrothermally altered oceanic crust, which supplies 10 - 25 % of the net ferric iron flux to the global mantle Fe3+/FeTOT budget (Lécuyer and Ricard, 1999). Secondly, the degree of oxidation of the upper oceanic crust provides a measure of the biomass of microbial life sub-basement (Bach and Edwards, 2003). Thirdly, oxidation state analyses of oceanic basalt give information on the environment and relative timings of local hydrothermal alteration events. To date comprehensive measurements of Fe3+/FeTOT for the oceanic crust are lacking. Post crystallisation oxidation processes, occurring predominantly in the upper basaltic layers of the crust, elevate ratios of ferric to total iron (Fe3+/FeTOT) from mantle levels of 0.16 ± 0.01 (Cottrell and Kelley, 2011). Ferrous (Fe2+/) iron is oxidised to ferric (Fe3+/) iron during reaction with oxidised seawater, which circulates through oceanic crust for tens of millions of years following crustal formation. This study integrates published data with new analyses from six ocean crustal boreholes to categorise the global oxidation state of the upper crust. Samples range from <1 to 129 Ma, and represent basalt from medium to superfast spreading centres, depths between <100 - 2000 mbsf, and at a variety of sedimentary cover rates and thicknesses. Results show that by 1 Ma, the Fe3+/FeTOT ratio of the bulk crust is already raised to an average of 0.28 ± 0.07, implying that the oxidation state is established very early in the lifetime of the ocean crust. Post 1 Ma, Fe3+/FeTOT ratios are more variable, reflecting the effects of prolonged exposure to circulating seawater, but are on average ~0.35.

  16. Direct Determination of the Intracellular Oxidation State of Plutonium

    PubMed Central

    Gorman-Lewis, Drew; Aryal, Baikuntha P.; Paunesku, Tatjana; Vogt, Stefan; Lai, Barry; Woloschak, Gayle E.; Jensen, Mark P.

    2013-01-01

    Microprobe X-ray absorption near edge structure (μ-XANES) measurements were used to determine directly, for the first time, the oxidation state of intracellular plutonium in individual 0.1 μm2 areas within single rat pheochromocytoma cells (PC12). The living cells were incubated in vitro for 3 hours in the presence of Pu added to the media in different oxidation states (Pu(III), Pu(IV), and Pu(VI)) and in different chemical forms. Regardless of the initial oxidation state or chemical form of Pu presented to the cells, the XANES spectra of the intracellular Pu deposits was always consistent with tetravalent Pu even though the intracellular milieu is generally reducing. PMID:21755934

  17. Oxygenic Photosynthesis and the Oxidation State of Mars

    NASA Technical Reports Server (NTRS)

    Hartman, Hyman; McKay, Christopher P.

    1995-01-01

    The oxidation state of the Earth's surface is one of the most obvious indications of the effect of life on this planet. The surface of Mars is highly oxidized, as evidenced by its red color, but the connection to life is less apparent. Two possibilities can be considered. First, the oxidant may be photochemically produced in the atmosphere. In this case the fundamental source of O2 is the loss of H2 to space and the oxidant produced is H2O2. This oxidant would accumulate on the surface and thereby destroy any organic material and other reductants to some depth. Recent models suggest that diffusion limits this depth to a few meters. An alternative source of oxygen is biological oxygen production followed by sequestration of organic material in sediments - as on the Earth. In this case, the net oxidation of the surface was determined billions of years ago when Mars was a more habitable planet and oxidative conditions could persist to great depths, over 100 m. Below this must be a compensating layer of biogenic organic material. Insight into the nature of past sources of oxidation on Mars will require searching for organics in the martian subsurface and sediments.

  18. Oxygenic photosynthesis and the oxidation state of Mars.

    PubMed

    Hartman, H; McKay, C P

    1995-01-01

    The oxidation state of the Earth's surface is one of the most obvious indications of the effect of life on this planet. The surface of Mars is highly oxidized, as evidenced by its red color, but the connection to life is less apparent. Two possibilities can be considered. First, the oxidant may be photochemically produced in the atmosphere. In this case the fundamental source of O2 is the loss of H2 to space and the oxidant produced is H2O2. This oxidant would accumulate on the surface and thereby destroy any organic material and other reductants to some depth. Recent models suggest that diffusion limits this depth to a few meters. An alternative source of oxgyen is biological oxygen production followed by sequestration of organic material in sediments--as on the Earth. In this case, the net oxidation of the surface was determined billions of years ago when Mars was a more habitable planet and oxidative conditions could persist to great depths, over 100 m. Below this must be a compensating layer of biogenic organic material. Insight into the nature of past sources of oxidation on Mars will require searching for organics in the Martian subsurface and sediments.

  19. Solid state potentiometric gaseous oxide sensor

    NASA Technical Reports Server (NTRS)

    Wachsman, Eric D. (Inventor); Azad, Abdul Majeed (Inventor)

    2003-01-01

    A solid state electrochemical cell (10a) for measuring the concentration of a component of a gas mixture (12) includes first semiconductor electrode (14) and second semiconductor electrode (16) formed from first and second semiconductor materials, respectively. The materials are selected so as to undergo a change in resistivity upon contacting a gas component, such as CO or NO. An electrolyte (18) is provided in contact with the first and second semiconductor electrodes. A reference cell can be included in contact with the electrolyte. Preferably, a voltage response of the first semiconductor electrode is opposite in slope direction to that of the second semiconductor electrode to produce a voltage response equal to the sum of the absolute values of the control system uses measured pollutant concentrations to direct adjustment of engine combustion conditions.

  20. Changes in magmatic oxidation state induced by degassing

    NASA Astrophysics Data System (ADS)

    Brounce, M. N.; Stolper, E. M.; Eiler, J. M.

    2015-12-01

    Temporal variations in the oxygen fugacity (fO2) of the mantle may have been transmitted to Earth's atmosphere and oceans by volcanic degassing. However, it is unclear how redox states of volatiles relate to their source magmas because degassing and assimilation can impact fO2 before or during eruption. To explore this, we present µ-XANES measurements of the oxidation states of Fe and S and laser fluorination measurements of 18O/16O ratios in submarine glasses from two settings where degassing is recorded: 1) submarine glasses from the Reykjanes Ridge as it shoals to Iceland, including subglacial glasses from the Reykjanes Peninsula; and 2) submarine glasses from Mauna Kea recovered by the Hawaii Shield Drilling Program (HSDP). Glasses from both settings are basalts with 5.5-9.9 wt% MgO and 350-1790 ppm S. Submarine Reykjanes glasses are sulfide saturated. Subglacial Reykjanes and HSDP glasses are not sulfide saturated, and S and H2O contents are consistent with S+H2O degassing. Submarine Reykjanes glasses have 18O/16O indistinguishable from MORB and become progressively 18O-depleted as MgO decreases. Subglacial glasses have lower 18O/16O than submarine glasses at a given MgO, but both sample types project to a common 18O/16O near 10 wt% MgO, suggesting that 18O-depletion in these lavas is generated by fractional crystallization and assimilation of an 18O-depleted crustal component. The oxidation state of Fe increases only slightly as 18O/16O decrease, suggesting that the assimilant is not oxidized enough to change magmatic fO2. Fe and S do not oxidize or reduce with decreasing S or H2O, suggesting that relatively reduced magmas at depth degassed S+H2O without changing magmatic fO2, and that the fO2 of these lavas reflect the fO2of their mantle source. The oxidation states of Fe and S in HSDP glasses are broadly correlated and samples with the highest S concentrations are the most oxidized. Both Fe and S reduce with decreasing S and H2O contents. This suggests

  1. RAPID MEASUREMENTS OF NEPTUNIUM OXIDATION STATES USING CHROMATOGRAPHIC RESINS

    SciTech Connect

    Diprete, D; C Diprete, C; Mira Malek, M; Eddie Kyser, E

    2009-03-24

    The Savannah River Site's (SRS) H-Canyon facility uses ceric ammonium nitrate (CAN) to separate impure neptunium (Np) from a high sulfate feed stream. The material is processed using a two-pass solvent extraction purification which relies on CAN to oxidize neptunium to Np(VI) during the first pass prior to extraction. Spectrophotometric oxidation-state analyses normally used to validate successful oxidation to Np(VI) prior to extraction were compromised by this feed stream matrix. Therefore, a rapid chromatographic method to validate successful Np oxidation was developed using Eichrom Industries TRU and TEVA{reg_sign} resins. The method was validated and subsequently transferred to existing operations in the process analytical laboratories.

  2. GAS-PHASE FLAME SYNTHESIS AND PROPERTIES OF MAGNETIC IRON OXIDE NANOPARTICLES WITH REDUCED OXIDATION STATE

    PubMed Central

    Kumfer, Benjamin M; Shinoda, Kozo; Jeyadevan, Balachandran; Kennedy, Ian M

    2010-01-01

    Iron oxide nanoparticles of reduced oxidation state, mainly in the form of magnetite, have been synthesized utilizing a new continuous, gas-phase, nonpremixed flame method using hydrocarbon fuels. This method takes advantage of the characteristics of the inverse flame, which is produced by injection of oxidizer into a surrounding flow of fuel. Unlike traditional flame methods, this configuration allows for the iron particle formation to be maintained in a more reducing environment. The effects of flame temperature, oxygen-enrichment and fuel dilution (i.e. the stoichiometric mixture fraction), and fuel composition on particle size, Fe oxidation state, and magnetic properties are evaluated and discussed. The crystallite size, Fe(II) fraction, and saturation magnetization were all found to increase with flame temperature. Flames of methane and ethylene were used, and the use of ethylene resulted in particles containing metallic Fe(0), in addition to magnetite, while no Fe(0) was present in samples synthesized using methane. PMID:20228941

  3. Oxidation state of iron in plagioclase from lunar basalts.

    NASA Technical Reports Server (NTRS)

    Hafner, S. S.; Virgo, D.; Warburton, D.

    1971-01-01

    Determination of the oxidation state of iron in the plagioclase from the coarse-grained basalts 10044 and 12021, using Mossbauer spectroscopy. The location of iron in the crystal structure was also investigated. The spectra show that iron is in the high-spin ferrous state, and they located at least two distinct positions with different coordination numbers. Some excess resonant absorption is probably due to Fe(3+), although the Fe(3+) doublet could not be positively resolved.

  4. Oxidation state of iron in plagioclase from lunar basalts.

    NASA Technical Reports Server (NTRS)

    Hafner, S. S.; Virgo, D.; Warburton, D.

    1971-01-01

    Determination of the oxidation state of iron in the plagioclase from the coarse-grained basalts 10044 and 12021, using Mossbauer spectroscopy. The location of iron in the crystal structure was also investigated. The spectra show that iron is in the high-spin ferrous state, and they located at least two distinct positions with different coordination numbers. Some excess resonant absorption is probably due to Fe(3+), although the Fe(3+) doublet could not be positively resolved.

  5. IDENTIFYING CRITICAL CYSTEINE RESIDUES IN ARSENIC (+3 OXIDATION STATE) METHYLTRANSFERASE

    EPA Science Inventory

    Arsenic (+3 oxidation state) methyltransferase (AS3MT) catalyzes methylation of inorganic arsenic to mono, di, and trimethylated arsenicals. Orthologous AS3MT genes in genomes ranging from simple echinoderm to human predict a protein with five conserved cysteine (C) residues. In ...

  6. SESAME equation of state number 7611, beryllium oxide

    SciTech Connect

    Boettger, J.C.; Willis, J.M.

    1990-04-01

    A new equation of state (EOS) for beryllium oxide (BeO) has been constructed for the SESAME library as material number 7611. Unlike the existing EOS for BeO in the library (7610), this new EOS incorporates the effect of a structural phase transition which has been predicted by two independent theoretical calculations. 9 refs., 1 fig.

  7. IDENTIFYING CRITICAL CYSTEINE RESIDUES IN ARSENIC (+3 OXIDATION STATE) METHYLTRANSFERASE

    EPA Science Inventory

    Arsenic (+3 oxidation state) methyltransferase (AS3MT) catalyzes methylation of inorganic arsenic to mono, di, and trimethylated arsenicals. Orthologous AS3MT genes in genomes ranging from simple echinoderm to human predict a protein with five conserved cysteine (C) residues. In ...

  8. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    PubMed Central

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K.; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-01-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells. PMID:26056725

  9. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles.

    PubMed

    Szymanski, Craig J; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce(3+)/Ce(4+) ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce(3+)/Ce(4+) ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of the cells. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    SciTech Connect

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  11. Mapping the Iron Oxidation State in Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Martin, A. M.; Treimann, A. H.; Righter, K.

    2017-01-01

    Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

  12. Wannier function analysis of charge states in transition metal oxides

    NASA Astrophysics Data System (ADS)

    Quan, Yundi; Pickett, Warren

    2015-03-01

    The charge (or oxidation) state of a cation has been a crucial concept in analyzing the electronic and magnetic properties of oxides as well as interpreting ``charge ordering'' metal-insulator transitions. In recent years a few methods have been proposed for the objective identification of charge states, beyond the conventional (and occasionally subjective) use of projected densities of states, weighted band structures (fatbands), and Born effective charges. In the past two decades Wannier functions (WFs) and particularly maximally localized WFs (MLWFs), have become an indispensable tool for several different purposes in electronic structure studies. These developments have motivated us to explore the charge state picture from the perspective of MLWFs. We will illustrate with a few transition metal oxide examples such as AgO and YNiO3 that the shape, extent, and location of the charge centers of the MLWFs provide insights into how cation-oxygen hybridization determines chemical bonding, charge distribution, and ``charge ordering.'' DOE DE-FG02-04ER46111.

  13. Crystalline state and acoustic properties of zinc oxide films

    SciTech Connect

    Kal'naya, G.I.; Pryadko, I.F.; Yarovoi, Yu.A.

    1988-08-01

    We study the effect of the crystalline state of zinc oxide films, prepared by magnetron sputtering, on the efficiency of SAW transducers based on the layered system textured ZnO film-interdigital transducer (IDT)-fused quartz substrate. The crystalline perfection of the ZnO films was studied by the x-ray method using a DRON-2.0 diffractometer. The acoustic properties of the layered system fused quartz substrate-IDT-zinc oxide film were evaluated based on the squared electromechanical coupling constant K/sup 2/ for strip filters. It was found that K/sup 2/ depends on the magnitude of the mechanical stresses. When zinc oxide films are deposited by the method of magnetron deposition on fused quartz substrates, depending on the process conditions limitations can arise on the rate of deposition owing to mechanical stresses, which significantly degrade the efficiency of SAW transducers based on them, in the ZnO films.

  14. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    SciTech Connect

    Ma, Wen; Senanayake, Sanjaya D.; Herbert, F. William; Yildiz, Bilge

    2015-03-11

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr1+, Zr2+, and Zr3+ as non-equilibrium oxidation states, in addition to Zr4+ in the stoichiometric ZrO2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr0 and Zr4+ at the metal-oxide interface. As a result, the presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.

  15. Effects of oxygen content and oxide layer thickness on interface state densities for metal-oxynitride-oxide-silicon devices

    NASA Astrophysics Data System (ADS)

    Xu, Dan; Kapoor, Vik J.

    1991-08-01

    The interface state density of metal-oxynitride-oxide-silicon (MNOS) devices was investigated as a function of the tunnel oxide thickness and the amount of oxygen in the oxynitride films. Nitrous oxide gas was used to introduce oxygen into the oxynitride film during the deposition process. As 17 at. % oxygen was introduced into the oxynitride film, the lowest oxide-silicon interface state density increased from 3.0 to 3.5×1011 cm-2 eV-1 for 90-Å oxide MNOS devices, and decreased from 5.1 to 3.65×1011 cm-2 eV-1 for 20 Å oxide devices. The increase in interface state density with increasing oxygen for 90-Å oxide devices may be due to an increase in the loss of hydrogen passivation at the interfacial regions as more oxygen is introduced into the film. The higher interface state density for the 20 vs 90 Å oxide samples, for a given oxygen content of the oxynitride films, may be due to additional contributions from the trapping states near or at the oxide-oxynitride interface. However, the decrease in the interface state density for increasing oxygen concentration for 20-Å oxide MNOS devices may be due to passivation of trapping states at the oxide-oxynitride interface by oxygen. The silicon dangling bonds responsible for these trapping states may be compensated by oxygen introduced during the deposition process.

  16. Control of cerium oxidation state through metal complex secondary structures

    SciTech Connect

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

  17. Control of cerium oxidation state through metal complex secondary structures

    DOE PAGES

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; ...

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observedmore » when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

  18. Evolution of the Oxidation State of the Earth's Mantle

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  19. Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

    SciTech Connect

    Graves, Christopher R; Kiplinger, Jaqueline L

    2009-01-01

    This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

  20. Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides

    DOE PAGES

    Weimer, Matthew S.; Kim, In Soo; Guo, Peijun; ...

    2017-06-02

    We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V2O3, VO2, and V2O5 are realized via four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O3, H2O2, H2O/O2, and H2O2/H2. A clear distinction between non-oxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different non-metal precursors. This synergistic effect, providesmore » greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H2 gas. When H2 is dosed after H2O2 during growth, amorphous films of VO2 are deposited that are readily crystallized with a low temperature anneal. These VO2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO2.« less

  1. Interface state densities for metal-nitride-oxide-silicon devices

    NASA Astrophysics Data System (ADS)

    Xu, Dan; Kapoor, Vik J.

    1990-10-01

    The interface state density of metal-nitride-oxide-silicon (MNOS) devices was investigated as a function of silicon nitride (Si3N4) deposition temperature and postdeposition annealing conditions. The interface state density around the midgap of the oxide-silicon interface of the MNOS structures as a function of deposition temperature between 650 to 850 °C increased from 1.1 to 8.2×1011 cm-2 eV-1, for as-deposited silicon nitride films,; but decreased from 5.0 to 3.5×1011 cm-2 eV-1, for films annealed in nitrogen at 900 °C for 60 min; and further decreased and remained constant at 1.5×1011 cm-2 eV-1, for films which were further annealed in hydrogen at 900 °C for an additional 60 min. The interface state density increase is due to an increase in the loss of hydrogen at the interfacial region and also due to an increase in the thermal stress caused by differences in thermal expansion coefficients of silicon nitride and silicon dioxide films at higher deposition temperatures. The interface state density is subject to two opposing influences; an increase by thermal stress, and a reduction by hydrogen compensation of these states. Thus either low-temperature processing or subsequent hydrogen annealing after high processing temperatures is warranted.

  2. Oxidation states of uranium in depleted uranium particles from Kuwait.

    PubMed

    Salbu, B; Janssens, K; Lind, O C; Proost, K; Gijsels, L; Danesi, P R

    2005-01-01

    The oxidation states of uranium in depleted uranium (DU) particles were determined by synchrotron radiation based mu-XANES, applied to individual particles isolated from selected samples collected at different sites in Kuwait. Based on scanning electron microscopy with X-ray microanalysis prior to mu-XANES, DU particles ranging from submicrons to several hundred micrometers were observed. The median particle size depended on sources and sampling sites; small-sized particles (median 13 microm) were identified in swipes taken from the inside of DU penetrators holes in tanks and in sandy soil collected below DU penetrators, while larger particles (median 44 microm) were associated with fire in a DU ammunition storage facility. Furthermore, the (236)U/(235)U ratios obtained from accelerator mass spectrometry demonstrated that uranium in the DU particles originated from reprocessed fuel (about 10(-2) in DU from the ammunition facility, about 10(-3) for DU in swipes). Compared to well-defined standards, all investigated DU particles were oxidized. Uranium particles collected from swipes were characterized as UO(2), U(3)O(8) or a mixture of these oxidized forms, similar to that observed in DU affected areas in Kosovo. Uranium particles formed during fire in the DU ammunition facility were, however, present as oxidation state +5 and +6, with XANES spectra similar to solid uranyl standards. Environmental or health impact assessments for areas affected by DU munitions should therefore take into account the presence of respiratory UO(2), U(3)O(8) and even UO(3) particles, their corresponding weathering rates and the subsequent mobilisation of U from oxidized DU particles.

  3. Atomic solid state energy scale: Universality and periodic trends in oxidation state

    NASA Astrophysics Data System (ADS)

    Pelatt, Brian D.; Kokenyesi, Robert S.; Ravichandran, Ram; Pereira, Clifford B.; Wager, John F.; Keszler, Douglas A.

    2015-11-01

    The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (EG). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IP versus EG are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database are found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above -4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy -4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/-) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state.

  4. Oxidatively generated DNA/RNA damage in psychological stress states.

    PubMed

    Jørgensen, Anders

    2013-07-01

    Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8-oxodG and 8-oxoGuo, respectively). The main hypothesis was that psychological stress states are associated with increased DNA/RNA damage from oxidation. In a study of 40 schizophrenia patients and 40 healthy controls matched for age and gender, we found that 8-oxodG/8-oxoGuo excretion was increased in schizophrenia patients, providing a possible molecular link between schizophrenia and its associated signs of accelerated aging. We found no association between psychopathology, perceived stress or cortisol secretion and 8-oxodG/8-oxoGuo excretion in the patients. In the controls, there were positive correlations between 8-oxodG/8-ocoGuo excretion and 9AM plasma cortisol, but no associations to perceived stress. In an animal study of experimentally induced chronic stress performed in metabolism cages, we found no increase in urinary 8-oxodG/8-oxoGuo or cerebral (hippocampal and frontal cortex) levels of oxidatively generated nucleic acid damage. However, there was a trend towards an increased expression of genes involved in DNA repair, possibly reflecting a compensatory mechanism. In a study of 220 elderly, mostly healthy individuals from the Italian InChianti cohort, we found a significant association between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between

  5. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    NASA Astrophysics Data System (ADS)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  6. Achieving unusual oxidation state of matter under high pressure

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoli; Lin, Haiqing; Ma, Yanming; Miao, Maosheng

    2013-03-01

    Pressure has many effects to matter including the reduction of the volume, the increase of the coordination number and the broadening of the band-widths. In the past, most of the high-pressure studies focused on structural and electronic state phase transitions. Using first principles calculations and a bias-free structural search method, we will demonstrate that high pressure can lead to high oxidation state of elements that can never be achieved under ambient condition, making high pressure technique a nice tool to explore many traditional topics in solid state and molecular chemistry. As an example, we will show that Hg can transfer the electrons in its outmost d shell to F atoms and form HgF4 molecular crystals under pressure, thereby acting as a true transition metal. Group IIB elements, including Zn, Cd, and Hg are usually defined as post-transition metals because they are commonly oxidized only to the +2 state. Their d shells are completely filled and do not participate in the formation of chemical bonds. Although the synthesis of HgF4 molecules in gas phase was reported before, the molecules show strong instabilities and dissociate. Therefore, the transition metal propensity of Hg remains an open question.

  7. The oxidation state of sulfur in apatite: A new oxybarometer?

    NASA Astrophysics Data System (ADS)

    Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

    2016-12-01

    Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

  8. Arsenic removal from water using flame-synthesized iron oxide nanoparticles with variable oxidation states

    PubMed Central

    Abid, Aamir D.; Kanematsu, Masakazu; Young, Thomas M.; Kennedy, Ian M.

    2013-01-01

    We utilized gas-phase diffusion flame synthesis, which has potential for large-scale production of metal oxide nanoparticles, to produce iron oxide nanoparticles (IONPs) with variable oxidation states. The efficacy of these materials in removal of arsenate (As(V) ) from water was assessed. Two different flame configurations, a diffusion flame (DF) and an inverse diffusion flame (IDF), were employed to synthesize six different IONPs by controlling flame conditions. The IONPs produced in the IDF configuration (IDF-IONPs) had smaller particle diameters (4.8 – 8.2 nm) and larger surface areas (141–213 m2/g) than the IONPs produced in the DF configuration (29 nm, 36 m2/g), which resulted in their higher adsorption capacities. As(V) adsorption capacities of the IDF-IONPs increased when the IONPs were synthesized in more oxidizing conditions. The fully oxidized IDF-IONPs, maghemite (γ-Fe2O3), showed the highest As(V) adsorption capacity, comparable to that of magnetite nanocrystals synthesized by thermal decomposition of iron pentacarbonyl and equivalent to three to four times higher capacity than that of a commonly used goethite-based adsorbent. All IONPs were magnetically responsive, which is of great importance for solid−liquid separation. This study demonstrates that the IONPs synthesized in gas-phase flame, particularly IDF-IONPs, are excellent adsorbents because of their high As(V) sorption capacity, potential for large-scale production, and useful magnetic property. PMID:23645964

  9. Evaluating tantalum oxide stoichiometry and oxidation states for optimal memristor performance

    SciTech Connect

    Brumbach, Michael T. Mickel, Patrick R.; Lohn, Andrew J.; Mirabal, Alex J.; Kalan, Michael A.; Stevens, James E.; Marinella, Matthew J.

    2014-09-01

    Tantalum oxide has shown promising electrical switching characteristics for memristor devices. Consequently, a number of reports have investigated the electrical behavior of TaO{sub x} thin films. Some effort has been made to characterize the composition of the TaO{sub x} films and it is known that there must be an optimal stoichiometry of TaO{sub x} where forming and switching behavior are optimized. However, many previous reports lack details on the methodology used for identifying the chemistry of the films. X-ray photoelectron spectroscopy has been the most commonly used technique; however, peak fitting routines vary widely among reports and a native surface oxide of Ta{sub 2}O{sub 5} often confounds the analysis. In this report a series of large area TaO{sub x} films were deposited via sputtering with controlled O{sub 2} partial pressures in the sputtering gas, resulting in tunable oxide compositions. Spectra from numerous samples from each wafer spanning a range of oxide stoichiometries were used to develop a highly constrained peak fitting routine. This procedure allowed for the composition of the TaO{sub x} films to be identified with greater detail than elemental ratios alone. Additionally, the peak fitting routine was used to evaluate uniformity of deposition across individual wafers. The appearance of a greater contribution of Ta{sup 4+} oxidation states in the oxygen starved films are believed to relate to films with optimal forming characteristics.

  10. Arsenic removal from water using flame-synthesized iron oxide nanoparticles with variable oxidation states.

    PubMed

    Abid, Aamir D; Kanematsu, Masakazu; Young, Thomas M; Kennedy, Ian M

    2013-02-01

    We utilized gas-phase diffusion flame synthesis, which has potential for large-scale production of metal oxide nanoparticles, to produce iron oxide nanoparticles (IONPs) with variable oxidation states. The efficacy of these materials in removal of arsenate (As(V) ) from water was assessed. Two different flame configurations, a diffusion flame (DF) and an inverse diffusion flame (IDF), were employed to synthesize six different IONPs by controlling flame conditions. The IONPs produced in the IDF configuration (IDF-IONPs) had smaller particle diameters (4.8 - 8.2 nm) and larger surface areas (141-213 m(2)/g) than the IONPs produced in the DF configuration (29 nm, 36 m(2)/g), which resulted in their higher adsorption capacities. As(V) adsorption capacities of the IDF-IONPs increased when the IONPs were synthesized in more oxidizing conditions. The fully oxidized IDF-IONPs, maghemite (γ-Fe2O3), showed the highest As(V) adsorption capacity, comparable to that of magnetite nanocrystals synthesized by thermal decomposition of iron pentacarbonyl and equivalent to three to four times higher capacity than that of a commonly used goethite-based adsorbent. All IONPs were magnetically responsive, which is of great importance for solid-liquid separation. This study demonstrates that the IONPs synthesized in gas-phase flame, particularly IDF-IONPs, are excellent adsorbents because of their high As(V) sorption capacity, potential for large-scale production, and useful magnetic property.

  11. Chelation and stabilization of berkelium in oxidation state +IV

    NASA Astrophysics Data System (ADS)

    Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

    2017-09-01

    Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

  12. Americium separation from nuclear fuel dissolution using higher oxidation states.

    SciTech Connect

    Bruce J. Mincher

    2009-09-01

    Much of the complexity in current AFCI proposals is driven by the need to separate the minor actinides from the lanthanides. Partitioning and recycling Am, but not Cm, would allow for significant simplification because Am has redox chemistry that may be exploited while Cm does not. Here, we have explored methods based on higher oxidation states of Am (AmV and AmVI) to partition Am from the lanthanides. In a separate but related approach we have also initiated an investigation of the utility of TRUEX Am extraction from thiocyanate solution. The stripping of loaded TRUEX by Am oxidation or SCN- has not yet proved successful; however, the partitioning of inextractable AmV by TRUEX shows promise.

  13. Atomic solid state energy scale: Universality and periodic trends in oxidation state

    SciTech Connect

    Pelatt, Brian D.; Kokenyesi, Robert S.; Ravichandran, Ram; Pereira, Clifford B.; Wager, John F.; Keszler, Douglas A.

    2015-11-15

    The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (E{sub G}). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IP versus E{sub G} are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database are found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above −4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy −4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/−) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state. - Highlights: • Atomic solid-state energies are estimated for 64 elements from experimental data. • The relationship between atomic SSEs and oxidation state is assessed. • Cations are positioned above and absolute energy of −4.5 eV and anions below.

  14. Effect of microorganisms on the plutonium oxidation states.

    PubMed

    Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

    2012-03-01

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to (239)Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state.

  15. Oxidation states of uranium in DU particles from Kosovo.

    PubMed

    Salbu, B; Janssens, K; Lind, O C; Proost, K; Danesi, P R

    2003-01-01

    The oxidation states of uranium contained in depleted uranium (DU) particles were determined by synchrotron radiation based micro-XANES, applied to individual particles in soil samples collected at Ceja Mountain, Kosovo. Based on scanning electron microscopy (SEM) with XRMA prior to micro-XANES, DU particles ranging from submicrons to about 30 microm (average size: 2 microm or less) were identified. Compared to well-defined standards, all investigated DU particles were oxidized. About 50% of the DU particles were characterized as UO2, the remaining DU particles present were U3O8 or a mixture of oxidized forms (ca. 2/3 UO2, 1/3 U3O8). Since the particle weathering rate is expected to be higher for U3O8 than for UO2, the presence of respiratory U3O8 and UO2 particles, their corresponding weathering rates and subsequent remobilisation of U from DU particles should be included in the environmental or health impact assessments.

  16. Persistence of oxidation state III of gold in thione coordination

    NASA Astrophysics Data System (ADS)

    Jääskeläinen, Sirpa; Koskinen, Laura; Kultamaa, Matti; Haukka, Matti; Hirva, Pipsa

    2017-05-01

    Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra- and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method.

  17. How were Oxidation State Heterogeneities Formed in the Martian Interior?

    NASA Astrophysics Data System (ADS)

    Schmidt, M. E.; Schrader, C. M.; McCoy, T. J.

    2011-12-01

    The primary oxygen fugacity of basaltic melts reflects the mantle source oxidation state, dictates the crystallizing assemblage, and determines how the magma will evolve. On Earth, variabile fO2 among basaltic melts is linked to mass exchange between the surface and the interior by tectonic processes (subduction). Martian basalts represent samples of the planet's interior and we currently have two data sets with which to work: the Amazonian age shergottitic meteorites and early Hesperian age basaltic rocks examined in situ by the Spirit rover in Gusev Crater. The Gusev basalts are diverse and range from the K-poor Adirondack class (0.02 wt% K2O) to K-rich Backstay class (up to 1.2 wt% K2O). By combining the Fe3+/FeT of igneous minerals (olivine, pyroxene, and magnetite) determined by Mössbauer spectrometer, we estimated primary fO2 for the Gusev basalts to be -3.6 to 0.5 ΔQFM (quartz-fayalite-magnetite buffer). General similarity between the fO2 estimated for the Gusev basalts and ranges in fO2 for the shergottitic meteorites (-3.8 to 0.2 ΔQFM; Herd, 2003; Goodrich et al., 2003) suggests that the overall range of fO2 for the Martian igneous rocks and mantle is relatively restricted. Also like the shergottites (Herd et al., 2003), estimated fO2 of three Gusev classes (Adirondack, Barnhill and Irvine) correlates with a proxy for LREE enrichment (K/Ti). This suggests mixing between melts or fluids derived from reservoirs with contrasting fO2, such as reduced, LREE-depleted mantle and more oxidized, LREE-enriched crust. One exception to this trend is the high-K Backstay class, which has low fO2 like the low-K Adirondack class (-3.6 ΔQFM). Backstay and Adirondack are probably melts of similarly reduced mantle and contrasting alkali concentrations may reflect partial melting processes. If the high K2O (and K/Ti) of Backstay was obtained through partial melting of primary (i.e., never melted) mantle, then its relatively low fO2 may imply that the development of the

  18. Contraction, cation oxidation state and size effects in cerium oxide nanoparticles.

    PubMed

    Pelli Cresi, Jacopo Stefano; Spadaro, Maria Chiara; D'Addato, Sergio; Valeri, Sergio; Amidani, Lucia; Boscherini, Federico; Bertoni, Giovanni; Deiana, Davide; Luches, Paola

    2017-10-10

    An accurate description of the structural and chemical modifications of cerium oxide nanoparticles is mandatory for understanding their functionality in the applications. In this work we investigate the relation between local atomic structure, oxidation state, defectivity and size in cerium oxide nanoparticles with variable diameter below 10 nm, using X-ray absorption fine structure analysis in the near and extended energy range. The nanoparticles are prepared by physical methods under controlled conditions by physical methods and analyzed in morphology and crystalline quality by high resolution transmission electron microscopy. We resolve here an important question on the local structure of cerium oxide nanoparticles: we demonstrate a progressive contraction in the Ce-O interatomic distance with decreasing nanoparticle diameter and we relate the observed effect to the reduced dimensionality. The contraction is not significantly modified by inducing a 4-6% higher Ce3+ concentration through thermal annealing in high vacuum. The consequences of the observed average cation-anion distance contraction on the properties of the nanoparticles are discussed. © 2017 IOP Publishing Ltd.

  19. Proteomic indicators of oxidation and hydration state in colorectal cancer.

    PubMed

    Dick, Jeffrey M

    2016-01-01

    New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (Z C) can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ([Formula: see text]) is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean Z C or [Formula: see text] of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower Z C for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

  20. Andreev bound state at a strongly correlated oxide interface

    NASA Astrophysics Data System (ADS)

    Cheng, Guanglei; Tomczyk, Michelle; Tacla, Alexandre; Daley, Andrew; Lu, Shicheng; Veazey, Josh; Huang, Mengchen; Irvin, Patrick; Ryu, Sangwoo; Lee, Hyungwoo; Eom, Chang-Beom; Pekker, David; Levy, Jeremy

    Strongly correlated electrons at oxide interfaces give rise to a set of novel physics phenomena including superconductivity and magnetism. At the LaAlO3/SrTiO3 (LAO/STO) interface, signatures of strong electron pairing persist even for conditions where superconductivity is suppressed. Meanwhile, an Andreev bound state (ABS) is a single quasiparticle excitation that mediates pair transport in confined superconductor-normal systems. Here we report a transition from pair resonant transport to ABS in sketched single electron transistors at the LAO/STO interface. This transition is consistent with a change of electron-electron interaction from attractive to repulsive, occurring at or near the Lifshitz transition. Such new electronically tunable electron-electron interaction may be useful for quantum simulation and engineering of novel quantum states in oxide materials. We gratefully acknowledge support from AFOSR FA9550-10-1-0524 (JL, CBE), AFOSR FA9550-12-1-0057 (JL, CBE, AD), NSF DMR-1104191 (JL), ONR N00014-15-1-2847 (JL).

  1. Composition and oxidation state of sulfur in atmospheric particulate matter

    NASA Astrophysics Data System (ADS)

    Longo, Amelia F.; Vine, David J.; King, Laura E.; Oakes, Michelle; Weber, Rodney J.; Huey, Lewis Gregory; Russell, Armistead G.; Ingall, Ellery D.

    2016-10-01

    The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS) and X-ray fluorescence (XRF) microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm) analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  2. Water oxidation at hematite photoelectrodes: the role of surface states.

    PubMed

    Klahr, Benjamin; Gimenez, Sixto; Fabregat-Santiago, Francisco; Hamann, Thomas; Bisquert, Juan

    2012-03-07

    Hematite (α-Fe(2)O(3)) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical-chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement. © 2012 American Chemical Society

  3. Oxidation states of Fe and Ti in blue sapphire

    NASA Astrophysics Data System (ADS)

    Wongrawang, P.; Monarumit, N.; Thammajak, N.; Wathanakul, P.; Wongkokua, W.

    2016-02-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe2+ and Ti4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe3+ state; and Ti at 4984 eV, corresponding to Ti4+. From these results, we propose Fe3+-Ti4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV-vis absorption spectra, to describe the cause of the color of blue sapphire.

  4. A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis

    DOE PAGES

    Michaelos, Thoe K.; Shopov, Dimitar Y.; Sinha, Shashi Bhushan; ...

    2017-03-08

    Here, water-oxidation catalysis is a critical bottleneck in the direct generation of solar fuels by artificial photosynthesis. Catalytic oxidation of difficult substrates such as water requires harsh conditions, so that the ligand must be designed both to stabilize high oxidation states of the metal center and to strenuously resist ligand degradation. Typical ligand choices either lack sufficient electron donor power or fail to stand up to the oxidizing conditions. This research on Ir-based water-oxidation catalysts (WOCs) has led us to identify a ligand, 2-(2'-pyridyl)-2-propanoate or “pyalk” that fulfills these requirements.

  5. Spin-Orbital Entangled States in Transition Metal Oxides

    NASA Astrophysics Data System (ADS)

    Oleś, Andrzej M.

    The phenomenon of spin-orbital entanglement which occurs in superexchange models for transition metal oxides is introduced and explained. We present its consequences in the RVO_3 Mott insulators, with R=La,Pr,\\cdots ,Yb,Lu, and show that entanglement occurs here in excited states of the spin-orbital d^2 model and determines: (i) the temperature dependence of low-energy optical spectral weight, (ii) the phase diagram of the RVO_3 perovskites, and (iii) the dimerization observed in the magnon excitations in YVO_3. Entangled ground states occur in two other model systems: (i) the bilayer d^9 (Kugel-Khomskii) model, and (ii) the d^1 model on the triangular frustrated lattice. In such cases even the predictions concerning the magnetic exchange constants based on the mean field decoupling of spin and orbital operators are incorrect. On the example of a single hole doped to a Mott insulator with coexisting antiferromagnetic and alternating t_{2g} orbital order we show that transport is hindered by spin-orbital excitations. It is suggested that spin-orbital entanglement in Mott insulators might be controlled by doping, leading to orbital disordered states with possible new opportunities for thermoelectric applications.

  6. Oxidation state determination of uranium in various uranium oxides: Photoacoustic spectroscopy complimented by photoluminescence studies

    NASA Astrophysics Data System (ADS)

    Gupta, Santosh K.; Dhobale, A. R.; Kumar, M.; Godbole, S. V.; Natarajan, V.

    2015-03-01

    Photoacoustic spectroscopy (PAS) has been utilized for the determination of U(IV). Initial experiments were carried out for determination of U(IV) in uranium tetra fluoride, and were further extended to the determination of U(IV) in uranium oxide samples having various O/M ratios like UO2.00, UO2.17, U3O8, and U3O7. All these oxides, since dark gray/black in color, were having featureless spectra in the visible region, hence solid state reaction of uranium oxide with ammonium bi-fluoride was utilized for the formation of U(IV) and U(VI) oxyfluorides, having narrow well resolved spectra, prior to estimation by Photoacoustic spectroscopy technique. The strong absorption for U(IV) complex at 630 nm was monitored using a He-Ne laser resulting in good sensitivity for determination of U(IV). It was observed that fluorinated uranium dioxide (UO2) is having spectra similar to U(IV); fluorinated uranium trioxide (UO3) is having spectra of uranyl only whereas Triuranium octoxide (U3O8) spectra consist of both U(IV) and uranyl component. This was further supported by photoluminescence studies.

  7. Molybdenum Catalyzed Ammonia Borane Dehydrogenation: Oxidation State Specific Mechanisms

    PubMed Central

    2015-01-01

    Though numerous catalysts for the dehydrogenation of ammonia borane (AB) are known, those that release >2 equiv of H2 are uncommon. Herein, we report the synthesis of Mo complexes supported by a para-terphenyl diphosphine ligand, 1, displaying metal–arene interactions. Both a Mo0 N2 complex, 5, and a MoII bis(acetonitrile) complex, 4, exhibit high levels of AB dehydrogenation, releasing over 2.0 equiv of H2. The reaction rate, extent of dehydrogenation, and reaction mechanism vary as a function of the precatalyst oxidation state. Several Mo hydrides (MoII(H)2, [MoII(H)]+, and [MoIV(H)3]+) relevant to AB chemistry were characterized. PMID:25034459

  8. METHOD OF MAINTAINING PLUTONIUM IN A HIGHER STATE OF OXIDATION DURING PROCESSING

    DOEpatents

    Thompson, S.G.; Miller, D.R.

    1959-06-30

    This patent deals with the oxidation of tetravalent plutonium contained in an aqueous acid solution together with fission products to the hexavalent state, prior to selective fission product precipitation, by adding to the solution bismuthate or ceric ions as the oxidant and a water-soluble dichromate as a holding oxidant. Both oxidant and holding oxidant are preferably added in greater than stoichiometric quantities with regard to the plutonium present.

  9. Proteomic indicators of oxidation and hydration state in colorectal cancer

    PubMed Central

    2016-01-01

    New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC) can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue (\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$\\end{document}n¯H2O) is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$\\end{document}n¯H2O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic

  10. Catalytic partial oxidation of methane to synthesis gas over a ruthenium catalyst: the role of the oxidation state.

    PubMed

    Rabe, Stefan; Nachtegaal, Maarten; Vogel, Frédéric

    2007-03-28

    The catalytic partial oxidation of methane to synthesis gas over ruthenium catalysts was investigated by thermogravimetry coupled with infrared spectroscopy (TGA-FTIR) and in situ X-ray absorption spectroscopy (XAS). It was found that the oxidation state of the catalyst influences the product formation. On oxidized ruthenium sites, carbon dioxide was formed. The reduced catalyst yielded carbon monoxide as a product. The influence of the temperature was also investigated. At temperatures below the ignition point of the reaction, the catalyst was in an oxidized state. At temperatures above the ignition point, the catalyst was reduced. This was also confirmed by the in situ XAS spectroscopy. The results indicate that both a direct reaction mechanism as well as a combustion-reforming mechanism can occur. The importance of knowing the oxidation state of the surface is discussed and a method to determine it under reaction conditions is presented.

  11. Redox state of plutonium in irradiated mixed oxide fuels

    NASA Astrophysics Data System (ADS)

    Degueldre, C.; Pin, S.; Poonoosamy, J.; Kulik, D. A.

    2014-03-01

    Nowadays, MOX fuels are used in about 20 nuclear power plants around the world. After irradiation, plutonium co-exists with uranium oxide. Due to the redox sensitive nature of UO2 other plutonium oxides than PuO2 potentially present in the fuel may interact with the matrix. The aim of this study is to determine which plutonium species are present in heterogeneous and homogeneous MOX. The results provided by X-ray Absorption Near Edge Spectroscopy (XANES) for non-irradiated as well as irradiated (center and periphery) homogeneous MOX fuel were published earlier and are completed by Extended X-ray Fine Structure (EXAFS) analysis in this work. The EXAFS signals have been extracted using the ATHENA code and the analyses were carried using EXCURE98 as performed earlier for an analogous element. EXAFS shows that plutonium redox state remains tetravalent in the solid solution and that the minor fraction of trivalent Pu must be below 10%. Independently, the study of homogeneous MOX was also approached by thermodynamics of solid solution of (U,Pu)O2. Such solid solutions were modeled using the Gibbs Energy Minimisation (GEM)-Selektor code (developed at LES, NES, PSI) supported by the literature data on such solid solutions. A comparative study was performed showing which plutonium oxides in their respective mole fractions are more likely to occur in (U,Pu)O2. In the modeling, these oxides were set as ideal and non-ideal solid solutions, as well as separate pure phases. Pu exists mainly as PuO2 in the case of separate phases, but can exist under its reduced forms, PuO1.61 and PuO1.5 in minor fraction i.e. ~15% in ideal solid solution (unlikely) and ~10% in non-ideal solid solution (likely) and at temperature around 1300 K. This combined thermodynamic and EXAFS studies confirm independently the results obtained so far by Pu XANES for the same MOX samples.

  12. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    USGS Publications Warehouse

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  13. Iron Partitioning and Oxidation State in Earth's Lower Mantle

    NASA Astrophysics Data System (ADS)

    Piet, H.; Badro, J.; Nabiei, F.; Dennenwaldt, T.; Shim, S. H. D.; Cantoni, M.; Hébert, C.; Gillet, P.

    2015-12-01

    Valence state and concentrations of iron in lower mantle phases have strong effects on their chemical and physical properties. Experimental studies have reported stark differences in iron partitioning between bridgmanite (Brg) and ferropericlase (Fp) for San Carlos olivine [1] and pyrolite [2] systems. We recently performed experiments at lower mantle conditions for an Al-rich olivine system [3] and observed an iron enrichment of the silicate phase very similar to that in pyrolite. Mössbauer studies [4] have shown that in the presence of aluminum non negligible amounts of Fe3+ could be incorporated in bridgmanite explaining the observed iron enrichment. Non negligible amounts of Fe3+ in the lower mantle could influence transport properties of the phases [5]. The evaluation of ferrous and ferric iron concentrations in lower mantle mineral assemblages is then key to a thorough understanding of geophysical observations and associated mantle dynamics. We used electron energy loss spectroscopy technique to quantify the proportions of Fe2+ and Fe3+ iron in Brg and Fp phases previously synthesized from Al-rich olivine composition [3]. The oxidation state of iron in the lower mantle will be discussed as well as ensuing implications on transport properties for relevant lower mantle compositions. References [1] Sakai et al., 2009 [2] Prescher et al., 2014 [3] Piet et al., submitted [4] McCammon et al., 1996 [5] Xu et al., 1998

  14. The Concept of Oxidation States in Metal Complexes

    ERIC Educational Resources Information Center

    Steinborn, Dirk

    2004-01-01

    The concepts of oxidation numbers when applied means electrons that are shared between atoms in molecules are assigned to a specific atom. Oxidation numbers are assigned from the Lewis structure of a molecule, with knowledge of the electronegativities of elements.

  15. The Concept of Oxidation States in Metal Complexes

    ERIC Educational Resources Information Center

    Steinborn, Dirk

    2004-01-01

    The concepts of oxidation numbers when applied means electrons that are shared between atoms in molecules are assigned to a specific atom. Oxidation numbers are assigned from the Lewis structure of a molecule, with knowledge of the electronegativities of elements.

  16. Forest soil carbon oxidation state and oxidative ratio responses to elevated CO2

    DOE PAGES

    Hockaday, William C.; Gallagher, Morgan E.; Masiello, Caroline A.; ...

    2015-09-21

    The oxidative ratio (OR) of the biosphere is the stoichiometric ratio (O2/CO2) of gas exchange by photosynthesis and respiration a key parameter in budgeting calculations of the land and ocean carbon sinks. Carbon cycle-climate feedbacks could alter the OR of the biosphere by affecting the quantity and quality of organic matter in plant biomass and soil carbon pools. Here, this study considers the effect of elevated atmospheric carbon dioxide concentrations ([CO2]) on the OR of a hardwood forest after nine growing seasons of Free-Air CO2 Enrichment. We measured changes in the carbon oxidation state (Cox) of biomass and soil carbonmore » pools as a proxy for the ecosystem OR. The OR of net primary production, 1.039, was not affected by elevated [CO2]. However, the Cox of the soil carbon pool was 40% higher at elevated [CO2], and the estimated OR values for soil respiration increased from 1.006 at ambient [CO2] to 1.054 at elevated [CO2]. A biochemical inventory of the soil organic matter ascribed the increases in Cox and OR to faster turnover of reduced substrates, lignin and lipids, at elevated [CO2]. This implicates the heterotrophic soil community response to elevated [CO2] as a driver of disequilibrium in the ecosystem OR. The oxidation of soil carbon pool constitutes an unexpected terrestrial O2 sink. Carbon budgets constructed under the assumption of OR equilibrium would equate such a terrestrial O2 sink to CO2 uptake by the ocean. We find that the potential for climate-driven disequilibriua in the cycling of O2 and CO2 warrants further investigation.« less

  17. Forest soil carbon oxidation state and oxidative ratio responses to elevated CO2

    NASA Astrophysics Data System (ADS)

    Hockaday, William C.; Gallagher, Morgan E.; Masiello, Caroline A.; Baldock, Jeffrey A.; Iversen, Colleen M.; Norby, Richard J.

    2015-09-01

    The oxidative ratio (OR) of the biosphere is the stoichiometric ratio (O2/CO2) of gas exchange by photosynthesis and respiration—a key parameter in budgeting calculations of the land and ocean carbon sinks. Carbon cycle-climate feedbacks could alter the OR of the biosphere by affecting the quantity and quality of organic matter in plant biomass and soil carbon pools. This study considers the effect of elevated atmospheric carbon dioxide concentrations ([CO2]) on the OR of a hardwood forest after nine growing seasons of Free-Air CO2 Enrichment. We measured changes in the carbon oxidation state (Cox) of biomass and soil carbon pools as a proxy for the ecosystem OR. The OR of net primary production, 1.039, was not affected by elevated [CO2]. However, the Cox of the soil carbon pool was 40% higher at elevated [CO2], and the estimated OR values for soil respiration increased from 1.006 at ambient [CO2] to 1.054 at elevated [CO2]. A biochemical inventory of the soil organic matter ascribed the increases in Cox and OR to faster turnover of reduced substrates, lignin and lipids, at elevated [CO2]. This implicates the heterotrophic soil community response to elevated [CO2] as a driver of disequilibrium in the ecosystem OR. The oxidation of soil carbon pool constitutes an unexpected terrestrial O2 sink. Carbon budgets constructed under the assumption of OR equilibrium would equate such a terrestrial O2 sink to CO2 uptake by the ocean. The potential for climate-driven disequilibriua in the cycling of O2 and CO2 warrants further investigation.

  18. Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

    NASA Technical Reports Server (NTRS)

    Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

    2007-01-01

    Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

  19. Accuracy and Precision in Measurements of Biomass Oxidative Ratio and Carbon Oxidation State

    NASA Astrophysics Data System (ADS)

    Gallagher, M. E.; Masiello, C. A.; Randerson, J. T.; Chadwick, O. A.; Robertson, G. P.

    2007-12-01

    Ecosystem oxidative ratio (OR) is a critical parameter in the apportionment of anthropogenic CO2 between the terrestrial biosphere and ocean carbon reservoirs. OR is the ratio of O2 to CO2 in gas exchange fluxes between the terrestrial biosphere and atmosphere. Ecosystem OR is linearly related to biomass carbon oxidation state (Cox), a fundamental property of the earth system describing the bonding environment of carbon in molecules. Cox can range from -4 to +4 (CH4 to CO2). Variations in both Cox and OR are driven by photosynthesis, respiration, and decomposition. We are developing several techniques to accurately measure variations in ecosystem Cox and OR; these include elemental analysis, bomb calorimetry, and 13C nuclear magnetic resonance spectroscopy. A previous study, comparing the accuracy and precision of elemental analysis versus bomb calorimetry for pure chemicals, showed that elemental analysis-based measurements are more accurate, while calorimetry- based measurements yield more precise data. However, the limited biochemical range of natural samples makes it possible that calorimetry may ultimately prove most accurate, as well as most cost-effective. Here we examine more closely the accuracy of Cox and OR values generated by calorimetry on a large set of natural biomass samples collected from the Kellogg Biological Station-Long Term Ecological Research (KBS-LTER) site in Michigan.

  20. Discovery of New Luminescent Oxides by Combinatorial Solid State Chemistry

    NASA Astrophysics Data System (ADS)

    McFarland, Eric

    1998-03-01

    Combinatorial synthesis and screening of extraordinarily large numbers of different organic compounds has been widely applied in the pharmaceutical industry for drug discovery. Combinatorial chemistry is particularly well suited for ternary and higher order inorganic materials discovery where efforts to predict basic properties have been unsuccessful. New compounds for ultraviolet excited phosphors are important for flat panel displays and for lighting applications. Utilizing automated thin film synthesis and parallel screening techniques, combinatorial libraries with up to 25,000 compositions have been investigated for photoluminescence. Screening of the libraries identified Y_0.845Al_0.070La_0.060Eu_0.025VO4 as a new red phosphor which, when synthesized in bulk, has an intrinsic quantum efficiency under 254 nm excitation of 0.83 ± 0.06 (A COMBINATORIAL APPROACH TO THE DISCOVERY AND OPTIMIZATION OF LUMINESCENT MATERIALS, Earl Danielson, Josh Golden, Eric W. McFarland, Casper M. Reaves, W. Henry Weinberg, and Xin Di Wu, Nature), Vol. 389, (1997). In addition, the first one-dimensional (1-D) luminescent inorganic oxide, Sr_2CeO_4, has been discovered using combinatorial solid state chemistry. The elemental ratios from a diverse discovery library led to the synthesis of a bulk sample of single phase Sr_2CeO4 that was structurally characterized by Rietveld refinement of the powder X-ray data to possess a new structure type for a luminescent oxide built up from 1-D chains of edge sharing CeO6 octahedra, with two terminal O atoms per Ce center isolated from one another by Sr^2+ cations. The cerate shows broad excitation and emission maxima at 310 and 485 nm. The lifetime of the excited state, epr data, crystallographic structure, and magnetic susceptibility all suggest that the mechanism of luminescence originates from a ligand to metal Ce^4+ charge transfer. We speculate that the relatively electron rich terminal O atoms bonded to Ce^4+ in Sr_2CeO_4, which give rise

  1. Quantum confinement-induced tunable exciton states in graphene oxide

    PubMed Central

    Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M.; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

    2013-01-01

    Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology. PMID:23872608

  2. Valence-state reflectometry of complex oxide heterointerfaces

    DOE PAGES

    Hamann-Borrero, Jorge E.; Macke, Sebastian; Choi, Woo Seok; ...

    2016-09-16

    Emergent phenomena in transition-metal-oxide heterostructures such as interface superconductivity and magnetism have been attributed to electronic reconstruction, which, however, is difficult to detect and characterise. Here we overcome the associated difficulties to simultaneously address the electronic degrees of freedom and distinguish interface from bulk effects by implementing a novel approach to resonant X-ray reflectivity (RXR). Our RXR study of the chemical and valance profiles along the polar (001) direction of a LaCoO3 film on NdGaO3 reveals a pronounced valence-state reconstruction from Co3+ in the bulk to Co2+ at the surface, with an areal density close to 0.5 Co2+ ions permore » unit cell. An identical film capped with polar (001) LaAlO3 maintains the Co3+ valence over its entire thickness. As a result, we interpret this as evidence for electronic reconstruction in the uncapped film, involving the transfer of 0.5e– per unit cell to the subsurface CoO2 layer at its LaO-terminated polar surface.« less

  3. Stabilization of actinides and lanthanides in unusually high oxidation states

    SciTech Connect

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO/sub 3/ or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF/sub 5//HF solution or Pu(VII) in Li/sub 5/PuO/sub 6/). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs.

  4. Valence-state reflectometry of complex oxide heterointerfaces

    SciTech Connect

    Hamann-Borrero, Jorge E.; Macke, Sebastian; Choi, Woo Seok; Sutarto, Ronny; He, Feizhou; Radi, Abdullah; Elfimov, Ilya; Green, Robert J.; Haverkort, Maurits W.; Zabolotnyy, Volodymyr B.; Lee, Ho Nyung; Sawatzky, George A.; Hinkov, Vladimir

    2016-09-16

    Emergent phenomena in transition-metal-oxide heterostructures such as interface superconductivity and magnetism have been attributed to electronic reconstruction, which, however, is difficult to detect and characterise. Here we overcome the associated difficulties to simultaneously address the electronic degrees of freedom and distinguish interface from bulk effects by implementing a novel approach to resonant X-ray reflectivity (RXR). Our RXR study of the chemical and valance profiles along the polar (001) direction of a LaCoO3 film on NdGaO3 reveals a pronounced valence-state reconstruction from Co3+ in the bulk to Co2+ at the surface, with an areal density close to 0.5 Co2+ ions per unit cell. An identical film capped with polar (001) LaAlO3 maintains the Co3+ valence over its entire thickness. As a result, we interpret this as evidence for electronic reconstruction in the uncapped film, involving the transfer of 0.5e per unit cell to the subsurface CoO2 layer at its LaO-terminated polar surface.

  5. Effects of iron oxidation state on viscosity, lunar composition 15555

    NASA Technical Reports Server (NTRS)

    Cukierman, M.; Uhlmann, D. R.

    1974-01-01

    The viscous flow behavior of a 9.6-kg lunar rock containing 22.5 wt.% FeO was studied in the temperature ranges from 620 to 700 C and from 1215 to 1400 C. The material was synthesized under mildy reducing conditions to simulate the Fe(2+)/total Fe ratio of the lunar environment. The effect of iron oxidation state on flow behavior in the high viscosity region is studied for specimens of the 15555 composition with Fe(2+) concentration ratios of 0.94, 0.76, and 0.20. A change in ratio from 0.94 to 0.76 had no observable effect on viscosity, whereas a change from 0.76 to 0.20 was accompanied by a drastic increase in viscosity (some three orders of magnitude) at a given temperature, but without changing the form of the variation of viscosity with temperature. The flow behavior is analyzed as a function of the structural features of the glasses.

  6. [Oxidative modification of proteins, its role in pathologic states].

    PubMed

    Dubinina, E E; Pustygina, A V

    2008-01-01

    Generalized literature data covering principal mechanisms of oxidative modification of protein and its role in various pathologies are presented in the paper. It is emphasized that due to peculiarities of protein structure organization the process of oxidative modification is of complicated and specific character, which is determined by amino acid composition of the protein. Oxidative modification of protein can be connected with impairment of not only a polypeptide chain itself, but also particular amino acid residues with formation of several types of radicals. Mechanisms of formation of long-life hydroperoxides and their role in oxidative stress are discussed. The role of electron-transfer (migratory) reactions in formation of radical centers on a protein molecule surface is elucidated. Oxidative modification of protein is considered as a process of regulation of their synthesis and degradation connected with activation of multicatalytic proteases. Oxidative destruction of protein is one of early and most reliable markers of tissue lesion in reactive species pathology.

  7. The oxidation state of sulfur in magmatic fluids

    NASA Astrophysics Data System (ADS)

    Binder, Bernd; Keppler, Hans

    2011-01-01

    Sulfur compounds in volcanic gases are responsible for the global cooling after explosive eruptions and they probably controlled the early evolution of the Earth's atmosphere. We have therefore studied the oxidation state of sulfur in aqueous fluids under the pressure and temperature conditions and oxygen fugacities typical for magma chambers (0.5-3 kbar, 650-950 °C, Ni-NiO to Re-ReO2 buffer conditions). Sulfur speciation was determined by Raman spectroscopy of quenched fluids trapped as inclusions in quartz. Our results show that sulfur in hydrothermal fluids and volcanic gases is much more oxidized than previously thought and in particular, some explosive eruptions may release a significant fraction of sulfur as SO3 or its hydrated forms. In the pressure range from 500 to 2000 bar, the equilibrium constant K1 of the reaction 2H2S + 3O2 = 2SO2 + 2H2O in aqueous fluids can be described by lnK1 = -(57.1 ± 7.1) + (173,480 ± 7592)T- 1, where T is temperature in Kelvin. The equilibrium constant K2 for the reaction SO2 + ½O2 = SO3 in aqueous fluids, where SO3 may include hydrated forms, such as H2SO4, was found to be strongly pressure dependent, with lnK2 = -(5.2 ± 5.7) + (19,243 ± 5993)T- 1 at 1500 bar; lnK2 = -(11.1 ± 1.3) + (25,383 ± 1371)T- 1 at 2000 bar and lnK2 = -(22.1 ± 2.2) + (37,082 ± 2248)T- 1 at 2500 bar. Our data imply that volcanoes may directly inject hexavalent sulfur in the form of H2SO4 into the atmosphere, not only on Earth, but possibly also on Venus and on Mars, when it was still tectonically active. Remote measurements from satellites may have underestimated the sulfur yield of some recent eruptions. Moreover, the mechanisms of the interaction of volcanic gases with the stratosphere need to be reconsidered.

  8. Interconversion, reactivity and thermal stability of polyaniline in selected oxidation states

    SciTech Connect

    Masters, J.G.

    1992-01-01

    The objectives of this study were: (i) to determine if the base form of the conducting polymer, polyaniline, existed in a continuum of oxidation states ranging from the completely reduced leucoemeraldine oxidation state, (1 [minus] y) = 0, to the completely oxidized pernigraniline oxidation state, (1 [minus] y = 1). (ii) To investigate a novel type of reductive ring amination reaction of protonated polyaniline, of oxidation state 1 [minus] y = 0.50. (iii) Tascertain whether certain forms of polyaniline exhibited thermochromic behavior. (iv) To study factors responsible for enhancing the thermal/oxidative stability of [open quotes]doped[close quotes] polyaniline. (v) To study the reaction between polyaniline and C[sub 60]. The significant results and conclusions are: (a) In the oxidation state range between 1 [minus] y = 0.0 and 1 [minus] y = 1.0, polyaniline base exists in only three discrete oxidation states at the molecular level in the solid state and also in N-methylpyrrolidinone (NMP) solution. (b) Equimolar quantities of the two extreme oxidation states of polyaniline in the base form, leucoemeraldine, (1 [minus] y = 0.0), and pernigraniline, (1 [minus] y = 1.0), undergo a [open quotes]mutual[close quotes] oxidation and reduction when mixed in NMP solution. (c) In the oxidation state range between 1 [minus] y = 0.0 and 1 [minus] y = 0.50, only two species are observed in NMP solution of the polymer after the addition of excess aq. HCl, viz., fully protonated emeraldine salt and non-protonated leucoemeraldine base. (d) Protonation of emeraldine base, (1 [minus] y = 0.50), with nonvolatile acids has allowed the determination of the intrinsic thermal stability of the [open quotes]doped[close quotes] polymer. (e) A new reaction between emeraldine HCl and anhydrous amines results in reductive ring amination to produce leucoemeraldine base derivatives. (f) Reactions of the bases gave reversible thermochromic behavior and the formation of insoluble fullerenes.

  9. Forest soil carbon oxidation state and oxidative ratio responses to elevated CO2

    SciTech Connect

    Hockaday, William C.; Gallagher, Morgan E.; Masiello, Caroline A.; Baldock, Jeffrey A.; Iversen, Colleen M.; Norby, Richard J.

    2015-09-21

    The oxidative ratio (OR) of the biosphere is the stoichiometric ratio (O2/CO2) of gas exchange by photosynthesis and respiration a key parameter in budgeting calculations of the land and ocean carbon sinks. Carbon cycle-climate feedbacks could alter the OR of the biosphere by affecting the quantity and quality of organic matter in plant biomass and soil carbon pools. Here, this study considers the effect of elevated atmospheric carbon dioxide concentrations ([CO2]) on the OR of a hardwood forest after nine growing seasons of Free-Air CO2 Enrichment. We measured changes in the carbon oxidation state (Cox) of biomass and soil carbon pools as a proxy for the ecosystem OR. The OR of net primary production, 1.039, was not affected by elevated [CO2]. However, the Cox of the soil carbon pool was 40% higher at elevated [CO2], and the estimated OR values for soil respiration increased from 1.006 at ambient [CO2] to 1.054 at elevated [CO2]. A biochemical inventory of the soil organic matter ascribed the increases in Cox and OR to faster turnover of reduced substrates, lignin and lipids, at elevated [CO2]. This implicates the heterotrophic soil community response to elevated [CO2] as a driver of disequilibrium in the ecosystem OR. The oxidation of soil carbon pool constitutes an unexpected terrestrial O2 sink. Carbon budgets constructed under the assumption of OR equilibrium would equate such a terrestrial O2 sink to CO2 uptake by the ocean. We find that the potential for climate-driven disequilibriua in the cycling of O2 and CO2 warrants further investigation.

  10. Formation of oxidative and non-oxidative dimers in metallothioneins: Implications for charge state analysis for structural determination.

    PubMed

    Irvine, Gordon W; Heinlein, Lina; Renaud, Justin B; Sumarah, Mark W; Stillman, Martin J

    2017-10-07

    Metallothioneins (MTs) are a class of dynamic proteins that have been investigated extensively using mass spectrometric methods due to their amenability to ionization. Here we detect the formation of oxidative and non-oxidative MT dimers using high resolution mass spectrometry which has previously been overlooked with lower resolution techniques. Recombinant human MT1a and its isolated domain fragments were analyzed by high-resolution Thermo Q-Exactive and Bruker-TOF MS. Covalent Cys modification was performed using N-ethylmalemide to probe the effect of Cys oxidation on dimer formation. Dimerization was detected in the analysis of select charge states of Zn7 MT and apo-βMT. Specifically, high resolution (140k) revealed the +6 dimer peaks overlapping with the +3 charge state, but not with the other charge states (+4, +5, +6). The proteins with covalently modified Cys did not show dimer formation in any of their charge states. Apo-α and apo-βαMT also did not form dimers under the conditions tested. Dimerization of MT was detected for zinc metalated and certain apo-MT forms with high resolution mass spectrometry, which was not seen with lower resolution techniques. These dimers appear overlapped only with certain charge states, confounding their analysis for structural characterization of MTs. The Zn-MT dimers appeared to be non-oxidative, however, the formation of dimers in the apo-protein is likely dependent on Cys oxidation. This article is protected by copyright. All rights reserved.

  11. Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; Shiraiwa, Manabu; Arangio, Andrea; Su, Hang; Pöschl, Ulrich; Wang, Jian; Knopf, Daniel A.

    2017-02-01

    Chemical aging of organic aerosol (OA) through multiphase oxidation reactions can alter their cloud condensation nuclei (CCN) activity and hygroscopicity. However, the oxidation kinetics and OA reactivity depend strongly on the particle phase state, potentially influencing the hydrophobic-to-hydrophilic conversion rate of carbonaceous aerosol. Here, amorphous Suwannee River fulvic acid (SRFA) aerosol particles, a surrogate humic-like substance (HULIS) that contributes substantially to global OA mass, are oxidized by OH radicals at different temperatures and phase states. When oxidized at low temperature in a glassy solid state, the hygroscopicity of SRFA particles increased by almost a factor of two, whereas oxidation of liquid-like SRFA particles at higher temperatures did not affect CCN activity. Low-temperature oxidation appears to promote the formation of highly-oxygenated particle-bound fragmentation products with lower molar mass and greater CCN activity, underscoring the importance of chemical aging in the free troposphere and its influence on the CCN activity of OA.

  12. Changes to carbon oxidation state during the photochemical aging of organic aerosol

    NASA Astrophysics Data System (ADS)

    Kroll, J. H.; Kessler, S. H.; Smith, J. D.; Che, D.; Worsnop, D. R.; Wilson, K. R.

    2009-12-01

    Oxidation reactions of organic species in the earth's atmosphere necessarily result in an increase in the oxidation state of the organic carbon. Thus the oxidation state of the carbon makes for an excellent metric of the degree of photochemical processing ("aging") of atmospheric organic aerosol. This quantity can be calculated from elemental ratios (O/C and H/C) of the organics, and so can be determined using state-of-the-art analytical techniques for measuring aerosol elemental composition, such as the Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Here we present results from laboratory studies of the heterogeneous oxidation of model organic aerosol particles. Particles are oxidized in a flow reactor and their size and chemical composition monitored using an HR-ToF-AMS and a scanning mobility particle sizer (SMPS). Changes to the carbon oxidation state are presented as a function of degree of oxidative processing and molecular structure. Results are interpreted in terms of the two possible reactive pathways that occur during oxidation: functionalization (addition of oxygen-containing functional groups) and fragmentation (breaking of the carbon skeleton). These laboratory results are compared to measurements of the oxidation state of ambient organic aerosol.

  13. Implementation of Inverse Photoelectron Spectroscopy for Measuring the Empty Electronic States of Metal Oxide Surfaces

    DTIC Science & Technology

    2014-11-05

    and initial results on oxidized zirconium have been performed. (a) Papers published in peer-reviewed journals (N/A for none) Enter List of papers...the electronic states of the surface with changes in the photoluminescence spectrum. The results of some of our first experiments on zirconium ...clean” zirconium oxide. The occupied valence electronic states are mainly composed of oxygen 2p electrons. The unoccupied states are zirconium 4d

  14. Three Dimensional Mapping of Nicle Oxidation States Using Full Field Xray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, G.J.; Chu, Y.; Harris, W.M.; Izzo, J.R.; Grew, K.N., Chiu, W.K.S.; Yi, J.; Andrews, J.C.; Liu, Y., Pierro, P.

    2011-04-28

    The reduction-oxidation cycling of the nickel-based oxides in composite solid oxide fuel cells and battery electrodes is directly related to cell performance. A greater understanding of nickel redox mechanisms at the microstructural level can be achieved in part using transmission x-ray microscopy (TXM) to explore material oxidation states. X-ray nanotomography combined with x-ray absorption near edge structure (XANES) spectroscopy has been applied to study samples containing distinct regions of nickel and nickel oxide (NiO) compositions. Digitally processed images obtained using TXM demonstrate the three-dimensional chemical mapping and microstructural distribution capabilities of full-field XANES nanotomography.

  15. Solid State, Surface and Catalytic Studies of Oxides

    SciTech Connect

    Kung, H. H.

    2004-11-23

    This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO{sub x}. Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO{sub x}, it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO{sub 2}/Al{sub 2}O{sub 3}. Ag/Al{sub 2}O{sub 3}, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.

  16. Oxidation states of graphene: Insights from computational spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Wenhua; Carravetta, Vincenzo; Li, Zhenyu; Luo, Yi; Yang, Jinlong

    2009-12-01

    When it is oxidized, graphite can be easily exfoliated forming graphene oxide (GO). GO is a critical intermediate for massive production of graphene, and it is also an important material with various application potentials. With many different oxidation species randomly distributed on the basal plane, GO has a complicated nonstoichiometric atomic structure that is still not well understood in spite of intensive studies involving many experimental techniques. Controversies often exist in experimental data interpretation. We report here a first principles study on binding energy of carbon 1s orbital in GO. The calculated results can be well used to interpret experimental x-ray photoelectron spectroscopy (XPS) data and provide a unified spectral assignment. Based on the first principles understanding of XPS, a GO structure model containing new oxidation species epoxy pair and epoxy-hydroxy pair is proposed. Our results demonstrate that first principles computational spectroscopy provides a powerful means to investigate GO structure.

  17. The Effects of Decomposition on the Oxidative Ratio and Carbon Oxidation State of Organic Matter

    NASA Astrophysics Data System (ADS)

    Gallagher, M. E.; Masiello, C. A.; Clark, N.; Randerson, J. T.; Robertson, G. P.

    2006-12-01

    Ecosystem oxidative ratio (OR) and the related parameter carbon oxidation state (Cox) are critical in the apportionment of anthropogenic CO2 between the terrestrial biosphere and ocean reservoirs. OR is the ratio of O2 to CO2 in gas exchange fluxes between the biosphere and the atmosphere (Fba and Fab). Accurate measurements of OR have been challenging (Seibt et al. 2004); instead we approach the problem by measuring Cox and calculating OR from biomass reservoirs. Cox can range from -4 to +4 (CH4 to CO2) and is driven by photosynthesis, respiration, and decomposition. The net OR of the biosphere varies with ecosystem type, and this can affect the apportionment of anthropogenic CO2 between the terrestrial biosphere and ocean reservoirs (Randerson et al. 2006). This makes it essential to constrain ecosystem Cox and OR values. Although small variations in global ecosystem OR have the potential to cause shifts in atmospheric O2 concentrations, no whole ecosystem measurements of Cox yet exist. To constrain ORba and ORab, and improve our understanding of how decomposition affects Cox, we performed a litter bag experiment at the Kellogg Biological Station-Long Term Ecological Research (KBS-LTER) in Michigan at the end of the 2005 agricultural season. We placed 15 corn biomass litter bags in an agricultural field and collected 3 bags at 2, 4, 7, 26, and 29 weeks. These samples were analyzed for %C, %H, %N, and %O via elemental analysis, and these data were used to calculate Cox. Aboveground Cox was measured similarly. We anticipated that the Cox of the corn litter would become more reduced with decomposition, as the percentage of carbohydrates would decrease with time, while that of protein, lignin, and lipids would increase (Baldock et al. 2004). We report differences between the Cox of biomass fixation and biomass degradation from our experiments. Using simple assumptions about ecosystem nitrogen cycling, we convert Cox to OR and report the existence or absence of a

  18. The oxidation state of the surface of Venus. [Abstract only

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Klingelhofer, G.; Brackett, R. A.; Izenberg, N.

    1994-01-01

    We present experimental results showing that basalt is oxidized in CO-CO2 gas mixtures having CO number densities close to those (approximately 2 times higher) at the surface of Venus. The results suggest that the red color observed by Pieters et al at the Venera 9 and 10 landing sites is due to subaerial oxidation of Fe(2+)-bearing basalt on the surface of Venus, and that hematite, instead of magnetite, is present on the surface of Venus. Well-characterized basalt powder was iosthermally heated in 1000 ppm CO-CO2 gas mixtures at atmospheric pressure for several days. The starting material and reacted samples were analyzed by Mossbauer spectroscopy to determine the amount of Fe(2+) and Fe(3+) in the samples. X-ray diffraction and optical microscopy were also used to characterize samples. The basalt oxidation occurs because the CO and CO2 do not equilibrate in the gas mixture at the low temperatures used. Thus, the basalt reacts with the more abundant CO2 and is oxidized. We propose that the red color of the surface of Venus is due to failure of CO and CO2 to equilibrate with one another in the near-surface atmosphere of Venus, leading to subaerial oxidation of erupted Fe(2+)-bearing basalts. Our interpretation is supported by our studies of magnetite oxidation, which show that synthetic magnetite powders are oxidized to hematite in CO-CO2 gas mixtures inside the magnetite stability field, by our studies of pyrite decomposition, and by independent work on CO-CO2 equilibration in furnace gases.

  19. Oxidation state of multivalent elements in high-level nuclear waste glass

    SciTech Connect

    Reynolds, J.G.

    2007-07-01

    Nuclear waste contains many different elements that have more than one oxidation state. When the nuclear waste is treated by vitrification, the behavior of the element in the melter and resulting glass product depends on the stable oxidation state. The stable oxidation state in any medium can be calculated from the standard potential in that medium. Consequently, the standard potential of multi-valent elements has been measured in many silicate-melts, including ones relevant to nuclear waste treatment. In this study, the relationship between the standard potential in molten nuclear waste glass and the standard potential in water will be quantified so that the standard potential of elements that have not been measured in glass can be estimated. The regression equation was found to have an R{sup 2} statistic of 0.96 or 0.83 depending on the number of electrons transferred in the reaction. The Nernst equation was then used to calculate the oxidation state of other relevant multi-valent elements in nuclear waste glass from these standard potentials and the measured ferrous to ferric iron ratio. The calculated oxidation states were consistent with all oxidation state measurements available. The calculated oxidation states were used to rationalize the behavior of many of the multi-valent elements. For instance, chromium increases glass crystallization because it is in the trivalent-state, iodine volatilises from the melter because it is in the volatile zero-valent state, and the leaching behavior of arsenic is driven by its oxidation state. Thus, these thermodynamic calculations explain the behavior of many trace elements during the vitrification process. (authors)

  20. Solid-state, surface, and catalytic properties of oxides

    NASA Astrophysics Data System (ADS)

    Kung, H. H.

    1981-08-01

    Catalysis by transition metal oxides was investigated and four areas are emphasized. In the first area, an adsorbed oxygen species on iron oxide was characterized. This species desorb, with an activation energy of 38 kcal/mole, and it has a coverage of 1.4 x 10(16) molecules/m(2). Its desorption follows a second order kinetics suggesting that it is an atomic species. The high activation energy suggests that the species may only be active in total oxidation. In the second area, ZnO surfaces containing controlled defects in the form of steps were studied. It is found that the nonpolar flat a stepped and a polar surface behave differently. The CO2 adsorbs with increasing strength on these three surfaces in this order. Methanol does not decompose on a stoichiometric. The stepped surface is active in methanol decomposition in the manner like the vacancy.

  1. Gender-related differences in the oxidant state of cells in Fanconi anemia heterozygotes.

    PubMed

    Petrovic, Sandra; Leskovac, Andreja; Kotur-Stevuljevic, Jelena; Joksic, Jelena; Guc-Scekic, Marija; Vujic, Dragana; Joksic, Gordana

    2011-07-01

    Abstract Fanconi anemia (FA) is a rare cancer-prone genetic disorder characterized by progressive bone marrow failure, chromosomal instability and redox abnormalities. There is much biochemical and genetic data, which strongly suggest that FA cells experience increased oxidative stress. The present study was designed to elucidate if differences in oxidant state exist between control, idiopathic bone marrow failure (idBMF) and FA cells, and to analyze oxidant state of cells in FA heterozygous carriers as well. The results of the present study confirm an in vivo prooxidant state of FA cells and clearly indicate that FA patients can be distinguished from idBMF patients based on the oxidant state of cells. Female carriers of FA mutation also exhibited hallmarks of an in vivo prooxidant state behaving in a similar manner as FA patients. On the other hand, the oxidant state of cells in FA male carriers and idBMF families failed to show any significant difference vs. controls. We demonstrate that the altered oxidant state influences susceptibility of cells to apoptosis in both FA patients and female carriers. The results highlight the need for further research of the possible role of mitochondrial inheritance in the pathogenesis of FA.

  2. The state of the components in copper-cerium catalysts supported on different oxides

    NASA Astrophysics Data System (ADS)

    Kosmambetova, G. R.; Kriventsov, V. V.; Moroz, E. M.; Pakharukova, V. P.; Strizhak, P. E.; Zyuzin, D. A.

    2009-05-01

    The phase composition and the state of the active components in the catalysts used for preferential oxidation (PROX) of CO in hydrogen-containing mixtures are considered. Cu-Ce catalysts supported on different oxides (ZrO 2, TiO 2, Al 2O 3, MnO 2) before and after PROX reaction are characterized.

  3. *Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate ciona intestinalis

    EPA Science Inventory

    Biotransformation of inorganic arsenic (iAs) involves methylation catalyzed by arsenic (+3 oxidation state) methyltransferase (As3mt) , yielding mono-, di-, and trimethylated arsenicals. A comparative genomic approach focused on Ciona intestinaJis, an invertebrate chordate, was u...

  4. Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate Ciona intestinalis

    EPA Science Inventory

    Biotransformation of inorganic arsenic (iAs) involves methylation catalyzed by arsenic (+3 oxidation state) methyltransferase (As3mt), yielding mono- , di- , and trimethylated arsenicals. To investigate the evolution of molecular mechanisms that mediate arsenic biotransformation,...

  5. Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate Ciona intestinalis

    EPA Science Inventory

    The biotransformation of inorganic arsenic (iAs) involves methylation by an arsenic (+3 oxidation state) methyltransferase (AS3MT), yielding methyl arsenic (MA), dimethyl arsenic (DMA), and trimethylarsenic (TMA). To identify molecular mechanisms that coordinate arsenic biotra...

  6. *Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate ciona intestinalis

    EPA Science Inventory

    Biotransformation of inorganic arsenic (iAs) involves methylation catalyzed by arsenic (+3 oxidation state) methyltransferase (As3mt) , yielding mono-, di-, and trimethylated arsenicals. A comparative genomic approach focused on Ciona intestinaJis, an invertebrate chordate, was u...

  7. Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate Ciona intestinalis

    EPA Science Inventory

    The biotransformation of inorganic arsenic (iAs) involves methylation by an arsenic (+3 oxidation state) methyltransferase (AS3MT), yielding methyl arsenic (MA), dimethyl arsenic (DMA), and trimethylarsenic (TMA). To identify molecular mechanisms that coordinate arsenic biotra...

  8. Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate Ciona intestinalis

    EPA Science Inventory

    Biotransformation of inorganic arsenic (iAs) involves methylation catalyzed by arsenic (+3 oxidation state) methyltransferase (As3mt), yielding mono- , di- , and trimethylated arsenicals. To investigate the evolution of molecular mechanisms that mediate arsenic biotransformation,...

  9. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.

    PubMed

    Kroll, Jesse H; Donahue, Neil M; Jimenez, Jose L; Kessler, Sean H; Canagaratna, Manjula R; Wilson, Kevin R; Altieri, Katye E; Mazzoleni, Lynn R; Wozniak, Andrew S; Bluhm, Hendrik; Mysak, Erin R; Smith, Jared D; Kolb, Charles E; Worsnop, Douglas R

    2011-02-01

    A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

  10. Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

    ERIC Educational Resources Information Center

    Ebisuzaki, Y.; Sanborn, W. B.

    1985-01-01

    Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

  11. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    SciTech Connect

    Bagus, Paul S.

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  12. Structural evolution and valence electron-state change during ultra thin silicon-oxide growth

    NASA Astrophysics Data System (ADS)

    Shimizu, A.; Abe, S.; Nakayama, H.; Nishino, T.; Iida, S.

    2000-06-01

    We have studied valence electron-state changes of Si during initial oxidation of Si(111) clean surface, HF-treated Si(001) and Si(111) surfaces by Auger valence electron spectroscopy (AVES). The results showed that the valence electron-state changes during initial oxidation were sensitively reflected in Si[2s,2p,V] (V=3s,3p) AVES spectra and that they depended on both initial surface treatment and surface orientation. The local valence electron-states, local density of states in other words, showed the characteristic-structure evolution depending on the initial surface treatment and surface orientation.

  13. Clay-mediated reactions of HCN oligomers - The effect of the oxidation state of the clay

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Alwis, K. W.; Edelson, E. H.; Mount, N.; Hagan, W. J., Jr.

    1981-01-01

    Montmorillonite clays which contain Fe(III) inhibit the oligomerization of aqueous solutions of HCN. The inhibitory effect is due to the rapid oxidation of diaminomaleonitrile, a key intermediate in HCN oligomerization, by the Fe(III) incorporated into the aluminosilicate lattice of the clay. The Fe(III) oxidizes diaminomaleonitrile to diiminosuccinonitrile, a compound which is rapidly hydrolyzed to HCN and oxalic acid derivatives. Diaminomaleonitrile is not oxidized when Fe(III) in the montmorillonite is reduced with hydrazine. The oxidation state of the clay is an important variable in experiments designed to simulate clay catalysis on the primitive earth.

  14. Clay-mediated reactions of HCN oligomers - The effect of the oxidation state of the clay

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Alwis, K. W.; Edelson, E. H.; Mount, N.; Hagan, W. J., Jr.

    1981-01-01

    Montmorillonite clays which contain Fe(III) inhibit the oligomerization of aqueous solutions of HCN. The inhibitory effect is due to the rapid oxidation of diaminomaleonitrile, a key intermediate in HCN oligomerization, by the Fe(III) incorporated into the aluminosilicate lattice of the clay. The Fe(III) oxidizes diaminomaleonitrile to diiminosuccinonitrile, a compound which is rapidly hydrolyzed to HCN and oxalic acid derivatives. Diaminomaleonitrile is not oxidized when Fe(III) in the montmorillonite is reduced with hydrazine. The oxidation state of the clay is an important variable in experiments designed to simulate clay catalysis on the primitive earth.

  15. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    SciTech Connect

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; John Noetzel; Larry Chick

    2003-12-08

    The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from January 1, 2003 to June 30, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; and Task 9 Stack Testing with Coal-Based Reformate.

  16. Epoxy and Oxidoannulene Oxidation Mechanisms of Fused-Pentagon Chlorofullerenes: Oxides Linked by a Pirouette-Type Transition State.

    PubMed

    Li, Qiao-Zhi; Zheng, Jia-Jia; He, Ling; Zhao, Xiang; Nagase, Shigeru

    2017-07-07

    Recently, the oxidative functionalization of double-fused-pentagon (DFP)-containing chlorofullerenes (#271)C50Cl10 and (#913)C56Cl10 was carried out, resulting in two monoepoxides with the oxygen atom added at the ortho site of pentalene on the DFP moiety. To uncover the reactivity of isolated-pentagon-rule violating fullerenes upon oxidation, two possible formation processes (ozone molecule and oxygen radical served as oxidation reagents) of these two oxides were systematically investigated through density functional theory calculations. For the ozone oxidation, two possible pathways were explored, and the results indicate that the biradical mechanism Pathos-RACDP is kinetically more favorable than Pathos-RABP, where R, A, and P represent reactants, ozonide intermediates, and oxidation products and B, C, and D represent another three oxygen-containing intermediates. The products obtained by ozone oxidation ([6,6]-55-closed epoxides P-C3-C29 for (#271)C50Cl10 and P-C42-C43 for (#913)C56Cl10 with oxygen atom added at the shortest and highest HOMO-contribution bonds) are consistent with experimental observations. However, the oxygen radical additions on these two chlorofullerenes favor generation of the [5,6]-66-open oxidoannulene adducts P-C3-C2 and P-C42-C54, respectively. Subsequent analyses of their geometrical features and structural stabilities suggest that these two oxidoannulene adducts are energetically unfavorable and could be converted to more stable epoxides mentioned above by undergoing a pirouette-type transition state. In these two diverse oxidation procedures, the favorable C-C bonds for ozone attacking and C atoms for oxygen-adsorption are rationalized in terms of their bond lengths and HOMO contributions as well as pyramidalization angles.

  17. A simple method of interface-state reduction in metal-nitride-oxide-semiconductor structures

    NASA Astrophysics Data System (ADS)

    Sheu, Yea-Dean

    1991-04-01

    A method for reducing the interface-state density in polysilicon gate metal-nitride-oxide-semiconductor (MNOS) capacitors is reported. The method involves deposition of a sacrificial blanket aluminum layer on top of a chemical-vapor-deposition (CVD) oxide over MNOS capacitors. The entire stack was then annealed at 450 °C in nitrogen and then the metal and CVD oxide were stripped away. The interface state density was reduced from 1011 to 1010 cm-2 eV-1 after this anneal. It is believed that Al reacts with trace water in the CVD oxide and generates active hydrogen. The hydrogen diffuses to the Si/SiO2 interface and passivates the interface states.

  18. Superparamagnetic Iron Oxide Nanoparticles with Variable Size and an Iron Oxidation State as Prospective Imaging Agents

    PubMed Central

    Kucheryavy, Pavel; He, Jibao; John, Vijay T.; Maharjan, Pawan; Spinu, Leonard; Goloverda, Galina Z.; Kolesnichenko, Vladimir L.

    2013-01-01

    Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r1 and r2 relaxivity measurements in water and diethylene glycol (for OH and CH2 protons) have shown a decrease in the r2/r1 ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe3O4 with the same particle size, but their r1 relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability. PMID:23249219

  19. A method for determining the oxidation state of uranium in natural waters

    NASA Astrophysics Data System (ADS)

    Anderson, Robert F.

    1984-06-01

    Uranium exhibits radically different geochemical properties in its two oxidation states. Hexavalent uranium is quite soluble, especially when complexed by carbonate ions in alkaline solutions. Tetravalent uranium, by contrast, is very insoluble, and it would be expected to be rapidly removed from natural waters either by precipitation of a mineral phase such as UO 2(s) or by adsorption to solid surfaces. It is important to know the oxidation state in which uranium will occur under specified conditions of Eh and pH as this relates both to processes forming economically valuable uranium deposits and to the mobility of uranium released to the environment during various stages of the nuclear fuel cycle. In this work, yield monitors in each oxidation state [ 232U(IV)], 236U(VI)] are added to water samples, and uranium oxidation states are separated by a NdF 3 coprecipitation in which only the U(IV) is carried. The precipitate is removed by filtration. Subsequently, TiCl 3 is added to reduce U(IV) and the NdF 3 coprecipitation is repeated. A similar method is widely used for separating oxidation states of plutonium. Results from a meromictic lake (Fayetteville Green Lake, Syracuse, New York, USA) and from an anoxic marine basin (Cariaco Trench, Venezuela) where total H 2S concentrations in the bottom waters reach 1 mM 1 -1 and 50 μM 1 -1 respectively show that in both cases the dissolved uranium is present in its oxidized form.

  20. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    SciTech Connect

    Grimes, Travis Shane; Mincher, Bruce Jay; Schmitt, Nicholas C

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  1. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    SciTech Connect

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; Larry Chick

    2004-05-07

    The objective of this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from July 1, 2003 to December 31, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; Task 9 Stack Testing with Coal-Based Reformate; and Task 10 Technology Transfer from SECA CORE Technology Program. In this reporting period, unless otherwise noted Task 6--System Fabrication and Task 7--System Testing will be reported within Task 1 System Design and Integration. Task 8--Program Management, Task 9--Stack Testing with Coal Based Reformate, and Task 10--Technology Transfer from SECA CORE Technology Program will be reported on in the Executive Summary section of this report.

  2. Monomethylioarsenicals are substratres for human arsenic (+3 oxidation state) methyltransferase

    EPA Science Inventory

    Monomethylthioarsenicals are substrates for human arsenic (+3 oxida1tion state) methyltransferase Methylated thioarsenicals are structural analogs of methylated oxyarsenic in which one or more oxygen atom bound t...

  3. Monomethylioarsenicals are substratres for human arsenic (+3 oxidation state) methyltransferase

    EPA Science Inventory

    Monomethylthioarsenicals are substrates for human arsenic (+3 oxida1tion state) methyltransferase Methylated thioarsenicals are structural analogs of methylated oxyarsenic in which one or more oxygen atom bound t...

  4. GaAs-oxide interface states - A gigantic photoionization effect and its implications to the origin of these states

    NASA Technical Reports Server (NTRS)

    Lagowski, J.; Walukiewicz, W.; Kazior, T. E.; Gatos, H. C.; Siejka, J.

    1981-01-01

    Gigantic photoionization was discovered on GaAs-oxide interfaces leading to the discharge of deep surface states with rates exceeding 1000 times those of photoionization transitions to the conduction band. It exhibits a peak similar to acceptor-donor transitions and is explained as due to energy transfer from photo-excited donor-acceptor pairs to deep surface states. This new process indicates the presence of significant concentrations of shallow donor and acceptor levels not recognized in previous interface models.

  5. Mantle redox evolution and the oxidation state of the Archean atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.; Eggler, D. H.; Raeburn, S. P.

    1993-01-01

    Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.

  6. Water and the Oxidation State of Subduction Zone Magmas

    SciTech Connect

    Kelley, K.; Cottrell, E

    2009-01-01

    Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe{sup 3+}/{Sigma}Fe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H{sub 2}O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe{sup 3+}/{Sigma}Fe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H{sub 2}O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

  7. Water and the oxidation state of subduction zone magmas.

    PubMed

    Kelley, Katherine A; Cottrell, Elizabeth

    2009-07-31

    Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe3+/SigmaFe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H2O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe3+/SigmaFe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H2O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

  8. Arsenic (+3 oxidation state) methyltransferase genotype affects steady-state distribution and clearance of arsenic in arsenate-treated mice

    EPA Science Inventory

    Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes formation of mono-, di-, and tri-methylated metabolites of inorganic arsenic. Distribution and retention of arsenic were compared in adult female As3mt knockout mice and wild-type C57BL/6 mice using a regimen in whi...

  9. Arsenic (+3 oxidation state) methyltransferase genotype affects steady-state distribution and clearance of arsenic in arsenate-treated mice

    EPA Science Inventory

    Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes formation of mono-, di-, and tri-methylated metabolites of inorganic arsenic. Distribution and retention of arsenic were compared in adult female As3mt knockout mice and wild-type C57BL/6 mice using a regimen in whi...

  10. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Treesearch

    W.C. Hockaday; C.A. Masiello; J.T. Randerson; R.J. Smernik; J.A. Baldock; O. A. Chadwick; J.W. Harden

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2...

  11. Effect of environment on iodine oxidation state and reactivity with aluminum.

    PubMed

    Smith, Dylan K; McCollum, Jena; Pantoya, Michelle L

    2016-04-28

    Iodine oxide is a highly reactive solid oxidizer and with its abundant generation of iodine gas during reaction, this oxidizer also shows great potential as a biocidal agent. A problem with using I2O5 in an energetic mixture is its highly variable reactive behavior. This study isolates the variable reactivity associated with I2O5 as a function of its chemical reaction in various environments. Specifically, aluminum fuel and iodine oxide powder are combined using a carrier fluid to aid intermixing. The carrier fluid is shown to significantly affect the oxidation state of iodine oxide, thereby affecting the reactivity of the mixture. Four carrier fluids were investigated ranging in polarity and water miscibility in increasing order from hexane < acetone < isopropanol < water as well as untreated, dry-mixed reactants. Oxidation state and reactivity were examined with experimental techniques including X-ray photoelectric spectroscopy (XPS) and differential scanning calorimetry (DSC). Results are compared with thermal equilibrium simulations. Flame speeds increased with polarity of the fluid used to intermix the powder and ranged from 180 to 1202 m s(-1). The I2O5 processed in the polar fluids formed hydrated states of iodine oxide: HIO3 and HI3O8; and, the nonpolar and dry-mixed samples formed: I2O4 and I4O9. During combustion, the hydrated iodine oxides rapidly dehydrated from HIO3 to HI3O8 and from HI3O8 to I2O5. Both steps release 25% of their mass as vapor during combustion. Increased gas generation enhances convective energy transport and accounts for the increase in reactivity seen in the mixtures processed in polar fluids. These results explain the chemical mechanisms underlying the variable reactivity of I2O5 that are a function of the oxide's highly reactive nature with its surrounding environment. These results will significantly impact the selection of carrier fluid in the synthesis approach for iodine containing reactive mixtures.

  12. Identification of the oxidation state of americium by thin-layer chromatography using domestic plates

    SciTech Connect

    Molochnikova, N.P.; Myasoedov, B.F.

    1994-10-01

    Methods of precipitation, solvent extraction, ion exchange, and extraction chromatography were suggested to identify trace amounts of americium in different oxidation states. Thin-layer chromatography (TLC) has not been used previously for these purposes. At the same time, this method is widely used in the separation of small quantities of elements in different valence states. Previously, the chromatographic mobility of actinide ions on thin layers of silica gel and cellulose on Silufol plates (CSFR) and plates from Merck (Germany) was investigated. The behavior of americium in different oxidation states on domestic TLC plates in nitric acid solutions was determined to be of interest.

  13. Reactions of lanthanide atoms with oxygen difluoride and the role of the Ln oxidation state.

    PubMed

    Mikulas, Tanya; Chen, Mingyang; Dixon, David A; Peterson, Kirk A; Gong, Yu; Andrews, Lester

    2014-01-06

    Laser-ablated lanthanide metal atoms were condensed with OF2 in excess argon or neon at 4 K. New infrared absorption bands were observed and assigned to the oxidative addition products OLnF2 and OLnF on the basis of (18)O isotopic substitution and electronic structure calculations of the vibrational frequencies. The dominant absorptions in the 500 cm(-1) region are identified as Ln-F stretching modes, which follow the lanthanide contraction. The Ln-O stretching frequency is an important measure of the oxidation states of the Ln and oxygen and the spin state of the complex. The OCeF2, OPrF2, and OTbF2 molecules have higher frequency Ln-O stretching modes. The Ce is assigned to the IV oxidation state and the Pr and Tb are assigned to a mixed III/IV oxidation state. The remaining OLnF2 compounds have lower Ln-O stretches, and the Ln is in the III oxidation state and the O is in the -1 oxidation state. For all of the OLnF compounds, the metal is in the III oxidation state, and the Ln-F bonds are ionic. In OCeF2, OLaF, and OLuF, the bonding between the Ln and O is best described as a highly polarized σ bond and two pseudo π bonds formed by donation from the two 2p lone pairs on the O to the Ln. Bonding for the OLnF2 compounds in the III oxidation state is predicted to be fully ionic. The bonding in OLnF2 and OLnF is dominated by the oxidation state on the lanthanide and the spin state of the molecule. The observation of larger neon to argon matrix shifts for Ln-O modes in several OLnF molecules as compared to their OLnF2 analogues is indicative of more ionic character in the OLnF species, consistent with the more formal negative charge on the oxygen in OLnF.

  14. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    ERIC Educational Resources Information Center

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  15. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    ERIC Educational Resources Information Center

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  16. Cpmmw Spectroscopy of Rydberg States of Nitric Oxide

    NASA Astrophysics Data System (ADS)

    Barnum, Timothy J.; Saladrigas, Catherine A.; Grimes, David; Coy, Stephen; Eyler, Edward E.; Field, Robert W.

    2016-06-01

    The spectroscopy of Rydberg states of NO has a long history [1], stimulating both experimental and theoretical advances in our understanding of Rydberg structure and dynamics. The closed-shell ion-core (1Σ+) and small NO+ dipole moment result in regular patterns of Rydberg series in the Hund's case (d) limit, which are well-described by long-range electrostatic models (e.g., [2]). We will present preliminary data on the core-nonpenetrating Rydberg states of NO (orbital angular momentum, ℓ ≥ 3) collected by chirped-pulse millimeter-wave (CPmmW) spectroscopy. Our technique directly detects electronic free induction decay (FID) between Rydberg states with Δn* ≈ 1 in the region of n* ˜ 40-50, providing a large quantity (12 GHz bandwidth in a single shot) of high quality (resolution ˜ 350 kHz) spectra. Transitions between high-ℓ, core-nonpenetrating Rydberg states act as reporters on the subtle details of the ion-core electric structure. * * [1] Huber KP. Die Rydberg-Serien im Absorptions-spektrum des NO-Molekuuls. Helv. Phys. Acta 3, 929 (1961). * * [2] Biernacki DT, Colson SD, Eyler EE. Rotationally resolved double resonance spectra of NO Rydberg states near the first ionization limit. J. Chem. Phys. 88, 2099 (1988).

  17. Oxide films state analysis by IR spectroscopy based on the simple oscillator approximation

    NASA Astrophysics Data System (ADS)

    Volkov, N. V.; Yakutkina, T. V.; Karpova, V. V.

    2017-05-01

    Stabilization of structure-phase state in a wide temperature range is one of the most important problems of improving properties of oxide compounds. As such, the search of new effective methods for obtaining metal oxides with desired physic-chemical, electro-physical and thermal properties and their control is important and relevant. The aim of this work is identification features state of the oxide films of some metals Be, Al, Fe, Cu, Zr on the metal surface of the polycrystalline samples by infrared spectroscopy. To identify the resonance emission bands the algorithm of IR-spectra processing was developed and realized on the basis of table processor EXCEL-2010, which allow revealing characteristic resonance bands successfully and identification of inorganic chemical compounds. In the frame of simple oscillator model, resonance frequencies of normal vibrations of water and some inorganic compounds: metal oxides - Be, Al, Fe, Cu, Zr were calculated and characteristic frequencies for different states (aggregate, deformation, phase) were specified. By means of IR-spectroscopy fundamental possibility of revealing oxides films on metal substrate features state is shown, that allow development and optimization of the technology for production of the oxide films with desired properties.

  18. Autodetachment spectroscopy of the aluminum oxide anion dipole bound state

    SciTech Connect

    Mascaritolo, Kyle J.; Gardner, Adrian M.; Heaven, Michael C.

    2015-09-21

    The {sup 1}Σ{sup +}←X{sup 1}Σ{sup +} ground state to dipole bound state (DBS) electronic transition of AlO{sup −} has been studied by means of autodetachment spectroscopy. Vibrational and rotational molecular constants for AlO{sup −} have been determined for both the ground state (υ″ = 0, 1) and the excited DBS (υ′ = 0, 1). These data provide an improved determination of the electron affinity for AlO (2.6110(7) eV) that is consistent with an earlier measurement. The electron binding energy of the DBS was found to be 52 ± 6 cm{sup −1}. Experimental results are compared with the predictions from high level ab initio calculations.

  19. Topological and unconventional magnetic states in transition metal oxides

    NASA Astrophysics Data System (ADS)

    Fiete, Gregory

    In this talk I describe some recent work on unusual correlated phases that may be found in bulk transition metal oxides with strong spin-orbit coupling. I will focus on model Hamiltonian studies that are motivated by the pyrocholore iridates, though the correlated topological phases described may appear in a much broader class of materials. I will describe a variety of fractionalized topological phases protected by time-reversal and crystalline symmetries: The weak topological Mott insulator (WTMI), the TI* phase, and the topological crystalline Mott insulator (TCMI). If time permits, I will also discuss closely related heterostructures of pyrochlore iridates in a bilayer and trilayer film geometry. These quasi-two dimensional systems may exhibit a number of interesting topological and magnetic phases. This work is generously funded by the ARO, DARPA, and the NSF.

  20. Solid oxide fuel cell commercialization in the United States

    SciTech Connect

    Williams, M.C.

    1995-03-01

    This paper discusses aspects of solid oxide fuel cell (SOFC) technology commercialization in the US. It provides the status of the major SOFC developments occurring in the US by addressing both intermediate- and high-temperature SOFC`s, several SOFC designs, including both planar and tubular, and SOFC system configurations. This paper begins with general characteristics, proceeds with designs and system configurations, and finishes with a discussion of commercialization, funding, and policies. The US Department of Energy`s (DOE) Morgantown Energy Technology Center (METC) is the lead US DOE center for the implementation of a Research, Development, and Demonstration Program to develop fuel cells for stationary power. METC`s stakeholders include the electric power and gas industries, as well as fuel cell developers and others. This paper offers some new perspectives on SOFC development and commercialization which come from the broad consideration of the commercialization efforts of the entire fuel cell industry.

  1. OXIDIZED NITROGEN DEPOSITION IN THE EASTERN UNITED STATES

    EPA Science Inventory


    Air quality and selected meteorological parameters have been monitored at rural sites in the United States (US) by EPA's Clean Air Status and Trends Network, (CASTNet) sites. The National Atmospheric Deposition Program (NADP) monitors wet deposition of numerous ions in precip...

  2. A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis.

    PubMed

    Michaelos, Thoe K; Shopov, Dimitar Y; Sinha, Shashi Bhushan; Sharninghausen, Liam S; Fisher, Katherine J; Lant, Hannah M C; Crabtree, Robert H; Brudvig, Gary W

    2017-03-08

    Water-oxidation catalysis is a critical bottleneck in the direct generation of solar fuels by artificial photosynthesis. Catalytic oxidation of difficult substrates such as water requires harsh conditions, so the ligand must be designed both to stabilize high oxidation states of the metal center and to strenuously resist ligand degradation. Typical ligand choices either lack sufficient electron donor power or fail to stand up to the oxidizing conditions. Our research on Ir-based water-oxidation catalysts (WOCs) has led us to identify a ligand, 2-(2'-pyridyl)-2-propanoate or "pyalk", that fulfills these requirements. Work with a family of Cp*Ir(chelate)Cl complexes had indicated that the pyalk-containing precursor gave the most robust WOC, which was still molecular in nature but lost the Cp* fragment by oxidative degradation. In trying to characterize the resulting active "blue solution" WOC, we were able to identify a diiridium(IV)-mono-μ-oxo core but were stymied by the extensive geometrical isomerism and coordinative variability. By moving to a family of monomeric complexes [Ir(III/IV)(pyalk)3] and [Ir(III/IV)(pyalk)2Cl2], we were able to better understand the original WOC and identify the special properties of the ligand. In this Account, we cover some results using the pyalk ligand and indicate the main features that make it particularly suitable as a ligand for oxidation catalysis. The alkoxide group of pyalk allows for proton-coupled electron transfer (PCET) and its strong σ- and π-donor power strongly favors attainment of exceptionally high oxidation states. The aromatic pyridine ring with its methyl-protected benzylic position provides strong binding and degradation resistance during catalytic turnover. Furthermore, the ligand has two additional benefits: broad solubility in aqueous and nonaqueous solvents and an anisotropic ligand field that enhances the geometry-dependent redox properties of its complexes. After discussion of the general properties, we

  3. Theoretical study of the structures of flavin in different oxidation and protonation states

    SciTech Connect

    Zheng, Y.J.; Ornstein, R.L.

    1996-10-02

    Ab initio molecular orbital theory was used to investigate the structure of flavin in different oxidation and protonation states using lumiflavin as a model compound. According to our study. oxidized flavin is planar no matter what its protonation state or whether it participates in hydrogen bonding. The structures of flavin semiquinone radicals are planar or very close to planar, but the reduced flavin H{sub 3}Fl{sub red} (9) is bent with a ring puckering angle of 27.3{degree} along the N5 and N10 axis. The calculations indicate that N1 is the site of protonation for oxidized flavin, which is in agreement with several crystallographic studies. The calculated spin density distribution for flavin semiquinone radicals is also consistent with experimental results. Electrostatic potential derived charges at the RHF/6-31G{sup *} level of theory are also provided for both oxidized and reduced flavins. 34 refs., 4 figs., 5 tabs.

  4. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  5. Engineering the defect state and reducibility of ceria based nanoparticles for improved anti-oxidation performance.

    PubMed

    Wang, Yan-Jie; Dong, Hao; Lyu, Guang-Ming; Zhang, Huai-Yuan; Ke, Jun; Kang, Li-Qun; Teng, Jia-Li; Sun, Ling-Dong; Si, Rui; Zhang, Jing; Liu, Yan-Jun; Zhang, Ya-Wen; Huang, Yun-Hui; Yan, Chun-Hua

    2015-09-07

    Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd(3+). Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes.

  6. The Effects of Iron Oxidation State on Clay Swelling,

    DTIC Science & Technology

    1983-03-07

    swelling, montmorillonite , nontronite, smectite, water, DLVO theory, surface charge, dissolution, methods, aluminum, silicon, inert atmosphere. 2G...that many physical properties of bulk water are changed when it is adsorbed between layers of Na4- montmorillonite (e.g., Oster and Low, 1964; Kolaian...Na+- montmorillonite accounted for about 13% of the total water content in the free-swelling state. We can therefore express the total water content

  7. Determining the Oxidation States of Manganese in NT2 Cells and Cultured Astrocytes

    SciTech Connect

    Gunter,K.; Aschner, M.; Miller, L.; Eliseev, R.; Salter, J.; Andersen, K.; Gunter, T.

    2006-01-01

    Excessive brain manganese (Mn) can produce a syndrome called 'manganism', which correlates with loss of striatal dopamine and cell death in the striatum and globus pallidus. The prevalent hypothesis for the cause of this syndrome has been oxidation of cell components by the strong oxidizing agent, Mn{sup 3+}, either formed by oxidation of intracellular Mn{sup 2+} or transported into the cell as Mn{sup 3+}. We have recently used X-ray absorption near edge structure spectroscopy (XANES) to determine the oxidation states of manganese complexes in brain and liver mitochondria and in nerve growth factor (NGF)-induced and non-induced PC12 cells. No evidence was found for stabilization or accumulation of Mn{sup 3+} complexes because of oxidation of Mn{sup 2+} by reactive oxygen species in these tissues. Here we extend these studies of manganese oxidation state to cells of brain origin, human neuroteratocarcinoma (NT2) cells and primary cultures of rat astrocytes. Again we find no evidence for stabilization or accumulation of any Mn{sup 3+} complex derived from oxidation of Mn{sup 2+} under a range of conditions.

  8. Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state

    DOE PAGES

    Slade, Jonathan H.; Shiraiwa, Manabu; Arangio, Andrea; ...

    2017-01-27

    Chemical aging of organic aerosol (OA) through multiphase oxidation reactions can alter their cloud condensation nuclei (CCN) activity and hygroscopicity. However, the oxidation kinetics and OA reactivity depend strongly on the particle phase state, potentially influencing the hydrophobic-to-hydrophilic conversion rate of carbonaceous aerosol. Here, amorphous Suwannee River fulvic acid (SRFA) aerosol particles, a surrogate humic-like substance (HULIS) that contributes substantially to global OA mass, are oxidized by OH radicals at different temperatures and phase states. When oxidized at low temperature in a glassy solid state, the hygroscopicity of SRFA particles increased by almost a factor of two, whereas oxidation ofmore » liquid-like SRFA particles at higher temperatures did not affect CCN activity. Low-temperature oxidation appears to promote the formation of highly-oxygenated particle-bound fragmentation products with lower molar mass and greater CCN activity, underscoring the importance of chemical aging in the free troposphere and its influence on the CCN activity of OA.« less

  9. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    SciTech Connect

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  10. Angle-resolved photoemission spectroscopy studies of metallic surface and interface states of oxide insulators.

    PubMed

    Plumb, Nicholas C; Radović, Milan

    2017-09-29

    Over the last decade, conducting states embedded in insulating transition metal oxides (TMOs) have served as gateways to discovering and probing surprising phenomena that can emerge in complex oxides, while also opening opportunities for engineering advanced devices. These states are commonly realized at thin film interfaces, such as the well-known case of LaAlO3 (LAO) grown on SrTiO3 (STO). In recent years, the use of angle-resolved photoemission spectroscopy (ARPES) to investigate the k-space electronic structure of such materials led to the discovery that metallic states can also be formed on the bare surfaces of certain TMOs. In this topical review, we report on recent studies of low-dimensional metallic states confined at insulating oxide surfaces and interfaces as seen from the perspective of ARPES, which provides a direct view of the occupied band structure. While offering a fairly broad survey of progress in the field, we draw particular attention to STO, whose surface is so far the best-studied, and whose electronic structure is probably of the most immediate interest, given the ubiquitous use of STO substrates as the basis for conducting oxide interfaces. The ARPES studies provide crucial insights into the electronic band structure, orbital character, dimensionality/confinement, spin structure, and collective excitations in STO surfaces and related oxide surface/interface systems. The obtained knowledge increases our understanding of these complex materials and gives new perspectives on how to manipulate their properties.

  11. [Superparamagnetic iron oxide particles: current state and future development].

    PubMed

    Taupitz, M; Schmitz, S; Hamm, B

    2003-06-01

    A wide range of applications for superparamagnetic iron oxide (SPIO) particles as contrast media for MRI has emerged over the last 15 years. SPIO particles can be manufactured with different particle sizes and surface coatings. Large SPIO particles (50-150 nm) predominantly produce a signal decrease or T2 -shortening and are used as contrast media for MRI of the liver and spleen. They have a high accuracy, especially in detecting liver metastases (approved for clinical use: AMI-25 (Endorem or Ferridex), SHU-555A (Resovist)). Smaller particles (about 20 nm in diameter) show a different organ distribution and have a potential for improving noninvasive lymph node assessment or characterizing vulnerable atherosclerotic plaques (in clinical trials: AMI-227 [Sinerem or Combidex]). Particles with an optimized T1-relaxivity and prolonged intravascular circulation time can be used as blood pool contrast media for MR angiography. The currently investigated indications are MR angiography of the trunk, peripheral vessels, and coronary arteries (e.g., SHU-555 C (Supravist), VSOP-C 184). Other applications of small SPIO particles include MRI of the bone marrow and the determination of perfusion parameters in tumors or other tissues like the myocardium. SPIO particles with a modified coat can be used in so-called molecular imaging, such as receptor-directed imaging, cell labeling for in-vivo monitoring of cell migration, e.g., stem cell labeling, and labeling of gene constructs for localization in genetic therapy. In tumor therapy SPIO particles can serve as mediators for hyperthermia. SPIO is a powerful MR contrast medium with manifold applications ranging from diagnostic imaging to molecular medicine.

  12. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    PubMed

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  13. Photoemission study of praseodymia in its highest oxidation state: The necessity of in situ plasma treatment

    SciTech Connect

    Schaefer, A.; Zielasek, V.; Baeumer, M.; Gevers, S.; Wollschlaeger, J.; Schroeder, T.; Falta, J.

    2011-02-07

    A cold radio frequency oxygen plasma treatment is demonstrated as a successful route to prepare clean, well-ordered, and stoichiometric PrO{sub 2} layers on silicon. High structural quality of these layers is shown by x-ray diffraction. So far unobserved spectral characteristics in Pr 3d x-ray photoelectron (XP) spectra of PrO{sub 2} are presented as a fingerprint for praseodymia in its highest oxidized state. They provide insight in the electronic ground state and the special role of praseodymia among the rare earth oxides. They also reveal that former XP studies suffered from a significant reduction at the surface.

  14. How far can we go? Quantum-chemical investigations of oxidation state +IX.

    PubMed

    Himmel, Daniel; Knapp, Carsten; Patzschke, Michael; Riedel, Sebastian

    2010-03-15

    The highest known oxidation state of any element is +VIII. After the recent discovery of Ir(VIII)O(4) under cryogenic conditions, we have investigated the stability of cationic species [MO(4)](+) (M=Rh,Ir,Mt). Such compounds would formally represent the new oxidation state +IX, which is experimentally unknown so far for the whole periodic table. [IrO(4)](+) is predicted to be the most promising candidate. The calculated spin-orbit (SO) coupling shows only minor effects on the stability of the iridium species, whereas SO-coupling increases enormously for the corresponding Eka-Iridium (Meitnerium) complexes and destabilizes these.

  15. Graphene oxide modification of plexciton states in the strong coupling limit

    NASA Astrophysics Data System (ADS)

    Fedele, Stefano; Murphy, Antony; Pollard, Robert; Rice, James

    2017-03-01

    We demonstrate that gold nanorod arrays support LSPR modes which coincide with Frankel excitons in an organic J-aggregate complex forming plexciton hybrid states when tuned to within the strong coupling limit. The addition of graphene oxide modifies the strong coupling resonance conditions and Rabi frequency. This demonstrates that the formation of exciton-plasmon plexciton states in the strong coupling limit can be modified and potentially controlled through the introduction of graphene oxide which can have implications for energy harvesting or biosensor device design.

  16. High oxidation state during formation of Martian nakhlites

    NASA Astrophysics Data System (ADS)

    Szymanski, Anja; Brenker, Frank E.; Palme, Herbert; El Goresy, Ahmed

    2010-01-01

    The oxygen fugacities recorded in the nakhlites Nakhla, Yamato-000593 (Y-000593), Lafayette, and NWA998 were studied by applying the Fe,Ti-oxide oxybarometer. Oxygen fugacities obtained cluster closely around the FMQ (Fayalite-Magnetite-Quartz) buffer (NWA998=FMQ-0.8 Y-000593=FMQ-0.7 Nakhla=FMQ Lafayette=FMQ+ 0.1). The corresponding equilibration temperatures are 810°C for Nakhla and Y-000593, 780°C for Lafayette and 710°C for NWA998. All nakhlites record oxygen fugacities significantly higher and with a tighter range than those determined for Martian basalts, i.e., shergottites whose oxygen fugacities vary from FMQ-1 to FMQ-4. It has been known for some time that nakhlites are different from other Martian meteorites in chemistry, mineralogy, and crystallization age. The present study adds oxygen fugacity to this list of differences. The comparatively large variation in fO2 recorded by shergottites was interpreted by Herd et al. (2002) as reflecting variable degrees of contamination with crustal fluids that would also carry a light rare earth element (REE)-enriched component. The high oxygen fugacities and the large light REE enrichment of nakhlites fit qualitatively in this model. In detail, however, it is found that the inferred contaminating phase in nakhlites must have been different from those in shergottites. This is supported by unique 182W/184W and 142Nd/144Nd ratios in nakhlites, which are distinct from other Martian meteorites. It is likely that the differences in fO2 between nakhlites and other Martian meteorites were established very early in the history of Mars. Parental trace element rich and trace element poor regions (reservoirs) of Mars mantle (Brandon et al. 2000) must have been kept isolated throughout Martian history. Our results further show significant differences in closure temperature among the different nakhlites. The observed range in equilibration temperatures together with similar fO2 values is attributable to crystallization of

  17. Light-induced metastable states in ferroelectric oxides

    NASA Astrophysics Data System (ADS)

    Liu, G. K.; Vikhnin, V. S.; Kapphan, S. E.

    2007-07-01

    New Raman scattering lines (at 463 cm-1 and at 156 cm-1) induced by strong enough optical pumping in nominally pure KTaO3 crystals are manifested. The model of such effect is proposed. This model is based on the light-induced formation of metastable polar clusters constructed from bi-polaronic excitons - Charge Transfer Vibronic Excitons (CTVEs) with their high degree alignment. The CTVEs are caused by photo-carriers with high local concentration which are trapped to local potential wells related with long-range defect fields. CTVE formation are realized in these potential wells due to significant easing of charge transfer fluctuations induced by photo-carrier screening effects. This model is effective also for explanation of giant dielectric constant inducing by strong illumination which was detected recently in KTaO3 and SrTiO3 by Japanese investigators [M. Takesada, T. Yagi, M. Itoh, S. Koshihara, J. Phys. Soc. Jpn. 72 (2003) 37; T. Hasegawa, S. Mouri, Y. Yamada, K. Tanaka, J. Phys. Soc. Jpn. 72 (2003) 41; I. Katayama, Y. Ichikawa, K. Tanaka, Phys. Rev. B 67 (2003) 100102(R)]. Another aspect of the present study was specific recombination luminescence of CTVEs which was investigated here with respect to the influence of additional IR pumping. The present investigation has led to experimental evidence of new, mainly non-linear CTVE with good defined metastable behavior. Such an essentially anharmonic CTVE with respect to charge transfer and lattice displacements was predicted recently in our work [V.S. Vikhnin, Solid State Commun. 127 (2003) 283]. Here, we present experimental evidence of the existence of a new type of exciton state.

  18. Conformational Toggling of Yeast Iso-1-Cytochrome c in the Oxidized and Reduced States

    PubMed Central

    Yang, Zhongzheng; Zhu, Jing; Ying, Tianlei; Jiang, Xianwang; Zhang, Xu; Wu, Houming; Liu, Maili; Tan, Xiangshi; Cao, Chunyang; Huang, Zhong-Xian

    2011-01-01

    To convert cyt c into a peroxidase-like metalloenzyme, the P71H mutant was designed to introduce a distal histidine. Unexpectedly, its peroxidase activity was found even lower than that of the native, and that the axial ligation of heme iron was changed to His71/His18 in the oxidized state, while to Met80/His18 in the reduced state, characterized by UV-visible, circular dichroism, and resonance Raman spectroscopy. To further probe the functional importance of Pro71 in oxidation state dependent conformational changes occurred in cyt c, the solution structures of P71H mutant in both oxidation states were determined. The structures indicate that the half molecule of cyt c (aa 50–102) presents a kind of “zigzag riveting ruler” structure, residues at certain positions of this region such as Pro71, Lys73 can move a big distance by altering the tertiary structure while maintaining the secondary structures. This finding provides a molecular insight into conformational toggling in different oxidation states of cyt c that is principle significance to its biological functions in electron transfer and apoptosis. Structural analysis also reveals that Pro71 functions as a key hydrophobic patch in the folding of the polypeptide of the region (aa 50–102), to prevent heme pocket from the solvent. PMID:22087268

  19. Sulfur-Bridged Terthiophene Dimers: How Sulfur Oxidation State Controls Interchromophore Electronic Coupling.

    PubMed

    Cruz, Chad D; Christensen, Peter R; Chronister, Eric L; Casanova, David; Wolf, Michael O; Bardeen, Christopher J

    2015-10-07

    Symmetric dimers have the potential to optimize energy transfer and charge separation in optoelectronic devices. In this paper, a combination of optical spectroscopy (steady-state and time-resolved) and electronic structure theory is used to analyze the photophysics of sulfur-bridged terthiophene dimers. This class of dimers has the unique feature that the interchromophore (intradimer) electronic coupling can be modified by varying the oxidation state of the bridging sulfur from sulfide (S), to sulfoxide (SO), to sulfone (SO2). Photoexcitation leads to the formation of a delocalized charge resonance state (S1) that relaxes quickly (<10 ps) to a charge-transfer state (S1*). The amount of charge-transfer character in S1* can be enhanced by increasing the oxidation state of the bridging sulfur group as well as the solvent polarity. The S1* state has a decreased intersystem crossing rate when compared to monomeric terthiophene, leading to an enhanced photoluminescence quantum yield. Computational results indicate that electrostatic screening by the bridging sulfur electrons is the key parameter that controls the amount of charge-transfer character. Control of the sulfur bridge oxidation state provides the ability to tune interchromophore interactions in covalent assemblies without altering the molecular geometry or solvent polarity. This capability provides a new strategy for the design of functional supermolecules with applications in organic electronics.

  20. Effect of oxidation state on Bi mineral speciation in oxidized and reduced granitoids from the Uetsu region, NE Japan

    NASA Astrophysics Data System (ADS)

    Izumino, Yuya; Maruoka, Teruyuki; Nakashima, Kazuo

    2016-06-01

    The relationship between bismuth (Bi) mineral speciation and redox state in three types of granitoids from the Uetsu region, northeast Japan is investigated. Electron microprobe analysis of Bi minerals, sphalerite, Mg-Fe-bearing carbonate minerals, and muscovite, as well as sulfur isotope analysis of sulfide minerals and microthermometric study of fluid inclusions reveal that Bi mineral speciation varies according to the redox state of the granitoids. For example, native bismuth and bismuthinite are abundant and Bi sulfosalts are rare in the lowest fS2 and fO2 mineralized zones of the reduced Iwafune granite (S-type, ilmenite-series) while Bi sulfosalts (Bi3+) are abundant and trace amounts of native bismuth (Bi0) and bismuthinite are found in the highest fS2 and fO2 mineralized zones of the oxidized Wasada granodiorite (I-type, magnetite-series). Bismuthinite is a major Bi mineral, and native bismuth and Bi sulfosalts occur in only minor amounts in the mineralized zones of the Nishitagawa granodiorite (I-type, ilmenite-series), which has intermediate fS2 and fO2 to that of the Iwafune and Wasada samples. Our study indicates that Bi mineral speciation related to granitic intrusive activity is controlled by the redox state of the magmatism, such that native bismuth is typical of reducing conditions, whereas Bi sulfosalts are typical of oxidizing conditions.

  1. Fragility of surface states and robustness of topological order in Bi2Se3 against oxidation.

    PubMed

    Wang, Xiaoxiong; Bian, Guang; Miller, T; Chiang, T-C

    2012-03-02

    Topological surface states are protected against local perturbations, but this protection does not extend to chemical reaction over the whole surface, as demonstrated by theoretical studies of the oxidation of Bi(2)Se(3) and its effects on the surface spin polarization and current. While chemisorption of O(2) largely preserves the topological surface states, reaction with atomic O removes the original surface states and yields two new sets of surface states. One set forms a regular Dirac cone but is topologically trivial. The other set, while topologically relevant, forms an unusual rounded Dirac cone. The details are governed by the hybridization interaction at the interface.

  2. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    NASA Astrophysics Data System (ADS)

    Baltrusaitis, Jonas; Mendoza-Sanchez, Beatriz; Fernandez, Vincent; Veenstra, Rick; Dukstiene, Nijole; Roberts, Adam; Fairley, Neal

    2015-01-01

    Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  3. The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

    PubMed Central

    Angelini, Francesco; Pagano, Francesca; Bordin, Antonella; Milan, Marika; Valenti, Valentina; Marullo, Antonino; Schirone, Leonardo; Palmerio, Silvia; Sciarretta, Sebastiano; Frati, Giacomo

    2017-01-01

    Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS) in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human's current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject's profile will be discussed. PMID:28607629

  4. The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System.

    PubMed

    Angelini, Francesco; Pagano, Francesca; Bordin, Antonella; Milan, Marika; Chimenti, Isotta; Peruzzi, Mariangela; Valenti, Valentina; Marullo, Antonino; Schirone, Leonardo; Palmerio, Silvia; Sciarretta, Sebastiano; Murdoch, Colin E; Frati, Giacomo; De Falco, Elena

    2017-01-01

    Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS) in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human's current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject's profile will be discussed.

  5. Methionine oxidation of monomeric lambda repressor: the denatured state ensemble under nondenaturing conditions.

    PubMed

    Chugha, Preeti; Sage, Harvey J; Oas, Terrence G

    2006-03-01

    Although poorly understood, the properties of the denatured state ensemble are critical to the thermodynamics and the kinetics of protein folding. The most relevant conformations to cellular protein folding are the ones populated under physiological conditions. To avoid the problem of low expression that is seen with unstable variants, we used methionine oxidation to destabilize monomeric lambda repressor and predominantly populate the denatured state under nondenaturing buffer conditions. The denatured ensemble populated under these conditions comprises conformations that are compact. Analytical ultracentrifugation sedimentation velocity experiments indicate a small increase in Stokes radius over that of the native state. A significant degree of alpha-helical structure in these conformations is detected by far-UV circular dichroism, and some tertiary interactions are suggested by near-UV circular dichroism. The characteristics of the denatured state populated by methionine oxidation in nondenaturing buffer are very different from those found in chemical denaturant.

  6. Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges

    NASA Astrophysics Data System (ADS)

    Ganduglia-Pirovano, M. Verónica; Hofmann, Alexander; Sauer, Joachim

    2007-06-01

    Defects at transition metal (TM) and rare earth (RE) oxide surfaces, neutral oxygen vacancies in particular, play a major role in a variety of technological applications. This is the motivation of numerous studies of partially reduced oxide surfaces. We review, discuss, and compare theoretical data for structural and electronic properties and energetic quantities related to the formation of oxygen defects at TM and RE oxide surfaces using TiO 2, ZrO 2, V 2O 5, and CeO 2 as examples. Bulk defects, as far as relevant for comparison with the properties of reduced surfaces, are briefly reviewed. Special attention is given to the fate of the electrons left in the system upon vacancy formation and the ability of state-of-the-art quantum-mechanical methods to provide reliable energies and an accurate description of the electronic structure of the partially reduced oxide systems.

  7. How different oxidation states of crystalline myoglobin are influenced by X-rays.

    PubMed

    Hersleth, Hans-Petter; Andersson, K Kristoffer

    2011-06-01

    X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

  8. Compositional and Oxidation State Zoning in Martian Pyroxene: Paradox or Process Indicator

    NASA Technical Reports Server (NTRS)

    Delaney, Jeremy S.; Dyar, M. D.

    2002-01-01

    Coordinated zoning studies of major, minor, trace elements and oxidation states in Martian minerals elucidate the magmatic evolution of QUE94201 and suggest an important role for olivine and volatile fluxing in a complex magmatic history. Additional information is contained in the original extended abstract.

  9. The Silver Complexes of Porphyrins, Corroles, and Carbaporphyrins: Silver in the Oxidation States II and III

    ERIC Educational Resources Information Center

    Bruckner, Christian

    2004-01-01

    Studies in relation to the silver complexes of porphyrins, corroles and carbaporphyrins are presented especially with relation to silver in the oxidation states II and III. It is seen that the Ag(sub III) complex was electrochemically readily and reversibly reduced to the corresponding Ag(sub II) complex, thus indicating that the complex could be…

  10. Theory of the electronic and structural properties of solid state oxides

    SciTech Connect

    Chelikowsky, J.R.

    1990-01-01

    Studies on electronic and structural properties of solid state oxides continued. This quarter, studies have concentrated on silica. Progress is discussed in the following sections: interatomic potentials and the structural properties of silica; chemical reactivity and covalent/metallic bonding on Si clusters; and surface and thermodynamic interatomic forces fields for silicon. 64 refs., 20 figs., 5 tabs. (CBS)

  11. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides

    PubMed Central

    Lehninger, Albert L.; Vercesi, Anibal; Bababunmi, Enitan A.

    1978-01-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca2+ and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca2+ is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as β-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca2+. Successive cycles of Ca2+ release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca2+-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca2+, mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. Images PMID:25436

  12. Iron Oxidation States of Matrix in Carbonaceous Chondrites Acfer 094 and MIL 07687

    NASA Astrophysics Data System (ADS)

    Vaccaro, E.; King, A. J.; Schofield, P. F.; Abyaneh, M. K.; Kaulich, B.; Russell, S. S.

    2016-08-01

    STXM Fe-oxidation state study in Acfer 094 and MIL 07687 matrix revealed high Fe3+/ΣFe ratios likely to be a primordial signature. Terrestrial weathering cannot be ruled out but is unlikely to have a pervasive effect throughout entire meteorites.

  13. The Silver Complexes of Porphyrins, Corroles, and Carbaporphyrins: Silver in the Oxidation States II and III

    ERIC Educational Resources Information Center

    Bruckner, Christian

    2004-01-01

    Studies in relation to the silver complexes of porphyrins, corroles and carbaporphyrins are presented especially with relation to silver in the oxidation states II and III. It is seen that the Ag(sub III) complex was electrochemically readily and reversibly reduced to the corresponding Ag(sub II) complex, thus indicating that the complex could be…

  14. Compositional and Oxidation State Zoning in Martian Pyroxene: Paradox or Process Indicator

    NASA Technical Reports Server (NTRS)

    Delaney, Jeremy S.; Dyar, M. D.

    2002-01-01

    Coordinated zoning studies of major, minor, trace elements and oxidation states in Martian minerals elucidate the magmatic evolution of QUE94201 and suggest an important role for olivine and volatile fluxing in a complex magmatic history. Additional information is contained in the original extended abstract.

  15. ENVIRONMENTAL VARIABLES CONTROLLING NITRIC OXIDE EMISSIONS FROM AGRICULTURAL SOILS IN THE SOUTHEAST UNITED STATES

    EPA Science Inventory

    Fluxes of nitric oxide (NO) were measured during the summer of 1994 (12 July to 11 August) in the Upper Coastal Plain of North Carolina in a continuing effort to characterize NO emissions from intensively managed agricultural soils in the southeastern United States. Previous work...

  16. Teaching the Properties of Chromium's Oxidation States with a Case Study Method

    ERIC Educational Resources Information Center

    Ozdilek, Zehra

    2015-01-01

    The purpose of this study was to investigate how a mixed-method case study affects pre-service science teachers' awareness of hexavalent chromium pollution and content knowledge about the properties of chromium's different oxidation states. The study was conducted in Turkey with 55 sophomores during the fall semester of 2013-2014. The students…

  17. Teaching the Properties of Chromium's Oxidation States with a Case Study Method

    ERIC Educational Resources Information Center

    Ozdilek, Zehra

    2015-01-01

    The purpose of this study was to investigate how a mixed-method case study affects pre-service science teachers' awareness of hexavalent chromium pollution and content knowledge about the properties of chromium's different oxidation states. The study was conducted in Turkey with 55 sophomores during the fall semester of 2013-2014. The students…

  18. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides.

    PubMed

    Lehninger, A L; Vercesi, A; Bababunmi, E A

    1978-04-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca(2+) and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca(2+) is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as beta-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca(2+). Successive cycles of Ca(2+) release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca(2+)-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca(2+), mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport.

  19. ENVIRONMENTAL VARIABLES CONTROLLING NITRIC OXIDE EMISSIONS FROM AGRICULTURAL SOILS IN THE SOUTHEAST UNITED STATES

    EPA Science Inventory

    Fluxes of nitric oxide (NO) were measured during the summer of 1994 (12 July to 11 August) in the Upper Coastal Plain of North Carolina in a continuing effort to characterize NO emissions from intensively managed agricultural soils in the southeastern United States. Previous work...

  20. Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution.

    PubMed

    Lee, M H; Kim, J Y; Kim, W H; Jung, E C; Jee, K Y

    2008-12-01

    The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO(3) and HClO(4). The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III) approximately Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9M HCl medium was applied to IAEA reference soils where the activity concentrations of (239,240)Pu and (238)Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

  1. Theoretical comparison of advanced methods for calculating nitrous oxide fluxes using non-steady state chambers

    USDA-ARS?s Scientific Manuscript database

    Several flux-calculation (FC) schemes are available for determining soil-to-atmosphere emissions of nitrous oxide (N2O) and other trace gases using data from non-steady-state flux chambers. Recently developed methods claim to provide more accuracy in estimating the true pre-deployment flux (f0) comp...

  2. Using carbon oxidation state and ecosystem oxidative ratio to understand terrestrial ecosystem response to elevated CO2

    NASA Astrophysics Data System (ADS)

    Hockaday, W. C.; Masiello, C. A.; Gallagher, M. E.

    2015-12-01

    Here we show that an easily-measured biogeochemical tracer, carbon oxidation state (Cox) can be used to understand ecosystem response to elevated atmospheric CO2 concentrations. We briefly review the use of Cox in understanding C sink estimates, and its role in understanding the coupled nature of carbon and oxygen cycles, which derives from its relationship with ecosystem oxidative ratio (OR). The Cox of a carbon pool provides an integrated measure of all processes that create and destroy organic matter (e.g. photosynthesis, respiration, fire) and therefore, can be used to estimate the oxidative ratio (O2/CO2) of biosphere-atmosphere exchange. Our preliminary data suggest that the OR of temperate hardwood forest and grassland ecosystems are influenced by atmospheric CO2 concentration. The variation in ecosystem Cox with atmospheric CO2 concentration suggest that OR is not a conservative property of terrestrial ecosystems on annual or decadal timescales. In the grassland ecosystem, the Cox of plant biomass increased by as much as 50% across a CO2 concentration gradient of 190 ppm, but the response was highly dependent upon soil properties. In the temperate forest, the Cox of the soil C pool increased by 40% after 9 seasons of CO2 enrichment (by 175 ppm). We will discuss our interpretation of Cox as a proxy and its potential use in studies of coupled O2 and CO2 cycling.

  3. Oxidation state specific analysis of arsenic species in tissues of wild-type and arsenic (+3 oxidation state) methyltransferase-knockout mice.

    PubMed

    Currier, Jenna M; Douillet, Christelle; Drobná, Zuzana; Stýblo, Miroslav

    2016-11-01

    Arsenic methyltransferase (As3mt) catalyzes the conversion of inorganic arsenic (iAs) to its methylated metabolites, including toxic methylarsonite (MAs(III)) and dimethylarsinite (DMAs(III)). Knockout (KO) of As3mt was shown to reduce the capacity to methylate iAs in mice. However, no data are available on the oxidation states of As species in tissues of these mice. Here, we compare the oxidation states of As species in tissues of male C57BL/6 As3mt-KO and wild-type (WT) mice exposed to arsenite (iAs(III)) in drinking water. WT mice were exposed to 50mg/L As and As3mt-KO mice that cannot tolerate 50mg/L As were exposed to 0, 15, 20, 25 or 30mg/L As. iAs(III) accounted for 53% to 74% of total As in liver, pancreas, adipose, lung, heart, and kidney of As3mt-KO mice; tri- and pentavalent methylated arsenicals did not exceed 10% of total As. Tissues of WT mice retained iAs and methylated arsenicals: iAs(III), MAs(III) and DMAs(III) represented 55%-68% of the total As in the liver, pancreas, and brain. High levels of methylated species, particularly MAs(III), were found in the intestine of WT, but not As3mt-KO mice, suggesting that intestinal bacteria are not a major source of methylated As. Blood of WT mice contained significantly higher levels of As than blood of As3mt-KO mice. This study is the first to determine oxidation states of As species in tissues of As3mt-KO mice. Results will help to design studies using WT and As3mt-KO mice to examine the role of iAs methylation in adverse effects of iAs exposure. Copyright © 2016. Published by Elsevier B.V.

  4. Oxidation state specific analysis of arsenic species in tissues of wild-type and arsenic (+3 oxidation state) methyltransferase-knockout mice

    PubMed Central

    Currier, Jenna M.; Douillet, Christelle; Drobná, Zuzana; Stýblo, Miroslav

    2017-01-01

    Arsenic methyltransferase (As3mt) catalyzes the conversion of inorganic arsenic (iAs) to its methylated metabolites, including toxic methylarsonite (MAsIII) and dimethylarsinite (DMAsIII). Knockout (KO) of As3mt was shown to reduce the capacity to methylate iAs in mice. However, no data are available on the oxidation states of As species in tissues of these mice. Here, we compare the oxidation states of As species in tissues of male C57BL/6 As3mt-KO and wild-type (WT) mice exposed to arsenite (iAsIII) in drinking water. WT mice were exposed to 50 mg/L As and As3mt-KO mice that cannot tolerate 50 mg/L As were exposed to 0, 15, 20, 25 or 30 mg/L As. iAsIII accounted for 53% to 74% of total As in liver, pancreas, adipose, lung, heart, and kidney of As3mt-KO mice; tri- and pentavalent methylated arsenicals did not exceed 10% of total As. Tissues of WT mice retained iAs and methylated arsenicals: iAsIII, MAsIII and DMAsIII represented 55%–68% of the total As in the liver, pancreas, and brain. High levels of methylated species, particularly MAsIII, were found in the intestine of WT, but not As3mt-KO mice, suggesting that intestinal bacteria are not a major source of methylated As. Blood of WT mice contained significantly higher levels of As than blood of As3mt-KO mice. This study is the first to determine oxidation states of As species in tissues of As3mt-KO mice. Results will help to design studies using WT and As3mt-KO mice to examine the role of iAs methylation in adverse effects of iAs exposure. PMID:28007165

  5. Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

    SciTech Connect

    Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean - Francois; Ams, David; Richmann, M. K.; Khaing, H.; Swanson, J. S.

    2010-12-10

    The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

  6. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    SciTech Connect

    Liang, Wenchuan

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  7. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    PubMed

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-05

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  8. Electronic Structure and Oxidation State Changes in the Mn4Ca Cluster of Photosystem II

    SciTech Connect

    Yano, Junko; Pushkar, Yulia; Messinger, Johannes; Bergmann, Uwe; Glatzel, Pieter; Yachandra, Vittal K

    2007-08-03

    Oxygen-evolving complex (Mn4Ca cluster) of Photosystem II cycles through five intermediate states (Si-states, i =0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn4(III2,IV2) and Mn4(III,IV3) for S1 and S2 states, while it is still controversial for the S0 and S3 states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn4Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mncomplexes. The spectral changes in the Mn 1s2p3/2 RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S0 to S1, and S1 to S2 transitions is twice as large as that during the S2 to S3 transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms.

  9. Electronic Structure and Oxidation State Changes in the Mn (4) Ca Cluster of Photosystem II

    SciTech Connect

    Yano, J.; Pushkar, Y.; Messinger, J.; Bergmann, U.; Glatzel, P.; Yachandra, V.K.; /SLAC

    2012-08-17

    Oxygen-evolving complex (Mn{sub 4}Ca cluster) of Photosystem II cycles through five intermediate states (S{sub i}-states, i = 0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn{sub 4}(III{sub 2},IV{sub 2}) and Mn{sub 4}(III,IV{sub 3}) for S{sub 1} and S{sub 2} states, while it is still controversial for the S{sub 0} and S{sub 3} states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn{sub 4}Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mn complexes. The spectral changes in the Mn 1s2p{sub 3/2} RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S{sub 0} to S{sub 1}, and S{sub 1} to S{sub 2} transitions is twice as large as that during the S{sub 2} to S{sub 3} transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms.

  10. Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

    SciTech Connect

    Sallis, S.; Williams, D. S.; Butler, K. T.; Walsh, A.; Quackenbush, N. F.; Junda, M.; Podraza, N. J.; Fischer, D. A.; Woicik, J. C.; White, B. E.; Piper, L. F. J.

    2014-06-09

    The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

  11. Metal ion oxidation state assignment based on coordinating ligand hyperfine interaction.

    PubMed

    Oyala, Paul H; Stich, Troy A; Britt, R David

    2015-04-01

    In exchange-coupled mixed-valence spin systems, the magnitude and sign of the effective ligand hyperfine interaction (HFI) can be useful in determining the formal oxidation state of the coordinating metal ion, as well as provide information about the coordination geometry. This is due to the fact that the observed ligand HFI is a function of the projection factor (Clebsch-Gordon coefficient) that maps the site spin value S i of the local paramagnetic center onto the total spin of the exchange-coupled system, S T. Recently, this relationship has been successfully exploited in identifying the oxidation state of the Mn ion coordinated by the sole nitrogenous ligand to the oxygen-evolving complex in certain states of photosystem II. The origin and evolution of these efforts is described.

  12. Theory of the electronic and structural properties of solid state oxides. Annual technical report 1993

    SciTech Connect

    Chelikowsky, J.R.

    1993-06-01

    Emphasis has been on the electronic materials: silica, titania, and ruthenia. Fundamental interest centered on nature of microstructure of these solids in the amorphous state, or mixed oxide state. New theoretical techniques have been implemented to examine such issues, based on ab initio pseudopotential methods and interatomic potentials. Some areas examined under this project are: (1) Nature of the amorphization transformation of quartz under pressure. Specific focus is on the microscopic nature of the amorphous material and the driving forces for amorphization. (2) Equation of states of crystalline silica polymorphs. (3) Elastic anomalies in silica. In particular, the existence of a ``negative`` Poisson ratio in high temperature, low density forms of crystalline silica. (4) Optical and structural properties of titania and mixed oxides such as Ru{sub x}Ti{sub 1-x}O{sub 2}.

  13. Influence of oxidation state on water solubility of Si nanoparticles prepared by laser ablation in water

    NASA Astrophysics Data System (ADS)

    Ryabchikov, Yu. V.; Al-Kattan, A.; Chirvony, V.; Sanchez-Royo, J. F.; Sentis, M.; Timoshenko, V. Yu.; Kabashin, A. V.

    2017-02-01

    Femtosecond laser fragmentation from preliminarily prepared water-dispersed Si microcolloids was used to synthesize bare (ligand-free) spherical silicon nanoparticles (Si-NPs) with low size dispersion and controllable mean size from a few nm to several tens of nm. In order to control the oxidation state of Si-NPs, the fragmentation was performed in normal oxygen-saturated water (oxygen-rich conditions) or in water disoxygenated by pumping with noble gases (Ag, He) before and during the experiment (oxygen-free conditions). XPS and TEM studies revealed that Si-NPs were composed of Si nanocrystals with inclusions of silicon oxide species, covered by SiOx (1 < x < 2) shell, while the total oxide content depended whether Si-NPs were prepared in oxygen-rich or oxygen-free conditions. When placed into a dialysis box, waterdispersed Si-NPs rapidly dissolved, which was evidenced by TEM data. In this case, NPs prepared under oxygen-rich conditions demonstrated much faster dissolution kinetics and their complete disappearance after 7-10 days, while the dissolution process of less oxidized counterparts could last much longer (25-30 days). Much fast dissolution kinetics of more oxidized Si-NPs was attributed to more friable structure of nanoparticle core due to the presence of numerous oxidation-induced defects. Laser-synthesized Si-NPs are of paramount importance for biomedical applications.

  14. Plutonium distribution and oxidation states in a reactor leaching ponds system

    SciTech Connect

    Ibrahim, S.; Culp, T. )

    1989-10-01

    Concentrations of 239,240Pu and 238Pu in water, net plankton (algal material), suspended particulates and sediment, as well as Pu oxidation states in filtered water, were determined in a test reactor leaching ponds system in southeastern Idaho. The highest Pu concentration in the ponds system was found in net plankton, and concentrations varied significantly between sampling dates. Plutonium Concentration Ratios (CR) for plankton ranged from 3 X 10(4) to 4 X 10(5). The lowest Pu concentration was found in filtered water, primarily because of the absence of complexing agents. The majority of Pu in filtered water was in true solution (60-87%) or present in colloidal particles smaller than 0.22 micron. Plutonium association with sediment was inversely related to particle size. The environmental distribution coefficients (Kd) for Pu ranged from 1.6 X 10(4) to 1.2 X 10(5) reflecting the importance of sediments as the main reservoir for Pu in the ponds system. No significant differences were noted between CR or Kd values for 239,240Pu and 238Pu. The reduced Pu oxidation states (III and IV) fractions ranged from 57% to 71% of the total dissolved Pu in water. This is in contrast with oxidation states distribution from other large aquatic systems (Great Lakes and the Irish Sea) where Pu is predominately in oxidized (V and VI) forms.

  15. Oxidation states of iron in the terrestrial planets: Evidence and implications for accretion models

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.; Harris, S. L.

    1985-01-01

    Analyses of Mars spectra reveal that primary minerals may be more iron rich than average basalts on Earth, and the oxidation state of iron in the pyroxines suggests equally high or higher oxygen fugacities on Mars than Earth. Analysis of Mercury spectra reveal that silicate iron contents are substantially lower than those on Mars. Mercury, however, probably has a substantial iron core. This is consistent with a lower oxidation state of iron on Mercury than on Mars. These findings are consistent with predictions of models of equilibrium condensation and homogeneous accretion. Those models predict that Mercury would have negligible Fe(2+) in silicates (Fe/Fe+Mg approx. 0.5). For Mercury iron should be virtually all metallic, while for Mars the iron would be all oxidized as FeS and silicate. Surface measurements of Fe/Fe+Mg on Venus, Earth, and Mars further support the predicted relative increase in Fe/Fe+Mg ratio (increased oxidation state) with distance from the Sun. The implied high oxygen fugacities on Mars (Fe(3+) in silicates) provide additional consistence with the model predictions.

  16. Oxidation state, bioavailability & biochemical pathway define the fate of carbon in soil

    NASA Astrophysics Data System (ADS)

    Kuzyakov, Yakov; Apostel, Carolin; Gunina, Anna; Herrmann, Anke M.; Dippold, Michaela

    2015-04-01

    Numerous experiments under laboratory and field conditions analyzed microbial utilization and mean residence time (MRT) of carbon (C) from plant and microbial residues as well as root exudates in soil. Most of these studies tested the effects of various environmental factors, such as temperature, soil moisture, texture etc. on these parameters. However, only a few studies compared the properties of the substances themselves and there is no conceptual framework based on biochemical pathways. We hypothesize that the fate of C from organic substances in soil strongly depends on the first step of their microbial utilization, specifically, on biochemical pathway and initial C oxidation state, as well as its bioavailability in soils, defined by its hydrophobicity and molecular weight. Here we introduce and evaluate a new conceptual framework based on the following parameters: 1) C oxidation state, 2) molecular weight and hydrophobicity, 3) initial biochemical pathway of a substance class in microbial cells. To assess these parameters, two databases were prepared based on the literature and own studies. The first database included only the studies with 14C or 13C position specific labeled sugars, amino acids, carboxylic acids, phenols and lipids in soil. This database allowed us to analyze microbial utilization and mineralization of organics to CO2 depending on their C oxidation state (OS) and on functional groups. Additionally, we calculated data on the bond electronegativity of all compounds investigated in these studies. The second data base included the results of 14C and 13C studies with uniformly labeled substances of various classes. This database considered the free enthalpie (Delta H) per C unit from a variety of substrates differing in their aromaticity, hydrophobicity/electronegativity and location of the substance on the van Krevelen diagram. In addition, we calculated the hydrophobicity from the electronegativity of the individual bonds and recorded their

  17. The Miniaturized Mössbauer Spectrometer MIMOS II for the Asteroid Redirect Mission (ARM): Quantitative Iron Mineralogy and Oxidation States

    NASA Astrophysics Data System (ADS)

    Schröder, C.; Klingelhöfer, G.; Morris, R. V.; Yen, A. S.; Renz, F.; Graff, T. G.

    2016-10-01

    We propose a fully-qualified flight-spare Mössbauer spectrometer for the asteroid redirect mission to identify Fe-bearing mineral phases and Fe oxidation states, and for quantitative distribution of Fe between mineral phases and oxidation states.

  18. Extracellular redox state: refining the definition of oxidative stress in aging.

    PubMed

    Jones, Dean P

    2006-01-01

    Oxidative stress in aging can result from an imbalance of prooxidants and antioxidants with excessive, destructive free radical chemistry. Thiol systems are important in the control of these processes, both by protecting against damage and serving in redox signaling mechanisms to sense danger and repair the damage. Studies by a number of research groups in collaboration with the Emory Clinical Biomarkers Laboratory show that the redox state of the central tissue antioxidant, glutathione (GSH), can be measured in human plasma and provides a quantitative systemic indicator of oxidative stress. Plasma GSH/GSSG redox in humans becomes oxidized with age, in response to chemotherapy, as a consequence of cigarette smoking, and in association with common age-related diseases (e.g., type 2 diabetes, cardiovascular disease). However, the GSH/GSSG redox is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, and the Cys/CySS redox varies with age in a pattern that is distinct from that of GSH/GSSG redox. Furthermore, in vitro studies show that variation in Cys/CySS redox over the range found in vivo affects signaling pathways, which control cell proliferation and oxidant-induced apoptosis. The results point to the conclusion that free radical scavenging antioxidants are of increased importance when thiol/disulfide redox states are oxidized. Because thiol/disulfide redox states, per se, function in redox signaling and control as well as antioxidant protection, GSH/GSSG and Cys/CySS redox states may provide central parameters to link environmental influences and progression of changes associated with aging.

  19. Synthesis, structure, and reactivity of high oxidation state silver fluorides and related compounds

    SciTech Connect

    Lucier, George Michael

    1995-05-01

    This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF6-, RuF6-, or RhF6-, Ag(III) solv effectively oxidizes the anions to release the neutral hexafluorides. Such reactivity ranks cationic Ag(III) as the most powerfully oxidizing chemical agent known as far. Unlike its trivalent relative Ag (II) solv is thermodynamically stable in acid aHF. Nevertheless, it oxidizes IrF6- to IrF6 at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag2+ (MF6-2 salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag2+. The anion must also be a poor F- donor; otherwise, either AgF+ salts or AgF2 are generated.

  20. Simple relationship between oxidation state and electron affinity in gas-phase metal-oxo complexes.

    PubMed

    Waller, Sarah E; Ray, Manisha; Yoder, Bruce L; Jarrold, Caroline Chick

    2013-12-19

    The photoelectron spectra of WO3H(-) and WO2F(-) are presented and analyzed in the context of a series of previous similar measurements on MO(y)(-) (M = Mo, W; y = 0-3), MO4H(-) and AlMOy(-) (y ≤ 4) complexes. The electronic structures of the WO3H and WO2F anion and neutral complexes were investigated using the B3LYP hybrid density functional method. The spectra of WO3H(-), WO2F(-), and previously measured AlWO3(-) photoelectron spectra show that the corresponding neutrals, in which the transition metal centers are all in a +5 oxidation state, have comparable electron affinities. In addition, the electron affinities fit the general trend of monotonically increasing electron affinity with oxidation state, in spite of the WO3H(-), WO2F(-), and AlWO3(-) having closed shell ground states, suggesting that the oxidation state of the metal atom has more influence than shell closing on the electron affinity of these transition metal-oxo complexes. Results of DFT calculations suggest that the neutrals are pyramidal and the anions are planar. However, the barriers for inversion on the neutral surface are low, and attempts to generate simple Franck-Condon simulations based on simple normal coordinate displacement, ignoring the effects of inversion, are inadequate.

  1. Metallic quantum well states in artificial structures of strongly correlated oxide.

    PubMed

    Yoshimatsu, K; Horiba, K; Kumigashira, H; Yoshida, T; Fujimori, A; Oshima, M

    2011-07-15

    The quantum confinement of strongly correlated electrons in artificial structures provides a platform for studying the behavior of correlated Fermi-liquid states in reduced dimensions. We report the creation and control of two-dimensional electron-liquid states in ultrathin films of SrVO(3) grown on Nb:SrTiO(3) substrates, which are artificial oxide structures that can be varied in thickness by single monolayers. Angle-resolved photoemission from the SrVO(3)/Nb:SrTiO(3) samples shows metallic quantum well states that are adequately described by the well-known phase-shift quantization rule. The observed quantum well states in SrVO(3) ultrathin films exhibit distinctive features--such as orbital-selective quantization originating from the anisotropic orbital character of the V 3d states and unusual band renormalization of the subbands near the Fermi level--that reflect complex interactions in the quantum well.

  2. Interplay between strain, defect charge state, and functionality in complex oxides

    NASA Astrophysics Data System (ADS)

    Aschauer, Ulrich; Spaldin, Nicola A.

    2016-07-01

    We use first-principles calculations to investigate the interplay between strain and the charge state of point defect impurities in complex oxides. Our work is motivated by recent interest in using defects as active elements to provide novel functionality in coherent epitaxial films. Using oxygen vacancies as model point defects, and CaMnO3 and MnO as model materials, we calculate the changes in internal strain caused by changing the charge state of the vacancies, and conversely the effect of strain on charge-state stability. Our results show that the charge state is a degree of freedom that can be used to control the interaction of defects with strain and hence the concentration and location of defects in epitaxial films. We propose the use of field-effect gating to reversibly change the charge state of defects and hence the internal strain and corresponding strain-induced functionalities.

  3. Screening of dietary antioxidants against mitochondria-mediated oxidative stress by visualization of intracellular redox state.

    PubMed

    Maharjan, Sunita; Sakai, Yasuyoshi; Hoseki, Jun

    2016-01-01

    Mitochondrial impairment and the resulting generation of reactive oxygen species (ROS) have been associated with aging and its related pathological conditions. Recently, dietary antioxidants have gained significant attention as potential preventive and therapeutic agents against ROS-generated aging and pathological conditions. We previously demonstrated that food-derived antioxidants prevented intracellular oxidative stress under proteasome inhibition conditions, which was attributed to mitochondrial dysfunction and ROS generation, followed by cell death. Here, we further screened dietary antioxidants for their activity as redox modulators by visualization of the redox state using Redoxfluor, a fluorescent protein redox probe. Direct alleviation of ROS by antioxidants, but not induction of antioxidative enzymes, prevented mitochondria-mediated intracellular oxidation. The effective antioxidants scavenged mitochondrial ROS and suppressed cell death. Our study indicates that redox visualization under mitochondria-mediated oxidative stress is useful for screening potential antioxidants to counteract mitochondrial dysfunction, which has been implicated in aging and the pathogenesis of aging-related diseases.

  4. Morphology dependence of interfacial oxidation states of gallium arsenide under near ambient conditions

    SciTech Connect

    Zhang, Xueqiang; Lamere, Edward; Ptasinska, Sylwia; Liu, Xinyu; Furdyna, Jacek K.

    2014-05-05

    The manipulation of semiconductor surfaces by tuning their electronic properties and surface chemistry is an essential ingredient for key applications in areas such as electronics, sensors, and photovoltaic devices. Here, in-situ surface reactions on gallium arsenide (GaAs) are monitored for two morphologies: a simple planar crystalline surface with (100) orientation and an ensemble of GaAs nanowires, both exposed to oxygen environment. A variety of oxide surface species, with a significant enhancement in oxidation states in the case of nanowires, are detected via near ambient pressure X-ray photoelectron spectroscopy. This enhancement in oxidation of GaAs nanowires is due to their higher surface area and the existence of more active sites for O{sub 2} dissociation.

  5. Volatile organic compounds in indoor environment and photocatalytic oxidation: state of the art.

    PubMed

    Wang, Shaobin; Ang, H M; Tade, Moses O

    2007-07-01

    Volatile organic compounds (VOCs) are the major pollutants in indoor air, which significantly impact indoor air quality and thus influencing human health. A long-term exposure to VOCs will be detrimental to human health causing sick building syndrome (SBS). Photocatalytic oxidation of VOCs is a cost-effective technology for VOCs removal compared with adsorption, biofiltration, or thermal catalysis. In this paper, we review the current exposure level of VOCs in various indoor environment and state of the art technology for photocatalytic oxidation of VOCs from indoor air. The concentrations and emission rates of commonly occurring VOCs in indoor air are presented. The effective catalyst systems, under UV and visible light, are discussed and the kinetics of photocatalytic oxidation is also presented.

  6. Oxide-free InAs(111)A interface in metal-oxide-semiconductor structure with very low density of states prepared by anodic oxidation

    SciTech Connect

    Valisheva, N. A. Aksenov, M. S.; Golyashov, V. A.; Levtsova, T. A.; Kovchavtsev, A. P.; Gutakovskii, A. K.; Tereshchenko, O. E.; Khandarkhaeva, S. E.; Kalinkin, A. V.; Prosvirin, I. P.; Bukhtiyarov, V. I.

    2014-10-20

    In this letter, we present structural, compositional, and electrical characteristics of anodic oxide layer-based metal-oxide-semiconductor (MOS) capacitors on n-type InAs(111)A, along with the effect of a thin fluorinated interfacial passivation layer. Electrochemical oxidation in acid electrolyte with addition of fluorine (NH{sub 4}F) led to the formation of oxygen free well-ordered wide gap fluorinated interfacial layer at InAs(111)A with the fixed charge (Q{sub fix}) and density of interface states (D{sub it}) in the range of (4–6) × 10{sup 10 }cm{sup −2} and (2–12) × 10{sup 10 }eV{sup −1 }cm{sup −2}, respectively. We found that MOS capacitors showed excellent capacitance-voltage characteristics with very small frequency dispersion (<1% and <15 mV). Fluorinated interfacial layer consists of crystalline isostructural compound with the InAs substrate, which remains intact with the atomic smoothness and sharpness that explain unpinned behavior of the Fermi level.

  7. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

    USGS Publications Warehouse

    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  8. Exploring the Role of Adsorption and Surface State on the Hydrophobicity of Rare Earth Oxides.

    PubMed

    Lundy, Ross; Byrne, Conor; Bogan, Justin; Nolan, Kevin; Collins, Maurice N; Dalton, Eric; Enright, Ryan

    2017-04-19

    Rare earth oxides (REOs) are attracting attention for use as cost-effective, high-performance dropwise condensers because of their favorable thermal properties and robust nature. However, to engineer a suitable surface for industrial applications, the mechanism governing wetting must be first fully elucidated. Recent studies exploring the water-wetting state of REOs have suggested that these oxides are intrinsically hydrophobic owing to the unique electronic structure of the lanthanide series. These claims have been countered with evidence that they are inherently hydrophilic and that adsorption of contaminants from the environment is responsible for the apparent hydrophobic nature of these surfaces. Here, using X-ray photoelectron spectroscopy and dynamic water contact angle measurements, we provide further evidence to show that REOs are intrinsically hydrophilic, with ceria demonstrating advancing water contact angles of ≈6° in a clean surface state and similar surface energies to two transition metal oxides (≳72 mJ/m(2)). Using two model volatile species, it is shown that an adsorption mechanism is responsible for the apparent hydrophobic property observed in REOs as well as in transition metal oxides and silica. This is correlated with the screening of the polar surface energy contribution of the underlying oxide with apparent surface energies reduced to <40 mJ/m(2) for the case of nonane adsorption. Moreover, we show that the degree of surface hydroxylation plays an important role in the observed contact angle hysteresis with the receding contact angle of ceria increasing from ∼10° to 45° following thermal annealing in an inert atmosphere. Our findings suggest that high atomic number metal oxides capable of strongly adsorbing volatile species may represent a viable paradigm toward realizing robust surface coating for industrial condensers if certain challenges can be overcome.

  9. Metal Oxide Nanoparticles: The Importance of Size, Shape, Chemical Composition, and Valence State in Determining Toxicity

    NASA Astrophysics Data System (ADS)

    Dunnick, Katherine

    Nanoparticles, which are defined as a structure with at least one dimension between 1 and 100 nm, have the potential to be used in a variety of consumer products due to their improved functionality compared to similar particles of larger size. Their small size is associated with increased strength, improved catalytic properties, and increased reactivity; however, their size is also associated with increased toxicity in vitro and in vivo. Numerous toxicological studies have been conducted to determine the properties of nanomaterials that increase their toxicity in order to manufacture new nanomaterials with decreased toxicity. Data indicates that size, shape, chemical composition, and valence state of nanomaterials can dramatically alter their toxicity profile. Therefore, the purpose of this dissertation was to determine how altering the shape, size, and chemical composition of various metal oxide nanoparticles would affect their toxicity. Metal oxides are used in variety of consumer products, from spray-sun screens, to food coloring agents; thus, understanding the toxicity of metal oxides and determining which aspects affect their toxicity may provide safe alternatives nanomaterials for continued use in manufacturing. Tungstate nanoparticles toxicity was assessed in an in vitro model using RAW 264.7 cells. The size, shape, and chemical composition of these nanomaterials were altered and the effect on reactive oxygen species and general cytotoxicity was determined using a variety of techniques. Results demonstrate that shape was important in reactive oxygen species production as wires were able to induce significant reactive oxygen species compared to spheres. Shape, size, and chemical composition did not have much effect on the overall toxicity of these nanoparticles in RAW 264.7 cells over a 72 hour time course, implicating that the base material of the nanoparticles was not toxic in these cells. To further assess how chemical composition can affect toxicity

  10. Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

    NASA Astrophysics Data System (ADS)

    Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

    2017-04-01

    Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for

  11. Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

    NASA Astrophysics Data System (ADS)

    Kao, Wei-Chieh

    Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

  12. Size- and support-dependent evolution of the oxidation state and structure by oxidation of subnanometer cobalt clusters.

    PubMed

    Yin, Chunrong; Zheng, Fan; Lee, Sungsik; Guo, Jinghua; Wang, Wei-Cheng; Kwon, Gihan; Vajda, Viktor; Wang, Hsien-Hau; Lee, Byeongdu; DeBartolo, Janae; Seifert, Sönke; Winans, Randall E; Vajda, Stefan

    2014-09-18

    Size-selected subnanometer cobalt clusters with 4, 7, and 27 cobalt atoms supported on amorphous alumina and ultrananocrystalline diamond (UNCD) surfaces were oxidized after exposure to ambient air. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) and near-edge X-ray absorption fine structure (NEXAFS) were used to characterize the clusters revealed a strong dependency of the oxidation state and structure of the clusters on the surface. A dominant Co(2+) phase was identified in all samples. However, XANES analysis of cobalt clusters on UNCD showed that ∼10% fraction of a Co(0) phase was identified for all three cluster sizes and about 30 and 12% fraction of a Co(3+) phase in 4, 7, and 27 atom clusters, respectively. In the alumina-supported clusters, the dominating Co(2+) component was attributed to a cobalt aluminate, indicative of a very strong binding to the support. NEXAFS showed that in addition to strong binding of the clusters to alumina, their structure to a great extent follows the tetrahedral morphology of the support. All supported clusters were found to be resistant to agglomeration when exposed to reactive gases at elevated temperatures and atmospheric pressure.

  13. Size- and Support-Dependent Evolution of the Oxidation State and Structure by Oxidation of Subnanometer Cobalt Clusters

    SciTech Connect

    Yin, Chunrong; Zheng, Fan; Lee, Sungsik; Guo, Jinghua; Wang, Wei-Cheng; Kwon, Gihan; Vajda, Viktor; Wang, Hsien-Hau; Lee, Byeongdu; DeBartolo, Janae; Seifert, Sönke; Winans, Randall E.; Vajda, Stefan

    2014-09-18

    Size-selected subnanometer cobalt clusters with 4, 7 and 27 cobalt atoms supported on amorphous alumina and ultrananocrystalline diamond (UNCD) surfaces were oxidized after exposure to ambient air. Grazing incidence X-ray absorption near edge spectroscopy (GIXANES) and near edge X-ray absorption fine structure (NEXAFS) used to characterize the clusters revealed a strong dependency of the oxidation state and structure of the clusters on the surface. A dominant Co2+ phase was identified in all samples. However, form XANES analysis, on UNCD about 10% fraction of Co0 phase was identified for all three cluster sizes and about 30% and 12% fraction of Co3+ phase in 4, 7 and 27 atoms, respectively. In the alumina-supported clusters, the dominating Co2+ component was attributed to cobalt aluminate, indicative of a very strong binding to the support. NEXAFS showed that in addition to strong binding of the clusters to alumina, their structure in great extent follows the tetrahedral morphology of the support. The supported clusters of all three sizes were found resistant to agglomeration when exposed to reactive gases at elevated temperatures and atmospheric pressure.

  14. Oxidation state of the lithospheric mantle beneath Diavik diamond mine, central Slave craton, NWT, Canada

    NASA Astrophysics Data System (ADS)

    Creighton, Steven; Stachel, Thomas; Eichenberg, Dave; Luth, Robert W.

    2010-05-01

    Oxygen fugacity ( fO2) conditions were determined for 29 peridotite xenoliths from the A154-North and A154-South kimberlites of the Diavik diamond mine using the newly developed flank method modified specifically for measuring Fe3+ in mantle-derived pyropic garnets. The results indicate that the garnet-bearing lithospheric mantle beneath the central Slave craton is vertically layered with respect to oxidation state. The shallow (<140 km), “ultra-depleted” layer is the most oxidized section of garnet-bearing subcratonic mantle thus far measured, up to one log unit more oxidizing relative to the FMQ buffer [Δlog fO2 (FMQ) + 1]. The lower, more fertile layer has fO2 conditions that extend down to Δlog fO2 (FMQ) - 3.8, consistent with xenolith suites from other localities worldwide. Based on trace element concentrations in garnets, two distinct metasomatic events affected the mantle lithosphere at Diavik. An oxidized fluid imparted sinusoidal chondrite-normalized REE patterns on garnets throughout the entire depth range sampled. In contrast, a reducing melt metasomatic event affected only the lower portion of the lithospheric mantle. The fO2 state of the Diavik mantle sample suggests that diamond formation occurred by reduction of carbonate by fluids arising from beneath the lithosphere.

  15. Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

    DOE PAGES

    Bondi, Robert J.; Marinella, Matthew J.

    2015-02-28

    First-principles density-functional theory (DFT) calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (VOn; n=0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta2O5) and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. VOn of all oxidation states preferentially segregate at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta2O5, VO0 are characterized by structural contraction and electron density localization, while VO2+ promote structural expansion andmore » are depleted of electron density. In contrast, interfacial VO0 and VO2+ show nearly indistinguishable ionic and electronic signatures indicative of a reduced VO center. Interfacial VO2+ extract electron density from metallic Ta indicating VO2+ is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.« less

  16. Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

    SciTech Connect

    Bondi, Robert J. Marinella, Matthew J.

    2015-02-28

    First-principles density-functional theory calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (V{sub O}{sup n}; n = 0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta{sub 2}O{sub 5}), and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. V{sub O}{sup n} of all oxidation states preferentially segregates at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta{sub 2}O{sub 5}, V{sub O}{sup 0} is characterized by structural contraction and electron density localization, while V{sub O}{sup 2+} promotes structural expansion and is depleted of electron density. In contrast, interfacial V{sub O}{sup 0} and V{sub O}{sup 2+} show nearly indistinguishable ionic and electronic signatures indicative of a reduced V{sub O} center. Interfacial V{sub O}{sup 2+} extracts electron density from metallic Ta, indicating that V{sub O}{sup 2+} is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.

  17. Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Vinit; Krogel, Jaron T.; Kent, P. R. C.; Reboredo, Fernando A.

    One of the critical scientific challenges of contemporary research is to obtain an accurate theoretical description of the electronic properties of strongly correlated systems such as transition metal oxides and rare-earth compounds, since state-of-art ab-initio methods based on approximate density functionals are not always sufficiently accurate. Quantum Monte Carlo (QMC) methods, which use statistical sampling to evaluate many-body wave functions, have the potential to answer this challenge. Owing to the few fundamental approximations made and the direct treatment of electron correlation, QMC methods are among the most accurate electronic structure methods available to date. We assess the accuracy of the diffusion Monte Carlo method in the case of rocksalt manganese oxide (MnO). We study the electronic properties of this strongly-correlated oxide, which has been identified as a suitable candidate for many applications ranging from catalysts to electronic devices. ``This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.'' Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides.

  18. XANES studies of oxidation states of sulfur in aquatic and soil humic substances

    SciTech Connect

    Xia, K.; Weesner, F.; Bleam, W.F.; Helmke, P.A.; Bloom, P.R.; Skyllberg, U.L.

    1998-09-01

    Sulfur K-edge x-ray absorption near-edge structure spectroscopy (XANES) was used to identify multiple organic S oxidation states in aquatic and soil humic substances. The XANES results suggest that S in humic substances exists in four major oxidation groups similar to sulfate ester, sulfonate, sulfoxide, and thiol-sulfide. Thiol S cannot be separated from sulfide X and must be considered as a single thiol-sulfide peak. The second derivative spectra suggest the existence of thiophene and sulfone S. The relative quantities of each major S form in humic samples were estimated based on the integrated cross section of each s {r_arrow} p transition peak corresponding to different S oxidation states in the S K-edge XANES spectra. The XANES results of the four humic samples used in this study appear to reflect the environmental settings where the humic substances originally formed. The percentage of the most reduced organic S (thiol-sulfide and possibly thiophene) in humic substances follows the sequence:aquatic samples > organic soil sample > mineral soil sample. The percentage of most oxidized S (sulfate group) was the greatest in the humic substance from a mineral soil and the lowest in the aquatic humic substances.

  19. Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

    SciTech Connect

    Bondi, Robert J.; Marinella, Matthew J.

    2015-02-28

    First-principles density-functional theory (DFT) calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (VOn; n=0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta2O5) and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. VOn of all oxidation states preferentially segregate at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta2O5, VO0 are characterized by structural contraction and electron density localization, while VO2+ promote structural expansion and are depleted of electron density. In contrast, interfacial VO0 and VO2+ show nearly indistinguishable ionic and electronic signatures indicative of a reduced VO center. Interfacial VO2+ extract electron density from metallic Ta indicating VO2+ is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.

  20. No effect of H2O degassing on the oxidation state of magmatic liquids

    NASA Astrophysics Data System (ADS)

    Waters, Laura E.; Lange, Rebecca A.

    2016-08-01

    The underlying cause for why subduction-zone magmas are systematically more oxidized than those formed at mid-ocean spreading ridges is a topic of vigorous debate. It is either a primary feature inherited from the subduction of oxidized oceanic crust into the mantle or a secondary feature that develops because of H2O degassing and/or magma differentiation. Low total iron contents and high melt H2O contents render rhyolites sensitive to any effect of H2O degassing on ferric-ferrous ratios. Here, pre-eruptive magmatic Fe2+ concentrations, measured using Fe-Ti oxides that co-crystallized with silicate phenocrysts under hydrous conditions, are compared with Fe2+ post-eruptive concentrations in ten crystal-poor, fully-degassed obsidian samples; five are microlite free. No effect of H2O degassing on the ferric-ferrous ratio is found. In addition, Fe-Ti oxide data from this study and the literature show that arc magmas are systematically more oxidized than both basalts and hydrous silicic melts from Iceland and Yellowstone prior to extensive degassing. Nor is there any evidence that differentiation (i.e., crystal fractionation, crustal assimilation) is the cause of the higher redox state of arc magmas relative to those of Iceland/Yellowstone rhyolites. Instead, the evidence points to subduction of oxidized crust and the release of an H2O-rich fluid and/or melt with a high oxygen fugacity (fO2), which plays a role during H2O-flux melting of the mantle in creating basalts that are relatively oxidized.

  1. Engineering the defect state and reducibility of ceria based nanoparticles for improved anti-oxidation performance

    NASA Astrophysics Data System (ADS)

    Wang, Yan-Jie; Dong, Hao; Lyu, Guang-Ming; Zhang, Huai-Yuan; Ke, Jun; Kang, Li-Qun; Teng, Jia-Li; Sun, Ling-Dong; Si, Rui; Zhang, Jing; Liu, Yan-Jun; Zhang, Ya-Wen; Huang, Yun-Hui; Yan, Chun-Hua

    2015-08-01

    Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd3+. Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes.Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation

  2. Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, James F.

    1990-01-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

  3. Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

    NASA Astrophysics Data System (ADS)

    Kasting, James F.

    1990-05-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

  4. Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, James F.

    1990-01-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

  5. Reduction-oxidation state and protein degradation in skeletal muscle of fasted and refed rats

    NASA Technical Reports Server (NTRS)

    Fagan, Julie M.; Tischler, Marc E.

    1986-01-01

    Redox state and protein degradation were measured in isolated muscles of fasted (up to 10 d) and refed (up to 4 d) 7- to 14-wk-old rats. Protein degradation in the extensor digitorum longus muscle, but not in the soleus muscle, was greater in the fasted rats than in weight-matched muscle from fed rats. The NAD couple was more oxidized in incubated and fresh extensor digitorum longus muscles and in some incubated soleus muscles of fasted rats than in weight-matched muscle from fed rats. In the extensor digitorum longus muscle of refed or prolonged fasted rats, protein degradation was slower and the NAD couple was more reduced than in the fed state. Therefore, oxidation of the NAD couple was associated with increased muscle breakdown during fasting, whereas reduction of the NAD couple was associated with muscle conservation and deposition.

  6. Constraints on the Detection of the Solar Nebula's Oxidation State Through Asteroid Observations

    NASA Technical Reports Server (NTRS)

    Abell, P. A.; Gaffey, M. J.; Hardersen, P. S.

    2005-01-01

    Introduction: Asteroids represent the only in situ surviving population of planetesimals from the formation of the inner solar system and therefore include materials from the very earliest stages of solar system formation. Hence, these bodies can provide constraints on the processes and conditions that were present during this epoch and can be used to test current models and theories describing the late solar nebula, the early solar system and subsequent planetary accretion. From detailed knowledge of asteroid mineralogic compositions the probable starting materials, thermal histories, and oxidation states of asteroid parent bodies can be inferred. If such data can be obtained from specific mainbelt source regions, then this information can be used to map out the formation conditions of the late solar nebula within the inner solar system and possibly distinguish any trends in oxidation state that may be present.

  7. Reduction-oxidation state and protein degradation in skeletal muscle of fasted and refed rats

    NASA Technical Reports Server (NTRS)

    Fagan, Julie M.; Tischler, Marc E.

    1986-01-01

    Redox state and protein degradation were measured in isolated muscles of fasted (up to 10 d) and refed (up to 4 d) 7- to 14-wk-old rats. Protein degradation in the extensor digitorum longus muscle, but not in the soleus muscle, was greater in the fasted rats than in weight-matched muscle from fed rats. The NAD couple was more oxidized in incubated and fresh extensor digitorum longus muscles and in some incubated soleus muscles of fasted rats than in weight-matched muscle from fed rats. In the extensor digitorum longus muscle of refed or prolonged fasted rats, protein degradation was slower and the NAD couple was more reduced than in the fed state. Therefore, oxidation of the NAD couple was associated with increased muscle breakdown during fasting, whereas reduction of the NAD couple was associated with muscle conservation and deposition.

  8. Ge Interface Engineering with Ozone-oxidation for Low Interface State Density

    SciTech Connect

    Kuzum, Duygu; Krishnamohan, T.; Pethe, Abhijit J.; Okyay, Ali, K.; Oshima, Yasuhiro; Sun, Yun; McVittie, Jim P.; Pianetta, Piero A.; McIntyre, Paul C.; Saraswat, Krishna C.; /Stanford U., CIS

    2008-06-02

    Passivation of Ge has been a critical issue for Ge MOS applications in future technology nodes. In this letter, we introduce ozone-oxidation to engineer Ge/insulator interface. Interface states (D{sub it}) values across the bandgap and close to conduction bandedge were extracted using conductance technique at low temperatures. D{sub it} dependency on growth conditions was studied. Minimum D{sub it} of 3 x 10{sup 11} cm{sup -2} V{sup -1} was demonstrated. Physical quality of the interface was investigated through Ge 3d spectra measurements. We found that the interface and D{sub it} is strongly affected by the distribution of oxidation states and quality of the suboxide.

  9. A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

    PubMed

    Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

    2005-05-04

    A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

  10. Theoretical insights into [NiFe]-hydrogenases oxidation resulting in a slowly reactivating inactive state.

    PubMed

    Breglia, Raffaella; Ruiz-Rodriguez, Manuel Antonio; Vitriolo, Alessandro; Gonzàlez-Laredo, Rubén Francisco; De Gioia, Luca; Greco, Claudio; Bruschi, Maurizio

    2017-01-01

    [NiFe]-hydrogenases catalyse the relevant H2 → 2H(+) + 2e(-) reaction. Aerobic oxidation or anaerobic oxidation of this enzyme yields two inactive states called Ni-A and Ni-B. These states differ for the reactivation kinetics which are slower for Ni-A than Ni-B. While there is a general consensus on the structure of Ni-B, the nature of Ni-A is still controversial. Indeed, several crystallographic structures assigned to the Ni-A state have been proposed, which, however, differ for the nature of the bridging ligand and for the presence of modified cysteine residues. The spectroscopic characterization of Ni-A has been of little help due to small differences of calculated spectroscopic parameters, which does not allow to discriminate among the various forms proposed for Ni-A. Here, we report a DFT investigation on the nature of the Ni-A state, based on systematic explorations of conformational and configurational space relying on accurate energy calculations, and on comparisons of theoretical geometries with the X-ray structures currently available. The results presented in this work show that, among all plausible isomers featuring various protonation patterns and oxygenic ligands, the one corresponding to the crystallographic structure recently reported by Volbeda et al. (J Biol Inorg Chem 20:11-22, 19)-featuring a bridging hydroxide ligand and the sulphur atom of Cys64 oxidized to bridging sulfenate-is the most stable. However, isomers with cysteine residues oxidized to terminal sulfenate are very close in energy, and modifications in the network of H-bond with neighbouring residues may alter the stability order of such species.

  11. Visible light photoreactivity from hybridization states between carbon nitride bandgap states and valence states in Nb and Ti oxides

    NASA Astrophysics Data System (ADS)

    Lee, Hosik; Ohno, Takahisa

    2013-03-01

    For better efficiency as photocatalysts, N-doping for visible light reactivity has been intensively studied in Lamellar niobic and titanic solid acids (HNb3O8, H2Ti4O9), and its microscopic structures have been debated in this decade. We calculate the layered solid acids' structures and bandgaps. Bandgap reduction by carbon nitride adsorption in interlayer space is observed computationally. It originates from localized nitrogen states which form delocalized top-valence states by hybridizing with the host oxygen states and can contribute to photo-current.

  12. The oxidation state, and sulfur and Cu contents of arc magmas: implications for metallogeny

    NASA Astrophysics Data System (ADS)

    Richards, Jeremy P.

    2015-09-01

    Global data for measured Fe2O3/FeO ratios and Cu contents in unaltered volcanic and intrusive arc rocks indicate that, on average, they are slightly more oxidized than other magmas derived from depleted upper mantle (such as MORB), but contain similar Cu contents across their compositional ranges. Although Cu scatters to elevated values in some intermediate composition samples, the bulk of the data show a steady but gentle trend to lower concentrations with differentiation, reaching modal values of 50-100 ppm in andesitic rocks. These data suggest that Cu is mildly compatible during partial melting and fractionation processes, likely reflecting minor degrees of sulfide saturation throughout the magmatic cycle. However, the volume of sulfides must be small such that significant proportions of the metal content remain in the magma during fractionation to intermediate compositions. Previous studies have shown that andesitic magmas containing 50 ppm Cu can readily form large porphyry-type Cu deposits upon emplacement in the upper crust. A review of the literature suggests that the elevated oxidation state in the asthenospheric mantle wedge source of arc magmas (ΔFMQ ≈ + 1 ± 1) derives from the subduction of seawater-altered and oxidized oceanic crust, and is transmitted into the mantle wedge via prograde metamorphic dehydration fluids carrying sulfate and other oxidizing components. Progressive hydration and oxidation of the mantle wedge may take up to 10 m.y. to reach a steady state from the onset of subduction, explaining the rarity of porphyry deposits in primitive island arcs, and the late formation of porphyries in continental arc magmatic cycles. Magmas generated from this metasomatized and moderately oxidized mantle source will be hydrous basalts containing high concentrations of sulfur, mainly dissolved as sulfate or sulfite. Some condensed sulfides (melt or minerals) may be present due to the high overall fS2, despite the moderately high oxidation state

  13. Surface-state spectra from thick-oxide MOS tunnel junctions

    NASA Technical Reports Server (NTRS)

    Ma, T. P.; Barker, R. C.

    1974-01-01

    The conductance and capacitance of thick-oxide MOS tunnel junctions (SiO2 thickness 40 to 65 A) have been measured from 35 Hz to 210 kHz. It is demonstrated that the use of a thick-oxide MOS tunnel junction makes it possible to obtain the surface-state data throughout the whole silicon band gap with better resolution and better sensitivity than the conventional MOS capacitance techniques. A slight departure from equilibrium may occur in the voltage range where large tunnel current flows. Corrections to the energy scale must be made in this voltage range. A method for the evaluation of the junction quality is discussed. The simplified equivalent circuits necessary for the calculation of surface-state data are constructed under various bias conditions by an approach different from that used in a previously published work. The present work supports the model that at least some of the observed surface states are a consequence of the diffusion of contact metals into the oxide.

  14. Highly mobile and reactive state of hydrogen in metal oxide semiconductors at room temperature

    PubMed Central

    Chen, Wan Ping; He, Ke Feng; Wang, Yu; Chan, Helen Lai Wah; Yan, Zijie

    2013-01-01

    Hydrogen in metal oxides usually strongly associates with a neighboring oxygen ion through an O-H bond and thus displays a high stability. Here we report a novel state of hydrogen with unusually high mobility and reactivity in metal oxides at room temperature. We show that freshly doped hydrogen in Nb2O5 and WO3 polycrystals via electrochemical hydrogenation can reduce Cu2+ ions into Cu0 if the polycrystals are immersed in a CuSO4 solution, while this would not happen if the hydrogenated polycrystals have been placed in air for several hours before the immersion. Time-dependent studies of electrochemically hydrogenated rutile single crystals reveal two distinct states of hydrogen: one as protons covalently bonded to oxygen ions, while the other one is highly unstable with a lifetime of just a few hours. Observation of this mobile and reactive state of hydrogen will provide new insight into numerous moderate and low temperature interactions between metal oxides and hydrogen. PMID:24193143

  15. Switching of the Fe Oxida-tion State in Ferro-cene-Capped Alkanethiols

    NASA Astrophysics Data System (ADS)

    Zheng, Fan; Luk, Yan-Yeung; Abbott, Nicholas L.; Himpsel, F. J.

    2005-03-01

    Molecular electronics has been a rapidly-growing area, due to the simplicity of building molecular devices by self-assembly and the promise of extremely low power consumption as a result of pushing the size down to a few molecules per device. A self-assembled monolayer (SAM) of ferrocene-capped alkanethiols is produced in two stable oxidation states of Fe (Fe^2+ and Fe^3+). The oxidation states of Fe are probed with sub-monolayer sensitivity by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy at the iron L2, 3 edges ^[1]. NEXAFS provides a direct method to distinguish between the oxidation states of submonolayer by comparing with the bulk sample spectrum. The native Fe^2+ layer is converted chemically to Fe^3+, and the Fe^3+ layer can be switched back to Fe^2+ or possibly Fe^0 by irradiation with soft x-rays. The results have implications on switching mechanisms in molecular electronics. [1] Fan Zheng, V. P'erez-Dieste, J. L. McChesney, Yan-Yeung Luk, Nicholas L. Abbott, and F. J. Himpsel, Appl. Phys. Lett, to be submitted.

  16. PROCESS OF SECURING PLUTONIUM IN NITRIC ACID SOLUTIONS IN ITS TRIVALENT OXIDATION STATE

    DOEpatents

    Thomas, J.R.

    1958-08-26

    >Various processes for the recovery of plutonium require that the plutonium be obtalned and maintained in the reduced or trivalent state in solution. Ferrous ions are commonly used as the reducing agent for this purpose, but it is difficult to maintain the plutonium in a reduced state in nitric acid solutions due to the oxidizing effects of the acid. It has been found that the addition of a stabilizing or holding reductant to such solution prevents reoxidation of the plutonium. Sulfamate ions have been found to be ideally suitable as such a stabilizer even in the presence of nitric acid.

  17. On the origin of interface states at oxide/III-nitride heterojunction interfaces

    NASA Astrophysics Data System (ADS)

    Matys, M.; Adamowicz, B.; Domanowska, A.; Michalewicz, A.; Stoklas, R.; Akazawa, M.; Yatabe, Z.; Hashizume, T.

    2016-12-01

    The energy spectrum of interface state density, Dit(E), was determined at oxide/III-N heterojunction interfaces in the entire band gap, using two complementary photo-electric methods: (i) photo-assisted capacitance-voltage technique for the states distributed near the midgap and the conduction band (CB) and (ii) light intensity dependent photo-capacitance method for the states close to the valence band (VB). In addition, the Auger electron spectroscopy profiling was applied for the characterization of chemical composition of the interface region with the emphasis on carbon impurities, which can be responsible for the interface state creation. The studies were performed for the AlGaN/GaN metal-insulator-semiconductor heterostructures (MISH) with Al2O3 and SiO2 dielectric films and AlxGa1-x layers with x varying from 0.15 to 0.4 as well as for an Al2O3/InAlN/GaN MISH structure. For all structures, it was found that: (i) Dit(E) is an U-shaped continuum increasing from the midgap towards the CB and VB edges and (ii) interface states near the VB exhibit donor-like character. Furthermore, Dit(E) for SiO2/AlxGa1-x/GaN structures increased with rising x. It was also revealed that carbon impurities are not present in the oxide/III-N interface region, which indicates that probably the interface states are not related to carbon, as previously reported. Finally, it was proven that the obtained Dit(E) spectrum can be well fitted using a formula predicted by the disorder induced gap state model. This is an indication that the interface states at oxide/III-N interfaces can originate from the structural disorder of the interfacial region. Furthermore, at the oxide/barrier interface we revealed the presence of the positive fixed charge (QF) which is not related to Dit(E) and which almost compensates the negative polarization charge ( Qp o l - ).

  18. Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

    NASA Astrophysics Data System (ADS)

    Lange, R. A.; Waters, L.

    2014-12-01

    The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ∆NNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

  19. Transient-state and steady-state kinetics of the oxidation of aliphatic and aromatic thiols by horseradish peroxidase.

    PubMed

    Burner, U; Obinger, C

    1997-07-14

    In the course of oxidation of thiols by peroxidases thiyl radicals are formed which are known to undergo several free-radical conjugative reactions, among others leading to hydrogen peroxide formation. The present paper for the first time presents a comparative transient-state and steady-state investigation of the reaction of 15 aliphatic and aromatic mono- and dithiols with horseradish peroxidase (HRP). Both sequential-stopped-flow spectrophotometric investigations of the reaction of HRP intermediates Compound I (k2) and Compound II (k3) with thiols and measurements of the overall thiol oxidation and the simultaneous oxygen consumption in the presence and absence of exogenously added hydrogen peroxide (10 microM) have been performed. With HRP as thiyl radical generator it was shown that three groups of thiols have to be distinguished: (i) Aromatic thiols (e.g. thiophenol, 2-mercaptopurine) were excellent electron donors of both Compounds (k2: 10(4)-10(7) M(-1) s(-1) and k3: 10(3)-10(6) M(-1) s(-1)); however, the overall reaction was shown to depend on addition of hydrogen peroxide, indicating insufficient peroxide regeneration by arylthiyl radicals. (ii) Aliphatic thiols which were extremely bad substrates (k3 < 10 M(-1) s(-1)) for HRP (e.g. homocysteine, glutathione) and/or have a pK(a,SH) > 9.5 (e.g. N-acetylcysteine, alpha-lipoic acid) were also shown to depend on exogenously added H2O2 to maintain the peroxidasic reaction, whereas (iii) with those thiols with rates of k3 between 11 and 1600 M(-1) s(-1) (e.g. cysteine, cysteamine, cysteine methyl ester, cysteine ethyl ester) and/or with a pK(a,SH) < 8 (penicillamine) thiol oxidation was independent of exogenously added hydrogen peroxide, indicating sufficient hydrogen peroxide regeneration.

  20. Spin-Orbit Coupling Controlled J =3 /2 Electronic Ground State in 5 d3 Oxides

    NASA Astrophysics Data System (ADS)

    Taylor, A. E.; Calder, S.; Morrow, R.; Feng, H. L.; Upton, M. H.; Lumsden, M. D.; Yamaura, K.; Woodward, P. M.; Christianson, A. D.

    2017-05-01

    Entanglement of spin and orbital degrees of freedom drives the formation of novel quantum and topological physical states. Here we report resonant inelastic x-ray scattering measurements of the transition metal oxides Ca3 LiOsO6 and Ba2 YOsO6 , which reveals a dramatic spitting of the t2 g manifold. We invoke an intermediate coupling approach that incorporates both spin-orbit coupling and electron-electron interactions on an even footing and reveal that the ground state of 5 d3-based compounds, which has remained elusive in previously applied models, is a novel spin-orbit entangled J =3 /2 electronic ground state. This work reveals the hidden diversity of spin-orbit controlled ground states in 5 d systems and introduces a new arena in the search for spin-orbit controlled phases of matter.

  1. Oxidation and magnetic states of chalcopyrite CuFeS2: A first principles calculation

    NASA Astrophysics Data System (ADS)

    Klekovkina, V. V.; Gainov, R. R.; Vagizov, F. G.; Dooglav, A. V.; Golovanevskiy, V. A.; Pen'kov, I. N.

    2014-06-01

    The ground state band structure, magnetic moments, charges and population numbers of electronic shells of Cu and Fe atoms have been calculated for chalcopyrite CuFeS2 using density functional theory. The comparison between our calculation results and experimental data (X-ray photoemission, X-ray absorption and neutron diffraction spectroscopy) has been made. Our calculations predict a formal oxidation state for chalcopyrite as Cu1+Fe3+S{2/2-}. However, the assignment of formal valence state to transition metal atoms appears to be oversimplified. It is anticipated that the valence state can be confirmed experimentally by nuclear magnetic and nuclear quadrupole resonance and Mössbauer spectroscopy methods.

  2. Status in calculating electronic excited states in transition metal oxides from first principles.

    PubMed

    Bendavid, Leah Isseroff; Carter, Emily Ann

    2014-01-01

    Characterization of excitations in transition metal oxides is a crucial step in the development of these materials for photonic and optoelectronic applications. However, many transition metal oxides are considered to be strongly correlated materials, and their complex electronic structure is challenging to model with many established quantum mechanical techniques. We review state-of-the-art first-principles methods to calculate charged and neutral excited states in extended materials, and discuss their application to transition metal oxides. We briefly discuss developments in density functional theory (DFT) to calculate fundamental band gaps, and introduce time-dependent DFT, which can model neutral excitations. Charged excitations can be described within the framework of many-body perturbation theory based on Green's functions techniques, which predominantly employs the GW approximation to the self-energy to facilitate a feasible solution to the quasiparticle equations. We review the various implementations of the GW approximation and evaluate each approach in its calculation of fundamental band gaps of many transition metal oxides. We also briefly review the related Bethe-Salpeter equation (BSE), which introduces an electron-hole interaction between GW-derived quasiparticles to describe accurately neutral excitations. Embedded correlated wavefunction theory is another framework used to model localized neutral or charged excitations in extended materials. Here, the electronic structure of a small cluster is modeled within correlated wavefunction theory, while its coupling to its environment is represented by an embedding potential. We review a number of techniques to represent this background potential, including electrostatic representations and electron density-based methods, and evaluate their application to transition metal oxides.

  3. Surface-potential dependence of interface-state passivation in metal-tunnel-oxide-silicon diodes

    NASA Astrophysics Data System (ADS)

    Andersson, M. O.; Lundgren, A.; Lundgren, P.

    1994-10-01

    Interface-state passivation during dc biased postmetallization annealing at ~350 °C was studied in very thin oxide (~31 Å) metal-tunnel-oxide-silicon structures. The gate metal was aluminum and the substrate was <111> oriented and of p type. Capacitance-voltage and tunnel-current-voltage measurements were used after the anneals to monitor the passivation of interface states. It was found that the passivation process of the initially present interface states is directly dependent on the surface potential but not on the average oxide electric field or the tunnel current. A negative gate voltage increases the passivation rate, whereas a positive gate voltage decreases it as compared to unbiased annealing. The interface states bear significant resemblances to Pb centers, which are dangling bonds on trivalently bonded Si atoms at the interface. The present observations are found to agree well with the theoretical calculations by Edwards [Phys. Rev. B 44, 1832 (1991)] on the surface-potential dependence of the passivation of Pb centers by molecular hydrogen. Furthermore, we report on the impact of biased annealing on the tunnel current and the flatband voltage and also on the behavior of electrically stressed devices during biased annealing. The beneficial effect of a negatively biased annealing makes it possible to find an optimum time and voltage, roughly 1000 s at a gate voltage of -1.2 V in our case, for simultaneously minimizing the dc tunnel current, flatband voltage shifts, and the density of fast interface states in these diodes. None of the passivation events was found to be promoted by annealing in a 10% H2/Ar ambient compared to annealing in an N2 ambient.

  4. Low-oxidation state indium-catalyzed C-C bond formation.

    PubMed

    Schneider, Uwe; Kobayashi, Shu

    2012-08-21

    The development of innovative metal catalysis for selective bond formation is an important task in organic chemistry. The group 13 metal indium is appealing for catalysis because indium-based reagents are minimally toxic, selective, and tolerant toward various functional groups. Among elements in this group, the most stable oxidation state is typically +3, but in molecules with larger group 13 atoms, the chemistry of the +1 oxidation state is also important. The use of indium(III) compounds in organic synthesis has been well-established as Lewis acid catalysts including asymmetric versions thereof. In contrast, only sporadic examples of the use of indium(I) as a stoichiometric reagent have been reported: to the best of our knowledge, our investigations represent the first synthetic method that uses a catalytic amount of indium(I). Depending on the nature of the ligand or the counteranion to which it is coordinated, indium(I) can act as both a Lewis acid and a Lewis base because it has both vacant p orbitals and a lone pair of electrons. This potential ambiphilicity may offer unique reactivity and unusual selectivity in synthesis and may have significant implications for catalysis, particularly for dual catalytic processes. We envisioned that indium(I) could be employed as a metallic Lewis base catalyst to activate Lewis acidic boron-based pronucleophiles for selective bond formation with suitable electrophiles. Alternatively, indium(I) could serve as an ambiphilic catalyst that activates both reagents at a single center. In this Account, we describe the development of low-oxidation state indium catalysts for carbon-carbon bond formation between boron-based pronucleophiles and various electrophiles. We discovered that indium(I) iodide was an excellent catalyst for α-selective allylations of C(sp(2)) electrophiles such as ketones and hydrazones. Using a combination of this low-oxidation state indium compound and a chiral semicorrin ligand, we developed catalytic

  5. Molecular water oxidation mechanisms followed by transition metals: state of the art.

    PubMed

    Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

    2014-02-18

    One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for

  6. Hydrogen peroxide effects on chromium oxidation state and solubility in four diverse, chromium-enriched soils.

    PubMed

    Rock, M L; James, B R; Helz, G R

    2001-10-15

    High concentrations of H2O2 are being tested for in situ oxidation and remediation of buried organic contaminants in soils and groundwater. Peroxide is being considered as a direct chemical oxidant in Fenton-type reactions or as a source of oxidizing equivalents in bioremediation schemes. How H2O2 affects the oxidation state and solubility of Cr(III) and Cr(VI), common co-contaminants with organic chemicals, is explored here in four chemically diverse soils containing elevated levels of Cr. Soil contaminated with soluble Cr(VI) from chromite ore processing residue and soil containing high levels of recently reduced Cr (III) from electroplating waste both released dissolved Cr(VI) after single applications of up to 24 mM H2O2. In no case was there evidence that H202 reduced preexisting Cr(VI) to Cr(III), even though this would be allowed thermodynamically. Chromate in the leachates exceeded the U.S. EPA drinking water standard for total dissolved Cr (2 microM) by a factor of 10-1000. Anaerobic conditions in an organic-rich, tannery waste-contaminated soil protected Cr(III) from oxidation and mobilization. Mineral forms of Cr in serpentinitic soil near a former chromite mine also resisted oxidation on the time scale of days. Mobilization of Cr(VI) could be a hazardous consequence of using H2O2 for in situ remediation of chemically complex wastes, but H2O2 could prove attractive for ex situ treatment (i.e., soil washing). This paper demonstrates marked differences among Cr-contaminated soils in their capacity to release Cr(VI) upon chemical treatment with H2O2.

  7. Reactive nitrogen oxides in the southeast United States national parks: source identification, origin, and process budget

    NASA Astrophysics Data System (ADS)

    Tong, Daniel Quansong; Kang, Daiwen; Aneja, Viney P.; Ray, John D.

    2005-01-01

    We present in this study both measurement-based and modeling analyses for elucidation of source attribution, influence areas, and process budget of reactive nitrogen oxides at two rural southeast United States sites (Great Smoky Mountains national park (GRSM) and Mammoth Cave national park (MACA)). Availability of nitrogen oxides is considered as the limiting factor to ozone production in these areas and the relative source contribution of reactive nitrogen oxides from point or mobile sources is important in understanding why these areas have high ozone. Using two independent observation-based techniques, multiple linear regression analysis and emission inventory analysis, we demonstrate that point sources contribute a minimum of 23% of total NOy at GRSM and 27% at MACA. The influence areas for these two sites, or origins of nitrogen oxides, are investigated using trajectory-cluster analysis. The result shows that air masses from the West and Southwest sweep over GRSM most frequently, while pollutants transported from the eastern half (i.e., East, Northeast, and Southeast) have limited influence (<10% out of all air masses) on air quality at GRSM. The processes responsible for formation and removal of reactive nitrogen oxides are investigated using a comprehensive 3-D air quality model (Multiscale Air Quality SImulation Platform (MAQSIP)). The NOy contribution associated with chemical transformations to NOz and O3, based on process budget analysis, is as follows: 32% and 84% for NOz, and 26% and 80% for O3 at GRSM and MACA, respectively. The similarity between NOz and O3 process budgets suggests a close association between nitrogen oxides and effective O3 production at these rural locations.

  8. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  9. Adaptation of oxidative phosphorylation to photoperiod-induced seasonal metabolic states in migratory songbirds.

    PubMed

    Trivedi, Amit Kumar; Malik, Shalie; Rani, Sangeeta; Kumar, Vinod

    2015-06-01

    Eukaryotic cells produce chemical energy in the form of ATP by oxidative phosphorylation of metabolic fuels via a series of enzyme mediated biochemical reactions. We propose that the rates of these reactions are altered, as per energy needs of the seasonal metabolic states in avian migrants. To investigate this, blackheaded buntings were photoperiodically induced with non-migratory, premigratory, migratory and post-migratory phenotypes. High plasma levels of free fatty acids, citrate (an intermediate that begins the TCA cycle) and malate dehydrogenase (mdh, an enzyme involved at the end of the TCA cycle) confirmed increased availability of metabolic reserves and substrates to the TCA cycle during the premigratory and migratory states, respectively. Further, daily expression pattern of genes coding for enzymes involved in the oxidative decarboxylation of pyruvate to acetyl-CoA (pdc and pdk) and oxidative phosphorylation in the TCA cycle (cs, odgh, sdhd and mdh) was monitored in the hypothalamus and liver. Reciprocal relationship between pdc and pdk expressions conformed with the altered requirements of acetyl-CoA for the TCA cycle in different metabolic states. Except for pdk, all genes had a daily expression pattern, with high mRNA expression during the day in the premigratory/migratory phenotypes, and at night (cs, odhg, sdhd and mdh) in the nonmigratory phenotype. Differences in mRNA expression patterns of pdc, sdhd and mdh, but not of pdk, cs and odgh, between the hypothalamus and liver indicated a tissue dependent metabolism in buntings. These results suggest the adaptation of oxidative phosphorylation pathway(s) at gene levels to the seasonal alternations in metabolism in migratory songbirds.

  10. Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

    PubMed

    Kurlak, Lesia O; Green, Amanda; Loughna, Pamela; Broughton Pipkin, Fiona

    2014-01-01

    Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE) and non-proteinuric new hypertension (gestational hypertension; GH) are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks postpartum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS) and antioxidants (ferric ion reducing ability of plasma; FRAP). Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential) hypertension (EH) without PE. Limited data were available from normotensive pregnancies (n = 7) and non-pregnant controls (n = 14). There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P = 0.001) and FRAP (P = 0.009) were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P = 0.013). In PE and GH, TBARS correlated with low density lipoprotein (LDL)-cholesterol (P = 0.036); this association strengthened with inclusion of EH (P = 0.011). The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P = 0.003). Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre

  11. The Oxidation State of Terrestrial Basalts and its Link with the Mantle

    NASA Astrophysics Data System (ADS)

    Mallmann, G.; O'Neill, H. S.; Berry, A. J.; Norman, M. D.; Eggins, S. M.; Kamenetsky, V.; Turner, S.; Smith, I. E.; Ballhaus, C.

    2011-12-01

    The prevailing paradigm is that the Earth's mantle is both laterally and vertically heterogeneous in regards to its oxidation state. This view has been motivated by the observation that, on average, primitive island arc basalts (IAB) preserve Fe3+/Fe2+ higher than ocean island (OIB) and, particularly, mid-ocean ridge basalts (MORB), and reinforced by the higher oxygen fugacities (fO2) determined in lithospheric (mantle wedge) arc peridotites. fO2 measurements in peridotites equilibrated over a range of pressures have also led to the notion that the mantle becomes more reduced with depth. V and Sc behave very similarly during partial melting of the mantle, but while V is redox-sensitive Sc is not. Their ratio in basalts has therefore a memory of the redox conditions during partial melting. Within the many assumptions involved in forward trace-element modeling, the bulk-rock V/Sc of MORBs, OIBs and IABs indicate that the partial melting events responsible for their genesis occurred at a relatively narrow range of fO2s between QFM and QFM-1. V olivine-liquid partition coefficients are also sensitive to oxidation state (normalization to Sc is useful to minimize the effect of variables other than fO2), and the values determined between olivine phenocrysts (Fo76-90) and quenched basaltic melts suggest that, at the time of olivine crystallization, terrestrial basalts have already oxidized about 1 log fO2 unit (IABs even more so, approximately 2 log fO2 units). The results reveal no statistically significant distinction between the oxidation states of MORBs and OIBs. This has been confirmed by Fe3+/Fe2+ determined by XANES.

  12. Study of GaAs-oxide interface by transient capacitance spectroscopy - Discrete energy interface states

    NASA Technical Reports Server (NTRS)

    Kamieniecki, E.; Kazior, T. E.; Lagowski, J.; Gatos, H. C.

    1980-01-01

    Interface states and bulk GaAs energy levels were simultaneously investigated in GaAs MOS structures prepared by anodic oxidation. These two types of energy levels were successfully distinguished by carrying out a comparative analysis of deep level transient capacitance spectra of the MOS structures and MS structures prepared on the same samples of epitaxially grown GaAs. The identification and study of the interface states and bulk levels was also performed by investigating the transient capacitance spectra as a function of the filling pulse magnitude. It was found that in the GaAs-anodic oxide interface there are states present with a discrete energy rather than with a continuous energy distribution. The value of the capture cross section of the interface states was found to be 10 to the 14th to 10 to the 15th/sq cm, which is more accurate than the extremely large values of 10 to the -8th to 10 to the -9th/sq cm reported on the basis of conductance measurements.

  13. GaAs-oxide interface states - Gigantic photoionization via Auger-like process

    NASA Technical Reports Server (NTRS)

    Lagowski, J.; Kazior, T. E.; Gatos, H. C.; Walukiewicz, W.; Siejka, J.

    1981-01-01

    Spectral and transient responses of photostimulated current in MOS structures were employed for the study of GaAs-anodic oxide interface states. Discrete deep traps at 0.7 and 0.85 eV below the conduction band were found with concentrations of 5 x 10 to the 12th/sq cm and 7 x 10 to the 11th/sq cm, respectively. These traps coincide with interface states induced on clean GaAs surfaces by oxygen and/or metal adatoms (submonolayer coverage). In contrast to surfaces with low oxygen coverage, the GaAs-thick oxide interfaces exhibited a high density (about 10 to the 14th/sq cm) of shallow donors and acceptors. Photoexcitation of these donor-acceptor pairs led to a gigantic photoionization of deep interface states with rates 1000 times greater than direct transitions into the conduction band. The gigantic photoionization is explained on the basis of energy transfer from excited donor-acceptor pairs to deep states.

  14. Resistive switching behavior and multiple transmittance states in solution-processed tungsten oxide.

    PubMed

    Wu, Wei-Ting; Wu, Jih-Jen; Chen, Jen-Sue

    2011-07-01

    In this work, a tungsten oxide (WO(x)) film is prepared using a thiourea-assisted solution process. We demonstrate a device composed of fluorine doped tin oxide (FTO)-glass/WO(x)/electrolyte/indium-tin oxide (ITO)-glass stacking electrochromic (EC) structure and Al electrodes that are locally patterned and interposed between the WO(x) film and electrolyte, which form an Al(top electrode)/WO(x)/FTO(bottom electrode) resistance random access memory (RRAM) unit. According to transmission electron microscopy and X-ray photoelectron spectroscopy analyses, the WO(x) film contains nanosize pores and metallic-tungsten nanoclusters which are scattered within the tungsten oxide layer and concentrated along the interface between the Al electrode and WO(x) film. With application of voltage to the ITO electrode, multiple transmittance states are achieved for the EC unit due to the different quantity of intercalated Li ions in the WO(x) film. As for the Al/WO(x)/FTO RRAM unit, a bipolar nonvolatile resistive switching behavior is attained by applying voltage on the Al top electrode, showing electrical bistability with an ON/OFF current ratio up to 1 × 10(4).

  15. Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.

    SciTech Connect

    Hornstein, B. J.; Dattelbaum, D. M.; Schoonover, J. R.; Meyer, T. J.

    2004-01-01

    Ruthenium polypyridyl oxalate complexes are precursors to high oxidation state species that can catalyze the oxidation of a variety of substrates. Covalent attachment of these reactive species to surfaces such at ZrO{sub 2} or TiO{sub 2} inhibit catalyst deactivation and provide supports from which to build electrocatalytic and photoelectrocatalytic devices. Unfortunately, few details of the effects of surface binding on reactivity are available in the literature. To this end, precursors such as, Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4})(H{sub 2}O) and (C{sub 2}O{sub 4})(H{sub 2}O{sub 3}Ptpy)Ru-O-Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4}) (tpy is terpyridine) have been synthesized and attached to TiO{sub 2}. Quantitative surface binding studies were carried out and acid catalyzed solvolysis was used to form the aqua species. The complexes were oxidized with Ce(IV) to their high-valent analogs and their reactivity toward selected substrates was tested. These studies not only provide information about the effects of surface binding on the reactivity of metal oxides but also have implications for the development of light-driven catalysts.

  16. Anr, the anaerobic global regulator, modulates the redox state and oxidative stress resistance in Pseudomonas extremaustralis.

    PubMed

    Tribelli, Paula M; Nikel, Pablo I; Oppezzo, Oscar J; López, Nancy I

    2013-02-01

    The role of Anr in oxidative stress resistance was investigated in Pseudomonas extremaustralis, a polyhydroxybutyrate-producing Antarctic bacterium. The absence of Anr caused increased sensitivity to hydrogen peroxide under low oxygen tension. This phenomenon was associated with a decrease in the redox ratio, higher oxygen consumption and higher reactive oxygen species production. Physiological responses of the mutant to the oxidized state included an increase in NADP(H) content, catalase activity and exopolysaccharide production. The wild-type strain showed a sharp decrease in the reduced thiol pool when exposed to hydrogen peroxide, not observed in the mutant strain. In silico analysis of the genome sequence of P. extremaustralis revealed putative Anr binding sites upstream from genes related to oxidative stress. Genes encoding several chaperones and cold shock proteins, a glutathione synthase, a sulfate transporter and a thiol peroxidase were identified as potential targets for Anr regulation. Our results suggest a novel role for Anr in oxidative stress resistance and in redox balance maintenance under conditions of restricted oxygen supply.

  17. Oxidation-state dependence of rheology in peralkaline glasses of phonolitic composition

    NASA Astrophysics Data System (ADS)

    Scherrer, M. C.; Hess, K.-U.; Fehr, K. T.; Dingwell, D. B.

    2012-04-01

    The precise description of magmatic melts rheology at the glass transition is crucial in understanding dynamic processes in volcanology. The glass transition has been described to scale with the viscosity of the material according to Maxwell's relaxation theory for viscoelastic liquids (Dingwell and Webb, 1989). The temperature dependence of the viscosity of multi-component systems can adequately be calculated using empirical models such as Hess et al. (1996), Giordano et al. (2008) and Hui and Zhang (2008); yet, within these calculations, the influence of oxidation state has been so far considered minor and was consequently neglected. The rheological behavior of some iron-rich silicate melts has shown noteworthy oxidation state-dependent variations (Cukierman and Uhlmann 1974, Dingwell and Virgo 1987). The focus of our study is to improve the viscosity models by investigating the necessity of an additional redox-parameter. Thirteen re-melted glass samples of natural phonolitic composition (peralkaline lavas with 8.5 wt. % FeOtot) were produced under different oxygen fugacity (fO2) conditions in a CO/CO2 gas-mixing furnace. Their oxidation-state (Fe3+/Fetot) ranges from 0.44 to 0.93 (±0.05). The viscosity above the liquidus was recorded via the concentric cylinder technique at a constant temperature of 1186 ° C. Additionally, viscosities were measured in the interval of 107to 1011Pa swith temperatures up to 900 ° C at ambient pressure via a BAEHR micro-penetration viscometer. Glass transition temperatures (Tg) have been determined with a constant heating/cooling rate of 10K/min on a SETARAM Sensys evo DSC using the peak of the specific heat capacity curve. Under a constant temperature in the super-liquidus state, the viscosity increases strongly with increasing fO2. In the sub-liquidus state, the measured calorimetric Tgis shifted to lower temperatures as the ratio of ferrous/total iron decreases from 638 ° C to 610 ° C. However, there is no equivalent

  18. WldS and PGC-1α Regulate Mitochondrial Transport and Oxidation State after Axonal Injury

    PubMed Central

    O'Donnell, Kelley C.; Vargas, Mauricio E.

    2013-01-01

    Mitochondria carry out many of the processes implicated in maintaining axon health or causing axon degeneration, including ATP and reactive oxygen species (ROS) generation, as well as calcium buffering and protease activation. Defects in mitochondrial function and transport are common in axon degeneration, but how changes in specific mitochondrial properties relate to degeneration is not well understood. Using cutaneous sensory neurons of living larval zebrafish as a model, we examined the role of mitochondria in axon degeneration by monitoring mitochondrial morphology, transport, and redox state before and after laser axotomy. Mitochondrial transport terminated locally after injury in wild-type axons, an effect that was moderately attenuated by expressing the axon-protective fusion protein Wallerian degeneration slow (WldS). However, mitochondrial transport arrest eventually occurred in WldS-protected axons, indicating that later in the lag phase, mitochondrial transport is not required for axon protection. By contrast, the redox-sensitive biosensor roGFP2 was rapidly oxidized in the mitochondrial matrix after injury, and WldS expression prevented this effect, suggesting that stabilization of ROS production may mediate axon protection. Overexpression of PGC-1α, a transcriptional coactivator with roles in both mitochondrial biogenesis and ROS detoxification, dramatically increased mitochondrial density, attenuated roGFP2 oxidation, and delayed Wallerian degeneration. Collectively, these results indicate that mitochondrial oxidation state is a more reliable indicator of axon vulnerability to degeneration than mitochondrial motility. PMID:24027278

  19. Room air versus carbon dioxide pneumoperitoneum: effects on oxidative state, apoptosis and histology of splanchnic organs.

    PubMed

    Ypsilantis, Petros; Lambropoulou, Maria; Tentes, Ioannis; Chryssidou, Maria; Georgantas, Themistoklis; Simopoulos, Constantinos

    2016-04-01

    Although CO2 is the insufflation gas of choice in laparoscopic procedures, room air is usually used in natural orifice transluminal endoscopic surgery. The aim of the present study was to compare the safety of room air versus CO2 pneumoperitoneum in terms of their effect on the oxidative state, apoptosis and tissue injury of splanchnic organs. Eighteen Wistar rats were assigned to three groups (n = 6 per group) and were subjected to 8 mm Hg room air (group Pne-Air) or CO2 pneumoperitoneum (group Pne-CO2) or sham operation for 60 min. Forty-five minutes postdeflation, tissue samples were excised from the liver, stomach, ileum and kidneys for reduced glutathione-to-glutathione disulfide (GSH/GSSG) ratio, caspase-8 and caspase-3 and hypoxia-inducible factor-1α (HIF-1α) immunohistochemical assessment and histopathologic examination. GSH/GSSG ratio substantially declined in both pneumoperitoneum groups. No change was noted in HIF-1α expression. Mild upregulation of caspase-8 and caspase-3 was noted in both pneumoperitoneum groups being less pronounced in group Pne-Air. Histopathologic score was increased in all organs studied, but the stomach, in both pneumoperitoneum groups. Pneumoperitoneum established by either room air or CO2 induced substantial oxidative stress, mild apoptosis and mild tissue injury in splanchnic organs. While air pneumoperitoneum conferred a less pronounced apoptotic effect, the oxidative state and histopathologic profile of splanchnic organs did not differ between insufflation gases.

  20. Micro-XANES Determination of Fe Oxidation State in MORB and its Relationship to Water Content

    NASA Astrophysics Data System (ADS)

    Posner, E. S.; Cottrell, E.; Kelley, K. A.; Ruebush, E.

    2009-12-01

    We report the oxidation state of iron and H2O content for a global suite of mid-ocean ridge basalt (MORB) glasses in order to assess the relationship between water and oxidation state in mantle-derived basalts unaffected by subduction zone processes. Fe3+/ΣFe ratios were determined with Fe K-edge μX-ray absorption near-edge structure spectroscopy (μXANES). Fe oxidation state was previously determined with microcolorimetry and/or direct titration on a subset of the samples. Fe3+/ΣFe ratios determined using the Mossbauer-based μXANES basalt calibration averaged 0.16±0.01 (n=46) and negatively correlate with MgO suggesting the influence of olivine fractionation. The subset of samples also analyzed by colorimetry ranged from 0.04-0.15 compared to 0.13-0.17 with XANES (n=27) and those also analyzed by direct titration ranged from 0.09-0.14 compared to 0.14-0.17 with XANES (n=9). To investigate the cause of these offsets, Fe3+/ΣFe ratios were determined directly by Mossbauer spectroscopy on two hand-picked, aphyric MORB glass separates and were found to be identical within error to values determined by μXANES. Experimentally equilibrated basaltic glasses from the original study of Kress and Carmichael (CMP, 1991), for which Fe3+/ΣFe ratios were determined by microcolorimetry, were also found to yield Fe3+/ΣFe ratios identical to those determined by μXANES within error. Acid digestion of olivine microphenocrysts in natural MORB samples may lead to an offset between XANES, which samples only glass, and wet-chemical determinations of Fe3+/ΣFe ratios. For example, acid digestion of 20% Fo85 olivine is sufficient to cause the observed offset between XANES and direct titration. Total H2O content, determined with FTIR on the same suite of glasses, shows no correlation with iron oxidation state globally (n=46) or locally within a cogenetic suite (n=10, CHEPR, EPR 6°-13° N, 6-9wt% MgO). In contrast, subduction-influenced back-arc basin (BABB) settings show clear

  1. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.

    PubMed

    Huang, Wei; Jiang, Ning; Schwarz, W H Eugen; Yang, Ping; Li, Jun

    2017-08-04

    The geometric and electronic ground-state structures of 30 isomers of six MS4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS4 species were compared to analogous MO4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4 , whereas a low MOS of two appeared in the high-spin septet D2d species Fe(S2 )2 and (slightly excited) metastable Fe(O2 )2 . The ground states of all other molecules had intermediate MOS values, with S(2-) , S2(2-) , S2(1-) (and O(2-) , O(1-) , O2(2-) , O2(1-) ) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n-1)p core and (n-1)d and (n-2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO4 and MS4 species provides insight into the periodicity of oxidation states and bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

    NASA Astrophysics Data System (ADS)

    Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

    2017-10-01

    Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

  3. Low-temperature, highly selective, gas-phase oxidation of benzyl alcohol over mesoporous K-Cu-TiO2 with stable copper(I) oxidation state.

    PubMed

    Fan, Jie; Dai, Yihu; Li, Yunlong; Zheng, Nanfeng; Guo, Junfang; Yan, Xiaoqing; Stucky, Galen D

    2009-11-04

    A newly developed mesoporous mixed metal oxide (K-Cu-TiO(2)) catalyst is capable of highly selective, gas-phase benzyl alcoholbenzaldehyde transformation at excellent yields (>99%) under surprisingly low temperatures (203 degrees C, bp of benzyl alcohol). The low-temperature reaction conditions and integration of K and Cu(I) components into the TiO(2) matrix are of vital importance for the stabilization of an active Cu(I) oxidation state and resultant stable, excellent catalytic performance.

  4. A study of conduction band edge states in complex oxides by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Fulton, C. C.; Edge, L. F.; Lucovsky, G.; Lüning, J.

    2006-11-01

    Conduction band edge d-states are compared for complex oxides: (i) mixed tetravalent-trivalent ZrO 2-Y 2O 3 alloys, (ii) tetravalent Zr(Hf)O 2-TiO 2 alloys, and (iii) trivalent La scandate and aluminate. Low Y 2O 3 content cubic ZrO 2-Y 2O 3 alloys display two crystal-field split 4d-features in O K 1 spectra. Alloys with higher Y 2O 3 content, as well as Zr(Hf)O 2-TiO 2 alloys display increased d-state multiplicity. O K 1 spectra of perovskite-structured LaScO 3 and LaAlO 3 indicate Jahn-Teller d-state term-splittings with contributions from both trivalent atomic species.

  5. Vibrational autoionization and predissociation in high Rydberg states of nitric oxide

    NASA Astrophysics Data System (ADS)

    Pratt, S. T.

    1998-05-01

    New results on the competition between autoionization and predissociation in the high Rydberg states of nitric oxide are presented. These results provide insight into the earlier work of Park et al. [Phys. Rev. Lett. 76, 1591 (1996)] that shows evidence for substantial mixing between Rydberg series and ionization continua with even and odd orbital angular momenta (l). New data based on fluorescence-dip spectroscopy, detection of neutral predissociation products, and photoelectron spectroscopy suggest that the A' 2Σ+ and I 2Σ+ dissociative valence states play an important role in this l mixing. Zeeman splittings observed in a magnetic bottle electron spectrometer also result in an improvement in the assignment of these high Rydberg states.

  6. Arsenic (+ 3 oxidation state) methyltransferase genotype affects steady-state distribution and clearance of arsenic in arsenate-treated mice

    SciTech Connect

    Hughes, Michael F.; Edwards, Brenda C.; Herbin-Davis, Karen M.; Saunders, Jesse; Styblo, Miroslav; Thomas, David J.

    2010-12-15

    Arsenic (+ 3 oxidation state) methyltransferase (As3mt) catalyzes formation of mono-, di-, and tri-methylated metabolites of inorganic arsenic. Distribution and retention of arsenic were compared in adult female As3mt knockout mice and wild-type C57BL/6 mice using a regimen in which mice received daily oral doses of 0.5 mg of arsenic as arsenate per kilogram of body weight. Regardless of genotype, arsenic body burdens attained steady state after 10 daily doses. At steady state, arsenic body burdens in As3mt knockout mice were 16 to 20 times greater than in wild-type mice. During the post dosing clearance period, arsenic body burdens declined in As3mt knockout mice to {approx} 35% and in wild-type mice to {approx} 10% of steady-state levels. Urinary concentration of arsenic was significantly lower in As3mt knockout mice than in wild-type mice. At steady state, As3mt knockout mice had significantly higher fractions of the body burden of arsenic in liver, kidney, and urinary bladder than did wild-type mice. These organs and lung had significantly higher arsenic concentrations than did corresponding organs from wild-type mice. Inorganic arsenic was the predominant species in tissues of As3mt knockout mice; tissues from wild-type mice contained mixtures of inorganic arsenic and its methylated metabolites. Diminished capacity for arsenic methylation in As3mt knockout mice prolongs retention of inorganic arsenic in tissues and affects whole body clearance of arsenic. Altered retention and tissue tropism of arsenic in As3mt knockout mice could affect the toxic or carcinogenic effects associated with exposure to this metalloid or its methylated metabolites.

  7. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    SciTech Connect

    Unknown

    2003-06-01

    This report summarizes the progress made during the September 2001-March 2002 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program''. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. The overall objective of the program is to demonstrate a modular SOFC system that can be configured to create highly efficient, cost-competitive, and environmentally benign power plants tailored to specific markets. When fully developed, the system will meet the efficiency, performance, life, and cost goals for future commercial power plants.

  8. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    SciTech Connect

    Nguyen Minh; Jim Powers

    2003-10-01

    This report summarizes the work performed for April 2003--September 2003 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U.S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid oxide Fuel Cell Program''. During this reporting period, the conceptual system design activity was completed. The system design, including strategies for startup, normal operation and shutdown, was defined. Sealant and stack materials for the solid oxide fuel cell (SOFC) stack were identified which are capable of meeting the thermal cycling and degradation requirements. A cell module was tested which achieved a stable performance of 0.238 W/cm{sup 2} at 95% fuel utilization. The external fuel processor design was completed and fabrication begun. Several other advances were made on various aspects of the SOFC system, which are detailed in this report.

  9. Oxidative Stress Modifies the Levels and Phosphorylation State of Tau Protein in Human Fibroblasts.

    PubMed

    Ibáñez-Salazar, Alejandro; Bañuelos-Hernández, Bernardo; Rodríguez-Leyva, Ildefonso; Chi-Ahumada, Erika; Monreal-Escalante, Elizabeth; Jiménez-Capdeville, María E; Rosales-Mendoza, Sergio

    2017-01-01

    Since the tau protein is closely involved in the physiopathology of Alzheimer's disease (AD), studying its behavior in cellular models might lead to new insights on understanding this devastating disease at molecular levels. In the present study, primary cultures of human fibroblasts were established and used to determine the expression and localization of the tau protein in distinct phosphorylation states in both untransfected and tau gene-transfected cells subjected to oxidative stress. Higher immunopositivity to phospho-tau was observed in cell nuclei in response to oxidative stress, while the levels of total tau in the cytosol remained unchanged. These findings were observed in both untransfected cells and those transfected with the tau gene. The present work represents a useful model for studying the physiopathology of AD at the cellular level in terms of tau protein implications.

  10. Influence of the Sn oxidation state in ferromagnetic Sn-doped In2O3 nanowires

    NASA Astrophysics Data System (ADS)

    Maloney, Francis Scott; Wang, Wenyong

    2016-12-01

    Sn-doped indium oxide nanowires were grown using a vapor-liquid-solid technique (VLS). The Sn content of the nanowires was tunable based on the source powder ratios used in the VLS process. The oxidation state of the Sn ions was examined using x-ray photoelectron spectroscopy. It was found that Sn2+ was the dominant ionic species in samples over 6% (atomic percentage) Sn. The nanowires were found to be ferromagnetic at room temperature, and their saturation magnetization increased with increasing Sn concentration, which could be associated with the spin-splitting of a defect band that was encouraged by the imbalance of Sn2+ to Sn4+ species at high Sn concentrations.

  11. Mouse arsenic (+3 oxidation state) methyltransferase genotype affects metabolism and tissue dosimetry of arsenicals after arsenite administration in drinking water

    EPA Science Inventory

    Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes methylation of inorganic arsenic producing a number of methylated arsenic metabolites. Although methylation has been commonly considered a pathway for detoxification of arsenic, some highly reactive methylated ars...

  12. Mouse arsenic (+3 oxidation state) methyltransferase genotype affects metabolism and tissue dosimetry of arsenicals after arsenite administration in drinking water

    EPA Science Inventory

    Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes methylation of inorganic arsenic producing a number of methylated arsenic metabolites. Although methylation has been commonly considered a pathway for detoxification of arsenic, some highly reactive methylated ars...

  13. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, R.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be

  14. Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state

    NASA Astrophysics Data System (ADS)

    Hosaynali Beygi, Z.; Fischer, H.; Harder, H. D.; Martinez, M.; Sander, R.; Williams, J.; Brookes, D. M.; Monks, P. S.; Lelieveld, J.

    2011-08-01

    Ozone (O3) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S-57° S, 46° W-34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NOx conditions (5-25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NOx mixing ratio and JNO2 intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°-60° S over the Atlantic Ocean.

  15. Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.

    1992-01-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

  16. Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.

    1992-01-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

  17. The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano

    NASA Astrophysics Data System (ADS)

    Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive

    2016-09-01

    Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

  18. A spontaneous change in the oxidation states of Pd/WO3 toward an active phase during catalytic cycles of CO oxidation

    NASA Astrophysics Data System (ADS)

    Jeon, Byungwook; Kim, Ansoon; Lee, Young-Ahn; Seo, Hyungtak; Kim, Yu Kwon

    2017-11-01

    CO oxidation over Pd/WO3 films prepared on a glass substrate has been examined at the substrate temperature of 150 - 250 °C and pressures less than 1 Torr with a stoichiometric mixture of CO and O2. Under the given reaction condition, the chemical states of the Pd/WO3 film gradually change into the most catalytically active form with the highest saturation reaction rate regardless of the initial oxidation states. The measured CO oxidation rate over the Pd/WO3 is strongly dependent on the chemical states of Pd and W. Either metallic Pd or fully oxidized PdO phase is not as catalytically active as the active form with mixed metallic Pd and thin PdO layers supported on WO3 with partially reduced W5+ state which is spontaneously obtained during the catalytic reaction cycles. Our results indicate that the facile oxygen transfer between Pd and WO3 layers not only facilitate the spontaneous changes into the active form, but also act as a promotional role in CO oxidation over the Pd layer.

  19. Evaluating the state of indium-tin oxide gels via estimation of their cohesive energy

    NASA Astrophysics Data System (ADS)

    Hirose, Daisuke; Shimoda, Tatsuya

    2014-02-01

    In the fabrication of metal oxide films by the solution process, it is very important to know the state of a gel. In this report, the type of for indium-tin oxide (ITO) gel was determined according to the cohesive energy for agglutinating a gel. We developed the new method of determining a gel’s state to elucidate the total cohesive energy of an ITO gel film and its components. We employed an optical method based on the Lifshitz-van der Waals theory and a contact angle measurement method based on the van Oss theory to estimate components of cohesive energy. The result showed that the van der Waals interaction was the dominant interaction in the agglutination of the ITO gel. This indicated that the ITO gel is a physical gel. This result coincided well with these obtained by conventional methods such as thermogravimetric-differential thermal analysis and resolvability tests. The new method will be very useful for evaluating the gel state nondestructively.

  20. Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state

    NASA Astrophysics Data System (ADS)

    Giuli, Gabriele; Cicconi, Maria Rita; Eeckhout, Sigrid Griet; Pratesi, Giovanni; Paris, Eleonora; Folco, Luigi

    2014-04-01

    The Fe oxidation state and coordination number of 29 impact glass spherules recently recovered from the Transantarctic Mountains (Antarctica) have been determined by X-ray absorption near edge structure (XANES) spectroscopy. Based on geochemical, isotopic, and fission track data, these spherules are considered as microtektites from the Australasian tektite/microtektite strewn field. Their find location is the farthest so far discovered from the possible source crater region, and their alkali content is the lowest compared with other published data on Australasian microtektite glasses. The Fe3+/(Fe2++Fe3+) ratio, determined from the analysis of the pre-edge peak energy position and integrated intensity, is below 0.1 (±0.04) for all the samples, and is comparable to that of most tektites and microtektites from the Australasian strewn field. Also, the pre-edge peak integrated intensity, which is sensitive to the average Fe coordination geometry, is comparable to that of other Australasian microtektites reported in the literature. The agreement of the Fe oxidation state and coordination number, between the Transantarctic Mountain microtektites (TAM) and the Australasian tektites and microtektites, further confirms the impact origin of these glass spherules and provides an independent suggestion that they represent a major extension southeastward of the Australasian strewn field. The fact that similar redox conditions are observed in tektites and microtektites within the Australasian strewn field regardless of the distance from the source crater area (up to approximately 11000 km) could be an important constraint for better understanding the different processes affecting microtektite formation and transport. The fact that the Fe oxidation state of microtektites does not increase with distance, as in the case of North American microtektites, means that thermal and redox histories of Australasian and TAM microtektites could differ significantly from those of North

  1. Total antioxidant and total oxidant states, and serum paraoxonase-1 in neonatal sepsis.

    PubMed

    Annagür, Ali; Örs, Rahmi; Altunhan, Hüseyin; Kurban, Sevil; Ertuğrul, Sabahattin; Konak, Murat; Uygun, Saime Sündüz; Pekcan, Sevgi; Erbay, Ekrem; Mehmetoğlu, İdris

    2015-08-01

    Paraoxonase-1 (PON-1) is an enzyme with a glycoprotein structure that depends on calcium and which is located in serum high-density lipoprotein (HDL). The aim of this study was to evaluate PON-1, and oxidant/antioxidant state, before and after treatment for neonatal sepsis, and to determine the usability of PON-1 in neonatal sepsis treatment. A total of 35 neonatal sepsis patients and 35 healthy controls were included in the study. Activity of PON-1, total oxidant state (TOS) and total antioxidant state (TAS) were measured and oxidative stress index (OSI) was calculated. In the neonatal sepsis patients, pre-treatment TAS, TOS and OSI were significantly higher than the post-treatment levels (P < 0.0001, P < 0.0001 and P < 0.0001, respectively), and PON-1 was significantly lower (P < 0.0001). Similarly, pre-treatment TAS, TOS and OSI in the sepsis group were also significantly higher than in the control group (P < 0.0001, P < 0.0001 and P < 0.0001, respectively) and PON-1 was significantly lower (P < 0.0001). Post-treatment TAS in the sepsis group was significantly higher than in the control group (P = 0.009), whereas post-treatment TOS, OSI and PON-1 in the sepsis group were not significantly different to the control group (P = 0.078, P = 0.597 and P = 0.086, respectively). Low serum PON-1 was found in neonatal sepsis. Serum PON-1 is thought to be a useful biomarker to evaluate the effectiveness of treatment and recovery in neonatal sepsis. © 2014 Japan Pediatric Society.

  2. The oxidation state of Hadean magmas and implications for early Earth's atmosphere.

    PubMed

    Trail, Dustin; Watson, E Bruce; Tailby, Nicholas D

    2011-11-30

    Magmatic outgassing of volatiles from Earth's interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron-wüstite buffer would yield volatile species such as CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth's history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching ∼4,400 Myr (refs 5-8). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite-magnetite-quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas as early as ∼4,350 Myr before present. These results suggest that outgassing of Earth's interior later than ∼200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.

  3. Identification of ground-state spin ordering in antiferromagnetic transition metal oxides using the Ising model and a genetic algorithm.

    PubMed

    Lee, Kyuhyun; Youn, Yong; Han, Seungwu

    2017-01-01

    We identify ground-state collinear spin ordering in various antiferromagnetic transition metal oxides by constructing the Ising model from first-principles results and applying a genetic algorithm to find its minimum energy state. The present method can correctly reproduce the ground state of well-known antiferromagnetic oxides such as NiO, Fe2O3, Cr2O3 and MnO2. Furthermore, we identify the ground-state spin ordering in more complicated materials such as Mn3O4 and CoCr2O4.

  4. Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

    NASA Astrophysics Data System (ADS)

    Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

    2017-01-01

    Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is

  5. Purification of Arsenic (+3 Oxidation State) Methyltransferase from Rat Liver Cytosol

    PubMed Central

    Drobna, Zuzana; Styblo, Miroslav; Thomas, David J.

    2015-01-01

    Demonstrating the enzymatic basis of arsenic methylation is critical to further studies of the pathway for the conversion of inorganic arsenic into a variety of methylated metabolites. This protocol describes a procedure for the purification of an arsenic methyltransferase from rat liver cytosol. Purification of this enzyme and subsequent cloning of its gene has permitted studies of enzyme structure and function and has lead to the identification of orthologous genes in genomes of organisms ranging in complexity from sea urchins to humans. These proteins are referred to as arsenic (+3 oxidation state) methyltransferases. PMID:20949431

  6. Synthesis, Characterization, and Electrochemistry of sigma-Bonded Cobalt Corroles in High Oxidation States.

    PubMed

    Will, Stefan; Lex, Johann; Vogel, Emanuel; Adamian, Victor A.; Van Caemelbecke, Eric; Kadish, Karl M.

    1996-09-11

    The synthesis, electrochemistry, spectroscopy, and structural characterization of two high-valent phenyl sigma-bonded cobalt corroles containing a central cobalt ion in formal +IV and +V oxidation states is presented. The characterized compounds are represented as phenyl sigma-bonded cobalt corroles, (OEC)Co(C(6)H(5)) and [(OEC)Co(C(6)H(5))]ClO(4), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. The electronic distribution in both molecules is discussed in terms of their NMR and EPR spectroscopic data, magnetic susceptibility, and electrochemistry.

  7. Energy state distributions at oxide-semiconductor interfaces investigated by Laplace DLTS

    NASA Astrophysics Data System (ADS)

    Dobaczewski, L.; Markevich, V. P.; Kruszewski, P.; Hawkins, I. D.; Peaker, A. R.

    2009-12-01

    At disordered Si/SiO2 interfaces the lattice mismatching results in dangling bond Pb centres forming a rather broad distribution of energy states. In this study these energy distributions have been determined using isothermal current Laplace deep level transient spectroscopy (DLTS) for the (1 0 0) and (1 1 1) interface orientations. The (1 1 1) distribution is 0.08 eV broad and centred at 0.38 eV below the silicon conduction band. This is consistent with only Pb0 states being present. While for the (1 0 0) orientation this distribution is broader (0.1 eV) and deeper (0.43 eV) on the energy scale. Detailed studies revealed two types of the interface states in this broad distribution: one similar to the (1 1 1) orientation while the other has a negative-U character in which the emission rate versus surface potential dependence is qualitatively different from that observed for Pb0 and is presumed to be Pb1. Discrepancies between Pb states energy distributions obtained with a use of the isothermal Laplace and conventional DLTS measurements are discussed. The presented experimental procedure can be used for analysis of interface states observed at interfaces of other semiconductor-oxide/dielectric systems.

  8. Potentiality of delocalized states in indium-involved amorphous silicon oxide

    NASA Astrophysics Data System (ADS)

    Wan, Y. Z.; Gao, M.; Li, Y.; Du, H. W.; Li, Y. H.; Guo, H. B.; Xu, F.; Ma, Z. Q.

    2017-05-01

    In this short report, the specific molecular coacervate and two kinds of quantum states in indium-involved amorphous silicon oxide [a-SiOx(In)] are studied. The a-SiOx(In) layer is prepared by the magnetron sputtering process for indium tin oxide (ITO) films deposited on n-type silicon substrates, which has been predicted by molecular dynamics simulation and density function theory calculation. The results have been applied to the interpretation of the electronic structure and hole tunneling transport in ITO-SiOx/n-Si photovoltaic (PV) devices. The most significant achievement is that there is either a transition level at 0.30 eV for p-type conductive conversion or an extra level at Ev + 4.60 eV induced by In-O-Si bonding, denoted as molecular orbital levels, within the dielectric amorphous oxide (a-SiOx). The cognizance is crucial for the concepts of passivation, tunneling, selective contact, inversion, and useful defects in modern PV devices.

  9. Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

    USGS Publications Warehouse

    Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

    2013-01-01

    Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

  10. Real-time plasmon spectroscopy study of the solid-state oxidation and Kirkendall void formation in copper nanoparticles.

    PubMed

    Susman, Mariano D; Feldman, Yishai; Bendikov, Tatyana A; Vaskevich, Alexander; Rubinstein, Israel

    2017-08-31

    Oxidation and corrosion reactions have a major effect on the application of non-noble metals. Kinetic information and simple theoretical models are often insufficient for describing such processes in metals at the nanoscale, particularly in cases involving formation of internal voids (nano Kirkendall effect, NKE) during oxidation. Here we study the kinetics of solid-state oxidation of chemically-grown copper nanoparticles (NPs) by in situ localized surface plasmon resonance (LSPR) spectroscopy during isothermal annealing in the range 110-170 °C. We show that LSPR spectroscopy is highly effective in kinetic studies of such systems, enabling convenient in situ real-time measurements during oxidation. Change of the LSPR spectra throughout the oxidation follows a common pattern, observed for different temperatures, NP sizes and substrates. The well-defined initial Cu NP surface plasmon (SP) band red-shifts continuously with oxidation, while the extinction intensity initially increases to reach a maximum value at a characteristic oxidation time τ, after which the SP intensity continuously drops. The characteristic time τ is used as a scaling parameter for the kinetic analysis. Evolution of the SP wavelength and extinction intensity during oxidation at different temperatures follows the same kinetics when the oxidation time is normalized to τ, thus pointing to a general oxidation mechanism. The characteristic time τ is used to estimate the activation energy of the process, determined to be 144 ± 6 kJ mol(-1), similar to previously reported values for high-temperature Cu thermal oxidation. The central role of the NKE in the solid-state oxidation process is revealed by electron microscopy, while formation of Cu2O as the major oxidation product is established by X-ray diffraction, XPS, and electrochemical measurements. The results indicate a transition of the oxidation mechanism from a Valensi-Carter (VC) to NKE mechanism with the degree of oxidation. To interpret the

  11. Arsenic in ground-water under oxidizing conditions, south-west United States.

    PubMed

    Robertson, F N

    1989-12-01

    Concentrations of dissolved arsenic in ground-water in alluvial basins of Arizona commonly exceed 50 μg L(-1) and reach values as large as 1,300 μg L(-1). Arsenic speciation analyses show that arsenic occurs in the fully oxidized state of plus 5 (As+5), most likely in the form of HAsO4(∼2), under existing oxidizing and pH conditions. Arsenic in source areas presumably is oxidized to soluble As before transport into the basin or, if after transport, before burial. Probable sources of arsenic are the sulphide and arsenide deposits in the mineralized areas of the mountains surrounding the basins. Arsenic content of alluvial material ranged from 2 to 88 ppm. Occurrence and removal of arsenic in ground-water are related to the pH and the redox condition of the ground-water, the oxidation state of arsenic, and sorption or exchange. Within basins, dissolved arsenic correlates (P<0.01) with dissolved molybdenum, selenium, vanadium, and fluoride and with pH, suggesting sorption of negative ions. The sorption hypothesis is further supported by enrichment of teachable arsenic in the basin-fill sediments by about tenfold relative to the crustal abundance and by as much as a thousandfold relative to concentrations found in ground-water. Silicate hydrolysis reactions, as defined within the alluvial basins, under closed conditions cause increases in pH basinward and would promote desorption. Within the region, large concentrations of arsenic are commonly associated with the central parts of basins whose chemistries evolve under closed conditions. Arsenic does not correlate with dissolved iron (r = 0.09) but may be partly controlled by iron in the solid phase. High solid-phase arsenic contents were found in red clay beds. Large concentrations of arsenic also were found in water associated with red clay beds. Basins that contain the larger concentrations are bounded primarily by basalt and andesite, suggesting that the iron content as well as the arsenic content of the basin

  12. Pomegranate juice sugar fraction reduces macrophage oxidative state, whereas white grape juice sugar fraction increases it.

    PubMed

    Rozenberg, Orit; Howell, Amy; Aviram, Michael

    2006-09-01

    The antiatherogenic properties of pomegranate juice (PJ) were attributed to its antioxidant potency and to its capacity to decrease macrophage oxidative stress, the hallmark of early atherogeneis. PJ polyphenols and sugar-containing polyphenolic anthocyanins were shown to confer PJ its antioxidant capacity. In the present study, we questioned whether PJ simple or complex sugars contribute to the antioxidative properties of PJ in comparison to white grape juice (WGJ) sugars. Whole PJ decreased cellular peroxide levels in J774A.1 macrophage cell-line by 23% more than PJ polyphenol fraction alone. Thus, we next determined the contribution of the PJ sugar fraction to the decrease in macrophage oxidative state. Increasing concentrations of the PJ sugar fraction resulted in a dose-dependent decrement in macrophage peroxide levels, up to 72%, compared to control cells. On the contrary, incubation of the cells with WGJ sugar fraction at the same concentrations resulted in a dose-dependent increment in peroxide levels by up to 37%. The two sugar fractions from PJ and from WGJ showed opposite effects (antioxidant for PJ and pro-oxidant for WGJ) also in mouse peritoneal macrophages (MPM) from control as well as from streptozotocin-induced diabetic Balb/C mice. PJ sugar consumption by diabetic mice for 10 days resulted in a small but significant decrement in their peritoneal macrophage total peroxide levels and an increment in cellular glutathione content, compared to MPM harvested from control diabetic mice administrated with water. In contrast, WGJ sugar consumption by diabetic mice resulted in a 22% increment in macrophage total peroxide levels and a 45% decrement in cellular glutathione content. Paraoxonase 2 activity in macrophages increases under oxidative stress conditions. Indeed, macrophage paraoxonase 2 activity was decreased after PJ sugars supplementation, but increased after WGJ sugars supplementation. We conclude that PJ sugar fraction, unlike WGJ sugar fraction

  13. Arsenic in ground-water under oxidizing conditions, south-west United States

    USGS Publications Warehouse

    Robertson, F.N.

    1989-01-01

    Concentrations of dissolved arsenic in ground-water in alluvial basins of Arizona commonly exceed 50 ??g L-1 and reach values as large as 1,300 ??g L-1. Arsenic speciation analyses show that arsenic occurs in the fully oxidized state of plus 5 (As+5), most likely in the form of HAsO4???2, under existing oxidizing and pH conditions. Arsenic in source areas presumably is oxidized to soluble As before transport into the basin or, if after transport, before burial. Probable sources of arsenic are the sulphide and arsenide deposits in the mineralized areas of the mountains surrounding the basins. Arsenic content of alluvial material ranged from 2 to 88 ppm. Occurrence and removal of arsenic in ground-water are related to the pH and the redox condition of the ground-water, the oxidation state of arsenic, and sorption or exchange. Within basins, dissolved arsenic correlates (P<0.01) with dissolved molybdenum, selenium, vanadium, and fluoride and with pH, suggesting sorption of negative ions. The sorption hypothesis is further supported by enrichment of teachable arsenic in the basin-fill sediments by about tenfold relative to the crustal abundance and by as much as a thousandfold relative to concentrations found in ground-water. Silicate hydrolysis reactions, as defined within the alluvial basins, under closed conditions cause increases in pH basinward and would promote desorption. Within the region, large concentrations of arsenic are commonly associated with the central parts of basins whose chemistries evolve under closed conditions. Arsenic does not correlate with dissolved iron (r = 0.09) but may be partly controlled by iron in the solid phase. High solid-phase arsenic contents were found in red clay beds. Large concentrations of arsenic also were found in water associated with red clay beds. Basins that contain the larger concentrations are bounded primarily by basalt and andesite, suggesting that the iron content as well as the arsenic content of the basin fill may

  14. Surface chemistry. Probing the transition state region in catalytic CO oxidation on Ru.

    PubMed

    Öström, H; Öberg, H; Xin, H; LaRue, J; Beye, M; Dell'Angela, M; Gladh, J; Ng, M L; Sellberg, J A; Kaya, S; Mercurio, G; Nordlund, D; Hantschmann, M; Hieke, F; Kühn, D; Schlotter, W F; Dakovski, G L; Turner, J J; Minitti, M P; Mitra, A; Moeller, S P; Föhlisch, A; Wolf, M; Wurth, W; Persson, M; Nørskov, J K; Abild-Pedersen, F; Ogasawara, H; Pettersson, L G M; Nilsson, A

    2015-02-27

    Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  15. Stabilization from chaotic to periodical states in a model of cellular automaton for oxidation of CO.

    PubMed

    Córdoba, A; Lemos, M C; Jiménez-Morales, F

    2006-07-01

    The chaotic behavior of a chemical reaction can be controlled perturbing periodically some of the parameters externally governing the reaction. Based on the resonance phenomenon, the method of external forcing can convert chaotic behavior into a periodical one through the application of a sinusoidal modulation. In this paper we analyze the effect of a periodical perturbation on room temperature in a model of cellular automaton that studies catalytic oxidation of CO. This model considers the reaction of carbon monoxide and oxygen adsorbed on a surface allowing the variation of the surface temperature and analyzing the time oscillations in the reaction. The results of simulations of this model show quasiperiodical and chaotic behaviors. Then the strategy of control through periodical forcing is able to remove the chaotic dynamics by means of the stabilization of periodical solutions, there being enough of a perturbing harmonic function with only one frequency to transform a chaotic state of the system into a periodical state with periodicity 1.

  16. Patterns in the stability of the lower oxidation states of the actinides and lanthanides

    SciTech Connect

    Mikheev, N.B.; Auerman, L.N.; Ionova, G.V.; Korshunov, B.G.; Spitsyn, V.I.

    1986-09-01

    The authors compare the first half of the lanthanides and the second half of the actinides by considering the specifics of the electronic structure of the valence atoms of the f-, d-, and s-orbitals, consisting of he following: The lanthanides from praseodymium to europium and from dysprosium to ytterbium, as well as the actinides from californium to nobelium, have the same electronic configuration f /SUP n/ s/sub 2/ in the state of free neutral atoms, which corresponds to their divalent state. On the basis of a consideration of the energy characteristics of the valence orbitals of the elements of the lanthanide and actinide famililies and as a result of an experimental determination of the standard oxidation potential of these elements, the authors consider the profound similarity between the elements of the first half of the lanthanide family and the second half of the actinide family to be established.

  17. Nitrous Oxide for Labor Analgesia: Expanding Analgesic Options for Women in the United States

    PubMed Central

    Collins, Michelle R; Starr, Sarah A; Bishop, Judith T; Baysinger, Curtis L

    2012-01-01

    Nitrous oxide (N2O) is a commonly used labor analgesic in many Western countries, but is used infrequently in the United States. The University of California at San Francisco has been offering N2O for labor analgesia for more than 30 years. Vanderbilt University Medical Center recently began offering N2O as an option for pain relief in laboring women. Many women report that N2O provides effective pain relief during labor and argue that it should be made more widely available in the United States. This article discusses the use of N2O for pain management during labor, including its history, properties, clinical indications, and use and environmental safety issues. Practical issues regarding implementation of N2O service in a medical center setting are also discussed. PMID:23483795

  18. On the chemical state of Co oxide electrocatalysts during alkaline water splitting.

    PubMed

    Friebel, Daniel; Bajdich, Michal; Yeo, Boon Siang; Louie, Mary W; Miller, Daniel J; Sanchez Casalongue, Hernan; Mbuga, Felix; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Bell, Alexis T; Nilsson, Anders

    2013-10-28

    Resonant inelastic X-ray scattering and high-resolution X-ray absorption spectroscopy were used to identify the chemical state of a Co electrocatalyst in situ during the oxygen evolution reaction. After anodic electrodeposition onto Au(111) from a Co(2+)-containing electrolyte, the chemical environment of Co can be identified to be almost identical to CoOOH. With increasing potentials, a subtle increase of the Co oxidation state is observed, indicating a non-stoichiometric composition of the working OER catalyst containing a small fraction of Co(4+) sites. In order to confirm this interpretation, we used density functional theory with a Hubbard-U correction approach to compute X-ray absorption spectra of model compounds, which agree well with the experimental spectra. In situ monitoring of catalyst local structure and bonding is essential in the development of structure-activity relationships that can guide the discovery of efficient and earth abundant water splitting catalysts.

  19. Isothermal depolarization current spectroscopy of localized states in metal oxide varistors

    NASA Astrophysics Data System (ADS)

    Tonkoshkur, Yu A.; Glot, A. B.

    2012-11-01

    A new method for the processing of time-dependent isothermal depolarization current in oxide varistors is proposed. It involves (i) a new model for kinetics of the depolarization current, which is related to the parameters of the localized states, (ii) an account of the distribution of the relaxation time (which takes place due to the structure inhomogeneity of ceramics) using the Kohlrausch-Williams-Watts stretched exponential function and (iii) the determination of the most probable relaxation time. The proposed method was tested using ZnO high-voltage varistors. The ionization energy (0.06 and 0.16 eV) and the electron capture cross-section (˜10-17 and ˜10-16 cm2) of the bulk donor states in two ZnO varistor ceramics were estimated.

  20. Probing the transition state region in catalytic CO oxidation on Ru

    SciTech Connect

    Ostrom, H.; Oberg, H.; Xin, H.; LaRue, J.; Beye, M.; Dell'Angela, M.; Gladh, J.; Ng, M. L.; Sellberg, J. A.; Kaya, S.; Mercurio, G.; Nordlund, D.; Hantschmann, M.; Hieke, F.; Kuhn, D.; Schlotter, W. F.; Dakovski, G. L.; Turner, J. J.; Minitti, M. P.; Mitra, A.; Moeller, S. P.; Fohlisch, A.; Wolf, M.; Wurth, W.; Persson, M.; Norskov, J. K.; Abild-Pedersen, F.; Ogasawara, H.; Pettersson, L. G. M.; Nilsson, A.

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  1. Iron oxidation state of FeTiO[subscript 3] under high pressure

    SciTech Connect

    Wu, X.; Steinle-Neumann, G.; Narygina, O.; Kantor, I.; McCammon, C.; Pascarelli, S.; Aquilanti, G.; Prakapenka, V.; Dubrovinsky, L.

    2009-08-13

    The oxidation state of iron in FeTiO{sub 3} under high pressure was investigated by combining x-ray diffraction, Moessbauer spectroscopy, x-ray-absorption spectroscopy, and density-functional theory based calculations. Our results demonstrate that the ilmenite-to-perovskite phase transition occurs above 20 GPa at room temperature and on compression two phases coexist to 40 GPa. The Fe{sup 3+}/{Sigma}Fe ratio increases up to 16 GPa, probably attributed to the d-electron drifting of cations via the oxygen bridge in the adjacent octahedral, then decreases at higher pressure due to the ilmenite-to-perovskite phase transition accompanied by a slight decrease in iron valence state. Our ab initio calculations further show that the most significant changes in the charge distribution in FeTiO{sub 3} are associated with Ti and O.

  2. Application of powerful oxidizers in the synthesis of new high-oxidation state actinide and related species

    SciTech Connect

    Yeh, S.M.

    1984-11-01

    The fluorinating and oxide scavenging ability of XeF/sub 6/ have been studied by bringing XeF/sub 6/ into interaction with oxide-fluoride compounds of the third-transition-series elements (W, Re and Os) and uranium, in their highest oxidation states. A/sup +/MOF/sub 5//sup -/ and A/sup +/M/sub 2/O/sub 2/F/sub 9//sup -/ (A = K or Cs, M = W or U) were converted to A/sup +/MF/sub 7//sup -/ by XeF/sub 6/, but the rhenium and osmium compounds, K/sup +/ReO/sub 2/F/sub 4//sup -/ and XeF/sub 5//sup +/OsO/sub 3/F/sub 3//sup -/, resisted interaction with XeF/sub 6/. Strong interactions between XeF/sub 2/ or KrF/sub 2/ and the solvent have been observed for their solutions in anhydrous HF. Both XeF/sub 2/ and KrF/sub 2/ are seen to be effective in breaking up the polymeric (HF)/sub n/ chains. Only weak interactions occur between cations and anions of KrF/sup +/AuF/sub 6//sup -/ and Kr/sub 2/F/sub 3//sup +/AuF/sub 6//sup -/ in HF. The AuF/sub 6//sup -/ anions are slightly distorted from O/sub h/ symmetry. Kr/sub 2/F/sub 3//sup +/ cations in HF have the same dissymmetric V-shape which occurs in crystalline salts. A low-temperature orthorhombic form, ..beta..-ReF/sub 6//sup +/SbF/sub 6//sup -/, a high-temperature rhombohedral form, ..cap alpha..-ReF/sub 6//sup +/SbF/sub 6//sup -/, and a ReF/sub 6//sup +/AuF/sub 6//sup -/ have been prepared. These compounds possess only kinetic stability at ambient temperature and at approx. 20/sup 0/C are best represented as ReF/sub 6//sup +/ReF/sub 7/MF/sub 6//sup -/MF/sub 5/. Thermochemical energy evaluations indicate that the ionization potential of ReF/sub 6/ is 261 kcal mole/sup -1/ and that the fluoride-ion affinity of ReF/sub 6//sup +/ is -214 kcal mole/sup -1/. This is more exothermal than the corresponding process for IF/sub 6//sup +/ (-208 kcal mole/sup -1/). In contrast, ReOF/sub 5/ is shown to be a better fluoro-base than IOF/sub 5/ and also is a better base than ReF/sub 7/. ReOF/sub 4//sup +/MF/sub 6//sup -/ (M = Sb, Au and As

  3. Silver corrole complexes: unusual oxidation states and near-IR-absorbing dyes.

    PubMed

    Sinha, Woormileela; Sommer, Michael G; Deibel, Naina; Ehret, Fabien; Sarkar, Biprajit; Kar, Sanjib

    2014-11-24

    Macrocycles such as porphyrins and corroles have important functions in chemistry and biology, including light absorption for photosynthesis. Generation of near-IR (NIR)-absorbing dyes based on metal complexes of these macrocycles for mimicking natural photosynthesis still remains a challenging task. Herein, the syntheses of four new Ag(III) corrolato complexes with differently substituted corrolato ligands are presented. A combination of structural, electrochemical, UV/Vis/NIR-EPR spectroelectrochemical, and DFT studies was used to decipher the geometric and electronic properties of these complexes in their various redox states. This combined approach established the neutral compounds as stable Ag(III) complexes, and the one-electron reduced species of all the compounds as unusual, stable Ag(II) complexes. The one-electron oxidized forms of two of the complexes display absorptions in the NIR region, and thus they are rare examples of mononuclear complexes of corroles that absorb in the NIR region. The appearance of this NIR band, which has mixed intraligand charge transfer/intraligand character, is strongly dependent on the substituents of the corrole rings. Hence, the present work revolves round the design principles for the generation of corrole-based NIR-absorbing dyes and shows the potential of corroles for stabilizing unusual metal oxidation states. These findings thus further contribute to the generation of functional metal complexes based on such macrocyclic ligands. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Reconciling Organic Aerosol Volatility, Hygroscopicity, and Oxidation State During the Colorado DISCOVER-AQ Deployment

    NASA Astrophysics Data System (ADS)

    Hite, J. R.; Moore, R.; Martin, R.; Thornhill, K. L., II; Winstead, E.; Anderson, B. E.; Nenes, A.

    2014-12-01

    The organic fraction of submicron aerosol can profoundly impact radiative forcing on climate directly, through enhancement of extinction, or indirectly through modulation of cloud formation. Semi-volatile constituents of organic ambient aerosol are of particular interest as their partitioning between the vapor and aerosol phases is not well constrained by current atmospheric models and appears to play an important role in the formation of cloud condensation nuclei (CCN) as suggested by recent research. An experimental setup consisting of a DMT CCN counter and SMPS downstream of a custom-built thermodenuder assembly was deployed during the summer 2014 DISCOVER-AQ field campaign to retrieve simultaneous, size-resolved volatility and hygroscopicity - through the use of scanning mobility CCN analysis (SMCA). Housed in the NASA Langley mobile laboratory, a suite of complimentary measurements were made available onboard including submicron aerosol composition and oxidation state provided by an HR-ToF-AMS, and aerosol optical properties provided by a range of other instruments including an SP2. Air masses sampled from locations across the Central Colorado region include influences from regional aerosol nucleation/growth events, long-range transport of Canadian biomass burning aerosols, cattle feedlot emissions and influences of the Denver urban plume - amidst a backdrop of widespread oil and gas exploration. The analysis focuses on the reconciliation of the retrieved aerosol volatility distributions and corresponding hygroscopicity and oxidation state observations, including the use of AMS factor analysis.

  5. Caesium in high oxidation states and as a p-block element.

    PubMed

    Miao, Mao-sheng

    2013-10-01

    The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry, rooted in the atomic shell structure. Within compounds, Group I elements, for example, invariably assume the +1 oxidation state, and their chemical properties differ completely from those of the p-block elements. These general rules govern our understanding of chemical structures and reactions. Here, first-principles calculations show that, under pressure, caesium atoms can share their 5p electrons to become formally oxidized beyond the +1 state. In the presence of fluorine and under pressure, the formation of CsF(n) (n > 1) compounds containing neutral or ionic molecules is predicted. Their geometry and bonding resemble that of isoelectronic XeF(n) molecules, showing a caesium atom that behaves chemically like a p-block element under these conditions. The calculated stability of the CsF(n) compounds shows that the inner-shell electrons can become the main components of chemical bonds.

  6. Stress Intensity Effect on Solid State Oxidation of Ni-Cr Alloy with Different Chromium Concentrates

    NASA Astrophysics Data System (ADS)

    Tirtom, Ismail; Das, Nishith Kumar; Shoji, Tetsuo

    Ni-base alloy is widely used in light water reactor component and the recent study has shown stress corrosion cracking (SCC). Over the years various attempts have been made to obtain mechanism of SCC but it still require more fundamental study to understand clearly. This study presents an approach based on the multiscale modeling, to assess the influence of alloy composition and stress intensity on the initial stage of solid state oxidation of the Ni-Cr alloy. The multiscale modeling considers different length scales such as finite element method (FEM) / quasi-continuum (QC) / quantum chemical molecular dynamics (QCMD), for analyzing crack tip molecular domain. The compact tension (CT) specimen of alloy 600 has been loaded for stress intensity, after that the micro region has chosen for the QC model which is a combination of continuum and atomic method. Finally, the deformed atomic position has picked for the QCMD simulation with some water molecules. The simulated results show that the chromium segregates faster than nickel atoms from the surface and make preferential bonding with oxygen. The preferential bonding forms a passive film. Applied stress intensity deformed the structure which may increase the atomic distance. As distance increases the absorption of water molecule or OH or oxygen into lattice increases. The stress intensity raises the crack tip solid state oxidation that may enhance SCC initiation.

  7. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    PubMed Central

    Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

    2013-01-01

    Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance. PMID:23698776

  8. Steady-state coupling of four membrane systems in mitochondrial oxidative phosphorylation.

    PubMed Central

    Hill, T L

    1979-01-01

    According to Alexandre, Reynafarje, and Lehninger, four different membrane systems are involved, with definite stoichiometry, in the mitochondrial synthesis of ATP by electron transport, via proton transport. We adopt this model and pursue some of its thermodynamic consequences. At steady state, each of the four systems must have the same flux J through the membrane and the overall thermodynamic force X for oxidative phosphorylation is the sum of the four separate forces. From these properties, using an empirical linear flux-force relation for each system, it is easy to obtain J as a function of X. In turn, X depends on the inside [NAD+]/[NADH] and the outside [ATP]/[ADP][Pi] quotients (and on the pH inside). Thus, J is related to these quotients. The relationship we derive is similar to that described by Erecińska and Wilson, as deduced from a quite different model of oxidative phosphorylation. Proton transport is involved explicitly in three of the four systems of the present model. However, because of the steady-state stoichiometric coupling of the four systems, proton transport does not appear in the overall reaction. On the other hand, Erecińska and Wilson use, in their model, a direct connection between electron transport and ATP synthesis. The present paper demonstrates that J can be related to the quotients mentioned above without this direct connection. PMID:287064

  9. Quantized conductance coincides with state instability and excess noise in tantalum oxide memristors

    PubMed Central

    Yi, Wei; Savel'ev, Sergey E.; Medeiros-Ribeiro, Gilberto; Miao, Feng; Zhang, M.-X.; Yang, J. Joshua; Bratkovsky, Alexander M.; Williams, R. Stanley

    2016-01-01

    Tantalum oxide memristors can switch continuously from a low-conductance semiconducting to a high-conductance metallic state. At the boundary between these two regimes are quantized conductance states, which indicate the formation of a point contact within the oxide characterized by multistable conductance fluctuations and enlarged electronic noise. Here, we observe diverse conductance-dependent noise spectra, including a transition from 1/f2 (activated transport) to 1/f (flicker noise) as a function of the frequency f, and a large peak in the noise amplitude at the conductance quantum GQ=2e2/h, in contrast to suppressed noise at the conductance quantum observed in other systems. We model the stochastic behaviour near the point contact regime using Molecular Dynamics–Langevin simulations and understand the observed frequency-dependent noise behaviour in terms of thermally activated atomic-scale fluctuations that make and break a quantum conductance channel. These results provide insights into switching mechanisms and guidance to device operating ranges for different applications. PMID:27041485

  10. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    NASA Astrophysics Data System (ADS)

    Seo, Jihoon; Moon, Jinok; Kim, Joo Hyun; Lee, Kangchun; Hwang, Junha; Yoon, Heesung; Yi, Dong Kee; Paik, Ungyu

    2016-12-01

    In this study, we have investigated the role of the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surfaces for silicate adsorption. In aqueous medium, the Ce3+ sites lead to the formation of -OH groups at the CeO2 surface through H2O dissociation. Silicate ions can adsorb onto the CeO2 surface through interaction with the -OH groups (-Ce-OH- + -Si-O- ↔ -Ce-O-Si- + OH-). As the Ce3+ concentration increased from 19.3 to 27.6%, the surface density of -OH group increased from 0.34 to 0.72 OH/nm2. To evaluate the adsorption behaviors of silicate ions onto CeO2 NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (KF) and adsorption intensity (1/n) indicated that CeO2 NPs with high Ce3+ concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surface can have a significant influence on the silicate adsorption.

  11. Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

    NASA Astrophysics Data System (ADS)

    Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

    2009-12-01

    The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration

  12. Regulation of skeletal muscle carbohydrate oxidation during steady-state contraction.

    PubMed

    Timmons, J A; Poucher, S M; Constantin-Teodosiu, D; Macdonald, I A; Greenhaff, P L

    1998-05-01

    Pyruvate dehydrogenase complex (PDC) activation status has been described as being central in the regulation of tissue substrate oxidation as outlined by the glucose fatty-acid cycle. In the present study we examined the effects of reduced lipolysis, with use of nicotinate, and increased PDC activation, with use of dichloroacetate (DCA), on substrate utilization during 20 min of submaximal steady-state contraction (approximately 80% of maximal O2 uptake) in canine gracilis skeletal muscle. At rest, PDC activation was unchanged by nicotinate but was approximately 2.5-fold higher in the DCA group than in the control group (P < 0.05). During contraction, PDC activation status increased to 3.5 mmol acetyl-CoA.min-1.kg-1 at 37 degrees C in the control group, remained at 4.5 mmol acetyl-CoA.min-1.kg-1 at 37 degrees C in the DCA group, but only increased to 2.2 mmol acetyl-CoA.min-1.kg-1 at 37 degrees C in the nicotinate group (P < 0.05). However, the estimated amount of carbohydrate oxidized during the 20-min contraction was similar across groups and did not follow the degree of PDC activation (81.2 +/- 22.9, 95.9 +/- 11.7, and 89.3 +/- 18.9 mmol glucosyl units/kg dry muscle for control, nicotinate, and DCA, respectively). Thus it would appear that, during steady-state contraction, PDC activation status does not determine the rate of carbohydrate oxidation in skeletal muscle.

  13. Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

    Treesearch

    Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

    2015-01-01

    A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

  14. Influence of Sources on Plutonium Mobility and Oxidation State Transformations in Vadose Zone Sediments

    SciTech Connect

    Kaplan,D.; Powell, B.; Duff, M.; Demirkanli, D.; Denham, M.; Fjeld, R.; Molz, F.

    2007-01-01

    Well-defined solid sources of Pu(III) (PuCl3), Pu(IV) (Pu (NO3)4 and Pu (C2O4)2), and Pu(VI) (PuO2(NO3)2) were placed in lysimeters containing vadose zone sediments and exposed to natural weather conditions for 2 or 11 years. The objective of this study was to measure the release rate of Pu and the changes in the Pu oxidation states from these Pu sources with the intent to develop a reactive transport model source-term. Pu(III) and Pu(IV) sources had identical Pu concentration depth profiles and similar Pu release rates. Source release data indicate that PuIV(C2O4)2 was the least mobile, whereas PuVIO2(NO3)2 was the most mobile. Synchrotron X-ray fluorescence (SXRF) revealed that Pu was very unevenly distributed on the sediment and Mn concentrations were too low (630 mg kg-1) and perhaps of the wrong mineralogy to influence Pu distribution. The high stability of sorbed Pu(IV) is proposed to be due to the formation of a stable hydrolyzed Pu(IV) surface species. Plutonium X-ray absorption near-edge spectroscopy (XANES) analysis conducted on sediment recovered at the end of the study from the PuIV(NO3)4- and PuIIICl3-amended lysimeters contained essentially identical Pu distributions: approximately 37% Pu(III), 67% Pu(IV), 0% Pu(V), and 0% Pu(VI). These results were similar to those using a wet chemistry Pu oxidation state assay, except the latter method did not detect any Pu(III) present on the sediment but instead indicated that 93-98% of the Pu existed as Pu(IV). This discrepancy was likely attributable to incomplete extraction of sediment Pu(III) by the wet chemistry method. Although Pu has been known to exist in the +3 oxidation state under microbially induced reducing conditions for decades, to our knowledge, this is the first observation of steady-state Pu(III) in association with natural sediments. On the basis of thermodynamic considerations, Pu(III) has a wide potential distribution, especially in acidic environments, and as such may warrant further

  15. Normal-state nodal electronic structure in underdoped high-Tc copper oxides.

    PubMed

    Sebastian, Suchitra E; Harrison, N; Balakirev, F F; Altarawneh, M M; Goddard, P A; Liang, Ruixing; Bonn, D A; Hardy, W N; Lonzarich, G G

    2014-07-03

    An outstanding problem in the field of high-transition-temperature (high-Tc) superconductivity is the identification of the normal state out of which superconductivity emerges in the mysterious underdoped regime. The normal state uncomplicated by thermal fluctuations can be studied using applied magnetic fields that are sufficiently strong to suppress long-range superconductivity at low temperatures. Proposals in which the normal ground state is characterized by small Fermi surface pockets that exist in the absence of symmetry breaking have been superseded by models based on the existence of a superlattice that breaks the translational symmetry of the underlying lattice. Recently, a charge superlattice model that positions a small electron-like Fermi pocket in the vicinity of the nodes (where the superconducting gap is minimum) has been proposed as a replacement for the prevalent superlattice models that position the Fermi pocket in the vicinity of the pseudogap at the antinodes (where the superconducting gap is maximum). Although some ingredients of symmetry breaking have been recently revealed by crystallographic studies, their relevance to the electronic structure remains unresolved. Here we report angle-resolved quantum oscillation measurements in the underdoped copper oxide YBa2Cu3O6 + x. These measurements reveal a normal ground state comprising electron-like Fermi surface pockets located in the vicinity of the nodes, and also point to an underlying superlattice structure of low frequency and long wavelength with features in common with the charge order identified recently by complementary spectroscopic techniques.

  16. Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating.

    PubMed

    Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S; Takeuchi, Ichiro; Greene, Richard L

    2016-05-25

    The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2-xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of -2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected.

  17. Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating

    NASA Astrophysics Data System (ADS)

    Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S.; Takeuchi, Ichiro; Greene, Richard. L.

    2016-05-01

    The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2‑xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of ‑2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected.

  18. Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating

    PubMed Central

    Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S.; Takeuchi, Ichiro; Greene, Richard. L.

    2016-01-01

    The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2−xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of −2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected. PMID:27221198

  19. Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

    NASA Astrophysics Data System (ADS)

    Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

    2015-05-01

    The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

  20. Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.

    1989-01-01

    Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.

  1. Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.

    1989-01-01

    Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.

  2. Influence of the Oxidation States of 4-Methylcatechol and Catechin on the Oxidative Stability of β-Lactoglobulin.

    PubMed

    Jongberg, Sisse; Utrera, Mariana; Morcuende, David; Lund, Marianne N; Skibsted, Leif H; Estévez, Mario

    2015-09-30

    Chemical interactions between proteins and phenols affect the overall oxidative stability of a given biological system. To investigate the effect of protein-phenol adduct formation on the oxidative stability of β-lactoglobulin (β-LG), the protein was left to react with an equimolar concentration of 4-methylcatechol (4MC), catechin (Cat), or their respective quinone forms, 4-methylbenzoquinone (4MBQ) and catechin-quinone (CatQ), and subsequently subjected to metal-catalyzed oxidation by Fe(II)/H2O2 for 20 days at 37 °C. The reaction with 4MBQ resulted in 60% thiol loss and 22% loss of amino groups, whereas the addition of 4MC resulted in 12% thiol loss. The reaction with Cat or CatQ resulted in no apparent modification of β-LG. The oxidative stability of β-LG after reaction with each of 4MC, 4MBQ, Cat, or CatQ was impaired. Especially 4MC and 4MBQ were found to be pro-oxidative toward α-aminoadipic semialdehyde and γ-glutamic semialdehyde formation as well as the generation of fluorescent Schiff base products. The changes observed were ascribed to the redirection of oxidation as a result of the blocking of thiol groups but also to the oxidative deamination pathway, accelerating the production of semialdehydes and subsequently Schiff base structures.

  3. Electronic solution spectra for uranium and neptunium in oxidation states (III) to (VI) in anhydrous hydrogen fluoride

    SciTech Connect

    Baluka, M.; Edelstein, N.; O'Donnell, T. A.

    1981-10-01

    In this paper, spectra have been recorded for solutions in anhydrous hydrogen fluoride (AHF) of uranium and neptunium in oxidation states III to VI. The spectra for U(III), Np(III), and Np(IV) in AHF are very similar to those in acidified aqueous solution, but that for U(IV) suggests that the cationic species is UF22+. The AHF spectra for the elements in oxidation states V and VI are not comparable with those of the formally analogous aqueous solutions, where the elements exist as well-defined dioxo cations. Nonetheless, the AHF spectra can be related to spectra in the gas phase, in the solid state or in nonaqueous solvents for each element in its appropriate oxidation state.

  4. Revealing the role of oxidation state in interaction between nitro/amino-derived particulate matter and blood proteins

    PubMed Central

    Liu, Zhen; Li, Ping; Bian, Weiwei; Yu, Jingkai; Zhan, Jinhua

    2016-01-01

    Surface oxidation states of ultrafine particulate matter can influence the proinflammatory responses and reactive oxygen species levels in tissue. Surface active species of vehicle-emission soot can serve as electron transfer-mediators in mitochondrion. Revealing the role of surface oxidation state in particles-proteins interaction will promote the understanding on metabolism and toxicity. Here, the surface oxidation state was modeled by nitro/amino ligands on nanoparticles, the interaction with blood proteins were evaluated by capillary electrophoresis quantitatively. The nitro shown larger affinity than amino. On the other hand, the affinity to hemoglobin is 103 times larger than that to BSA. Further, molecular docking indicated the difference of binding intensity were mainly determined by hydrophobic forces and hydrogen bonds. These will deepen the quantitative understanding of protein-nanoparticles interaction from the perspective of surface chemical state. PMID:27181651

  5. Revealing the role of oxidation state in interaction between nitro/amino-derived particulate matter and blood proteins

    NASA Astrophysics Data System (ADS)

    Liu, Zhen; Li, Ping; Bian, Weiwei; Yu, Jingkai; Zhan, Jinhua

    2016-05-01

    Surface oxidation states of ultrafine particulate matter can influence the proinflammatory responses and reactive oxygen species levels in tissue. Surface active species of vehicle-emission soot can serve as electron transfer-mediators in mitochondrion. Revealing the role of surface oxidation state in particles-proteins interaction will promote the understanding on metabolism and toxicity. Here, the surface oxidation state was modeled by nitro/amino ligands on nanoparticles, the interaction with blood proteins were evaluated by capillary electrophoresis quantitatively. The nitro shown larger affinity than amino. On the other hand, the affinity to hemoglobin is 103 times larger than that to BSA. Further, molecular docking indicated the difference of binding intensity were mainly determined by hydrophobic forces and hydrogen bonds. These will deepen the quantitative understanding of protein-nanoparticles interaction from the perspective of surface chemical state.

  6. The Effect of Cerium Oxide Nanoparticle Valence State on Reactive Oxygen Species and Toxicity.

    PubMed

    Dunnick, Katherine M; Pillai, Rajalekshmi; Pisane, Kelly L; Stefaniak, Aleksandr B; Sabolsky, Edward M; Leonard, Stephen S

    2015-07-01

    Cerium oxide (CeO2) nanoparticles, which are used in a variety of products including solar cells, gas sensors, and catalysts, are expected to increase in industrial use. This will subsequently lead to additional occupational exposures, making toxicology screenings crucial. Previous toxicology studies have presented conflicting results as to the extent of CeO2 toxicity, which is hypothesized to be due to the ability of Ce to exist in both a +3 and +4 valence state. Thus, to study whether valence state and oxygen vacancy concentration are important in CeO2 toxicity, CeO2 nanoparticles were doped with gadolinium to adjust the cation (Ce, Gd) and anion (O) defect states. The hypothesis that doping would increase toxicity and decrease antioxidant abilities as a result of increased oxygen vacancies and inhibition of +3 to +4 transition was tested. Differences in toxicity and reactivity based on valence state were determined in RLE-6TN rat alveolar epithelial and NR8383 rat alveolar macrophage cells using enhanced dark field microscopy, electron paramagnetic resonance (EPR), and annexin V/propidium iodide cell viability stain. Results from EPR indicated that as doping increased, antioxidant potential decreased. Alternatively, doping had no effect on toxicity at 24 h. The present results imply that as doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant potential decreases, suggesting that differences in reactivity of CeO2 are due to the ability of Ce to transition between the two valence states and the presence of increased oxygen vacancies, rather than dependent on a specific valence state.

  7. Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

    NASA Technical Reports Server (NTRS)

    Hudman, Rynda C.; Jacob, Daniel J.; Turquety, Solene; Leinbensperger, E. M.; Murray, L. T.; Wu, Samuel; Gilliland, A. B.; Avery, Melody A.; Bertram, Timothy H.; Brune, W. H.; Cohen, Ronald C.; Dibb, Jack E.; Flocke, F. M.; Fried, Alan; Holloway, J.; Neuman, J. A.; Orville, R.; Perring, Anne; Ren, Xinrong; Ryerson, T. B.; Sachse, Glen W.; Singh, H. B.; Swanson, Aaron; Wooldridge, Paul J.

    2007-01-01

    We use observations from two aircraft during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of the regional sources, chemical evolution, and export of nitrogen oxides. The boundary layer NO(x) data provide top-down verification of a 50% decrease in power plant and industry NO(x) emissions over the eastern United States between 1999 and 2004. Observed 8-12 8 km NO(x) concentrations in ICARTT were 0.55 +/- 36 ppbv, much larger than in previous United States aircraft campaigns (ELCHEM, SUCCESS, SONEX). We show that regional lightning was the dominant source of this NO(x) and increased upper tropospheric ozone by 10 ppbv. Simulating the ICARTT upper tropospheric NO(x) observations with GEOS-Chem require a factor of 4 increase in the model NO(x) yield per flash (to 500 mol/flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, and if correct would imply a broader lightning influence in the upper troposphere than presently thought.An NO(y)-CO correlation analysis of the fraction f of North American NO(x) emissions vented to the free troposphere as NO(y) (sum of NO(x) and its oxidation products PAN and HNO3) s shows observed f=16+/-10 percent and modeled f=14 +/- 8 percent, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NO(y) export efficiency and speciation, supporting previous model estimates of a large U.S. contribution to tropospheric ozone through NO(x) and PAN export.

  8. Simulating the effect of photochemical aging on the oxidation state and hygroscopicity of organic aerosol

    NASA Astrophysics Data System (ADS)

    Tsimpidi, A.; Karydis, V.; Pandis, S. N.; Lelieveld, J.

    2016-12-01

    Hygroscopicity is an important property of aerosols which describes their propensity to absorb water vapor. The hygroscopicity of organic aerosol (OA) can change during its atmospheric aging affecting the total aerosol hygroscopicity. A more hygroscopic particle will grow more rapidly under humid conditions, scatter incident sunlight more efficiently; and it will more likely form cloud droplets. Both phenomena strongly influence the radiative forcing of climate through the direct and indirect effects of aerosols. Therefore, taking into account the hygrscopicity changes of OA during its atmospheric aging is of prime importance to accurately estimate the aerosol climatic impact. Here, we use a computationally efficient module for the description of OA composition and evolution in the atmosphere (ORACLE) (Tsimpidi et al., 2014) in the frame of the global chemistry climate model EMAC to simulate the global distribution of the OA oxidation state and hygroscopicity. To track the evolution of the OA oxidation state during its atmospheric aging, ORACLE is modified to include the description of the OA oxygen content change when mass from any OA surrogate species reacts with the OH radical. Subsequently, it is assumed that the cloud condensation nuclei (CCN) activity of OA, expressed in the form of the hygroscopicity parameter κ, will increase with increasing oxygen content (expressed by the oxygen per carbon ratio, O:C) and will range from κ = 0 (for O:C ≤ 0.2) to κ = 0.35 (for O:C = 1). The exact relationship between O:C and κ is determined based on aerosol mass spectrometer (AMS) and continuous flow CCN (CCNC) measurements of SOA (Lambe et al., 2011). Following a straightforward mixing rule, the hygroscopicity and oxygen content of total OA is calculated based on the hygroscopicities of the individual OA compounds and their degree of oxidation. A global dataset of O:C measurements is used to validate the model results. ReferencesLambe, A. T., et al. : Laboratory

  9. Iron Stable Isotopes, Magmatic Differentiation and the Oxidation State of Mariana Arc Magmas

    NASA Astrophysics Data System (ADS)

    Williams, H. M.; Prytulak, J.; Plank, T. A.; Kelley, K. A.

    2014-12-01

    Arc magmas are widely considered to be oxidized, with elevated ferric iron contents (Fe3+/ΣFe) relative to mid-ocean ridge lavas (1, 2). However, it is unclear whether the oxidized nature of arc basalts is a primary feature, inherited from the sub-arc mantle, or the product of magmatic differentiation and/or post eruptive alteration processes (3). Iron stable isotopes can be used to trace the distribution of Fe during melting and magmatic differentiation processes (4, 5). Here we present Fe isotope data for well-characterized samples (6-8) from islands of the Central Volcanic Zone (CVZ) of the intra-oceanic Mariana Arc to explore the effect of magmatic differentiation processes on Fe isotope systematics. The overall variation in the Fe isotope compositions (δ57Fe) of samples from the CVZ islands ranges from -0.10 ±0.04 to 0.29 ± 0.01 ‰. Lavas from Anatahan are displaced to lower overall δ57Fe values (range -0.10 ±0.04 to 0.18 ±0.01 ‰) relative to other CVZ samples. Fe isotopes in the Anatahan suite (range -0.10 ±0.04 to 0.18 ±0.01 ‰) are positively correlated with SiO2 and negatively correlated with Ca, Fe2O3(t), Cr and V and are displaced to lower overall δ57Fe values relative to other CVZ samples. These correlations can be interpreted in terms of clinopyroxene and magnetite fractionation, with magnetite saturation throughout the differentiation sequence. Magnetite saturation is further supported by negative correlations between V, Fe2O3(t), Cr and MgO (for MgO <3.5 wt%). The early saturation of magnetite in the Anatahan and CVZ lavas is likely to be a function of high melt water content (9, 10) and potentially elevated melt oxidation state. Future work will focus on determining the relationships between mineral Fe isotope partitioning effects and melt composition and oxidation state. 1. R. Arculus, Lithos (1994). 2. K. A. Kelley et al., Science (2009). 3. C.-T. A. Lee et al., J. Pet. (2005). 4. N. Dauphas et al., EPSL (2014). 5. P. A. Sossi et al

  10. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    NASA Astrophysics Data System (ADS)

    Danielson, L. R.; Righter, K.; Keller, L. P.; Rahman, Z.

    2015-12-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion [1], transitioned from reduced to oxidized [2,3,4], or from oxidized to reduced [1,5]. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P <4 GPa, Fe3+/ΣFe decreased slightly with increasing P, similar to terrestrial basalt [6,7,8]. For oxidizing experiments < 7GPa, Fe3+/ΣFe decreased as well [9], but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+ [1,10]. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 °C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after [11], but both resulted in a finer grained polyphase texture. Experiments are currently underway to test how different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and

  11. Structural studies of Proteus mirabilis catalase in its ground state, oxidized state and in complex with formic acid.

    PubMed

    Andreoletti, Pierre; Pernoud, Anaïs; Sainz, Germaine; Gouet, Patrice; Jouve, Hélène Marie

    2003-12-01

    The structure of Proteus mirabilis catalase in complex with an inhibitor, formic acid, has been solved at 2.3 A resolution. Formic acid is a key ligand of catalase because of its ability to react with the ferric enzyme, giving a high-spin iron complex. Alternatively, it can react with two transient oxidized intermediates of the enzymatic mechanism, compounds I and II. In this work, the structures of native P. mirabilis catalase (PMC) and compound I have also been determined at high resolution (2.0 and 2.5 A, respectively) from frozen crystals. Comparisons between these three PMC structures show that a water molecule present at a distance of 3.5 A from the haem iron in the resting state is absent in the formic acid complex, but reappears in compound I. In addition, movements of solvent molecules are observed during formation of compound I in a cavity located away from the active site, in which a glycerol molecule is replaced by a sulfate. These results give structural insights into the movement of solvent molecules, which may be important in the enzymatic reaction.

  12. Distribution of molybdenum oxidation states in reduced Mo/TiO sub 2 catalysts: Correlation with benzene hydrogenation activity

    SciTech Connect

    Quincy, R.B.; Houalla, M.; Proctor, A.; Hercules, D.M. )

    1990-02-22

    A 5 wt % MoO{sub 3}/TiO{sub 2} catalyst was reduced in hydrogen at various temperatures to produce a surface with average Mo oxidation states between +6 and 0. The changes in molybdenum oxidation states as a function of the extent of reduction were monitored by gravimetric analyses and x-ray photoelectron spectroscopy (XPS, ESCA), and the results were correlated with benzene hydrogenation activity. ESCA Mo 3d{sub 5/2} binding energy values for the various Mo oxidation states on a 5 wt % MoO{sub 3}/TiO{sub 2} catalyst show a shift of 5.1 eV between Mo{sup +6} (232.7 eV) and Mo{sup 0} (227.6 eV). The benzene hydrogenation activity was found to depend strongly on the extent of reduction of the Mo phase. Comparison of benzene hydrogenation activity with the distribution of Mo oxidation states determined by ESCA suggests that molybdenum ions with an oxidation state of +2 are the most active species.

  13. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    SciTech Connect

    Nelson, George; Harris, William; Izzo, John; Grew, Kyle N.

    2012-01-20

    Reduction-oxidation (redox) cycling of the nickel electrocatalyst phase in the solid oxide fuel cell (SOFC) anode can lead to performance degradation and cell failure. A greater understanding of nickel redox mechanisms at the microstructural level is vital to future SOFC development. Transmission x-ray microscopy (TXM) provides several key techniques for exploring oxidation states within SOFC electrode microstructure. Specifically, x-ray nanotomography and x-ray absorption near edge structure (XANES) spectroscopy have been applied to study samples of varying nickel (Ni) and nickel oxide (NiO) compositions. The imaged samples are treated as mock SOFC anodes containing distinct regions of the materials in question. XANES spectra presented for the individual materials provide a basis for the further processing and analysis of mixed samples. Images of composite samples obtained are segmented, and the distinct nickel and nickel oxide phases are uniquely identified using full field XANES spectroscopy. Applications to SOFC analysis are discussed.

  14. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    PubMed Central

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  15. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1 based on solid-state redox reaction of oxide ions.

  16. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    PubMed

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn(4+) with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g(-1) based on solid-state redox reaction of oxide ions.

  17. Variation of the oxidation state of verdoheme in the heme oxygenase reaction

    SciTech Connect

    Gohya, Tomohiko; Sato, Michihiko; Zhang Xuhong; Migita, Catharina T.

    2008-11-14

    Heme oxygenase (HO) converts hemin to biliverdin, CO, and iron applying molecular oxygen and electrons. During successive HO reactions, two intermediates, {alpha}-hydroxyhemin and verdoheme, have been generated. Here, oxidation state of the verdoheme-HO complexes is controversial. To clarify this, the heme conversion by soybean and rat HO isoform-1 (GmHO-1 and rHO-1, respectively) was compared both under physiological conditions, with oxygen and NADPH coupled with ferredoxin reductase/ferredoxin for GmHO-1 or with cytochrome P450 reductase for rHO-1, and under a non-physiological condition with hydrogen peroxide. EPR measurements on the hemin-GmHO-1 reaction with oxygen detected a low-spin ferric intermediate, which was undetectable in the rHO-1 reaction, suggesting the verdoheme in the six-coordinate ferric state in GmHO-1. Optical absorption measurements on this reaction indicated that the heme degradation was extremely retarded at verdoheme though this reaction was not inhibited under high-CO concentrations, unlike the rHO-1 reaction. On the contrary, the Gm and rHO-1 reactions with hydrogen peroxide both provided ferric low-spin intermediates though their yields were different. The optical absorption spectra suggested that the ferric and ferrous verdoheme coexisted in reaction mixtures and were slowly converted to the ferric biliverdin complex. Consequently, in the physiological oxygen reactions, the verdoheme is found to be stabilized in the ferric state in GmHO-1 probably guided by protein distal residues and in the ferrous state in rHO-1, whereas in the hydrogen peroxide reactions, hydrogen peroxide or hydroxide coordination stabilizes the ferric state of verdoheme in both HOs.

  18. Mantle oxidation state and its relationship to tectonic environment and fluid speciation.

    PubMed

    Wood, B J; Bryndzia, L T; Johnson, K E

    1990-04-20

    The earth's mantle is degassed along mid-ocean ridges, while rehydration and possibly recarbonaton occurs at subduction zones. These processes and the speciation of C-H-O fluids in the mantle are related to the oxidation state of mantle peridotite. Peridotite xenoliths from continental localities exhibit an oxygen fugacity (fo(2)) range from -1.5 to +1.5 log units relative to the FMQ (fayalite-magnetite-quartz) buffer. The lowest values are from zones of continental extension. Highly oxidized xenoliths (fo(2) greater than FMQ) come from regions of recent or acive subduction (for example, Ichinomegata, Japan), are commonly amphibole-bearing, and show trace element and isotopic evidence of fluid-rock interaction. Peridotites from ocean ridges are reduced and have an averae fo(2) of about -0.9 log units relative to FMQ, virtually coincident with values obtained from mid-ocean ridge basalt (MORB) glasses. These data are further evidence of the genetic link between MORB liquids and residual peridotite and indicate that the asthenosphere, although reducing, has CO(2) and H(2)O as its major fluid species. Incorporation of oxidized material from subduction zones into the continental lithosphere produces xenoliths that have both asthenospheric and subduction signatures. Fluids in the lithosphere are also dominated by CO(2) and H(2)O, and native C is generally unstable. Although the occurrence of native C (diamond) in deep-seated garnetiferous xenoliths and kimberlites does not require reducing conditions, calculations indicate that high Fe(3+) contents are stabilized in the garnet structure and that fo(2) deareases with increasing depth.

  19. Terpyridine Molybdenum Dinitrogen Chemistry: Synthesis of Dinitrogen Complexes That Vary by Five Oxidation States.

    PubMed

    Bezdek, Máté J; Guo, Sheng; Chirik, Paul J

    2016-03-21

    A bimetallic molybdenum complex bridged by an activated dinitrogen ligand and supported by phosphine and terpyridine ligands, [{((Ph)Tpy)(PPh2Me)2Mo}2(μ2-N2)][BArF(24)]2 [(Ph)Tpy = 4'-Ph-2,2',6',2″-terpyridine; ArF(24) = (C6H3-3,5-(CF3)2)4], was synthesized and structurally characterized, and its electronic structure was determined using a combination of experimental and density functional theory computational methods. Each molybdenum atom is best described as molybdenum(II) bridged by a modestly activated [N2](2-) ligand. The cyclic voltammogram of [{((Ph)Tpy)(PPh2Me)2Mo}2(μ2-N2)](2+) displays two reversible reductive and two reversible oxidative features, prompting the preparation and characterization of a series of molybdenum dinitrogen compounds spanning five oxidation states ([{((Ph)Tpy)(PPh2Me)2Mo}2(μ2-N2)][BArF(24)]n, where n = 4, 3, 2, 1, 0). Raman and (15)N NMR spectroscopic data establish that the bridging nitrogen ligand remains intact across the redox series. Electron paramagnetic resonance spectroscopy was used to probe the nature of the unpaired electron in the mixed-valent electronic oxidized and reduced products. The singly occupied molecular orbital is principally metal-based in [{((Ph)Tpy)(PPh2Me)2Mo}2(μ2-N2)](3+) and ligand-localized in [{((Ph)Tpy)(PPh2Me)2Mo}2(μ2-N2)](+).

  20. Determination of oxidation state of iron in normal and pathologically altered human aortic valves

    NASA Astrophysics Data System (ADS)

    Czapla-Masztafiak, J.; Lis, G. J.; Gajda, M.; Jasek, E.; Czubek, U.; Bolechała, F.; Borca, C.; Kwiatek, W. M.

    2015-12-01

    In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe3+ is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe3+ form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

  1. Cs in high oxidation states and as a p-block element

    NASA Astrophysics Data System (ADS)

    Miao, Maosheng

    2013-06-01

    A long time doctrine rooted in the atomic shell model states that the atoms maintain a complete inner shell while interacting with other atoms. Therefore, group IA elements, for example, are invariably stable in the +1 charge state because the p electrons of their inner shells do not react with other chemical species. This general rule governs our understanding of the structures and reactions of matter and has never been challenged. In this work, I will show for the first time a striking result that while mixing with fluorine under pressure, Cs atoms will share their 5p electrons and become oxidized to a higher charge state. It forms stable CsFn compounds, consisting of neutral or ionic CsFn molecules. Their geometry and bonding resemble isoelectronic XeFn molecules, showing that Cs chemically behaves like a p-block element. The stability of these remarkable compounds will change the understanding of the periodic table and chemistry of elements. The work was done by using an automatic crystal structure search based on particle swarm optimization algorithm and the first principles total energy calculations.

  2. The x ray microprobe determination of chromium oxidation state in olivine from lunar basalt and kimberlitic diamonds

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    The synchrotron x-ray microprobe is being used to obtain oxidation state information on planetary materials with high spatial resolution. Initial results on chromium in olivine from various sources including laboratory experiments, lunar basalt, and kimberlitic diamonds are reported. The lunar olivine was dominated by Cr(2+) whereas the diamond inclusions had Cr(2+/Cr(3+) ratios up to about 0.3. The simpliest interpretation is that the terrestrial olivine crystallized in a more oxidizing environment than the lunar olivine.

  3. The x ray microprobe determination of chromium oxidation state in olivine from lunar basalt and kimberlitic diamonds

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    The synchrotron x-ray microprobe is being used to obtain oxidation state information on planetary materials with high spatial resolution. Initial results on chromium in olivine from various sources including laboratory experiments, lunar basalt, and kimberlitic diamonds are reported. The lunar olivine was dominated by Cr(2+) whereas the diamond inclusions had Cr(2+/Cr(3+) ratios up to about 0.3. The simpliest interpretation is that the terrestrial olivine crystallized in a more oxidizing environment than the lunar olivine.

  4. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  5. Oxidation state of the atmosphere and crust of Venus from Pioneer Venus results

    NASA Technical Reports Server (NTRS)

    Lewis, J. S.; Kreimendahl, F. A.

    1980-01-01

    Recent spacecraft observations of Venus permit a detailed model of sulfur chemistry in the atmosphere-lithosphere system. Pioneer Venus experiments confirm that, as predicted, COS and H2S are dominant over SO2 in the lower atmosphere, and that the equilibrium concentrations of S2 and S3 are significant. Many criteria serve to bracket the oxidation state of the crust: it is nearly certain that the S2(2-)/SO4(2-) buffer regulates the oxygen fugacity, and that FeO is at least as abundant as F2O3 in crustal silicates. A highly oxidized crust (as, for example, would result from O2 absorption complementary to escape of vast amounts of H2) is incompatible with the gas-phase sulfur chemistry. If the Pioneer Venus mass spectrometer estimates of the abundance of sulfur gases are correct, earth-like models for the bulk composition of Venus are seriously in error, and a far lower FeO content is required for Venus.

  6. Using Metal Complex Reduced States to Monitor the Oxidation of DNA

    PubMed Central

    Olmon, Eric D.; Hill, Michael G.; Barton, Jacqueline K.

    2011-01-01

    Metallointercalating photooxidants interact intimately with the base stack of double-stranded DNA and exhibit rich photophysical and electrochemical properties, making them ideal probes for the study of DNA-mediated charge transport (CT). The complexes [Rh(phi)2(bpy′)]3+ (phi = 9,10-phenanthrenequinone diimine; bpy′ = 4-methyl-4′-(butyric acid)-2,2′-bipyridine), [Ir(ppy)2(dppz′)]+ (ppy = 2-phenylpyridine; dppz′ = 6-(dipyrido[3,2-a:2′,3′-c]phenazin-11-yl)hex-5-ynoic acid), and [Re(CO)3(dppz)(py′)]+ (dppz = dipyrido[2,3-a:2′,3′-c]phenazine; py′ = 3-(pyridin-4-yl)-propanoic acid) were each covalently tethered to DNA in order to compare their photooxidation efficiencies. Biochemical studies show that upon irradiation, the three complexes oxidize guanine by long-range DNA-mediated CT with the efficiency: Rh > Re > Ir. Comparison of spectra obtained by spectroelectrochemistry after bulk reduction of the free metal complexes with those obtained by transient absorption (TA) spectroscopy of the conjugates suggests that the reduced metal states form following excitation of the conjugates at 355 nm. Electrochemical experiments and kinetic analysis of the TA decays indicate that the thermodynamic driving force for CT, variations in the efficiency of back electron transfer, and coupling to DNA are the primary factors responsible for the trend observed in the guanine oxidation yield of the three complexes. PMID:22043853

  7. Tuning Sulfur Oxidation States on Thioether-Bridged Peptide Macrocycles for Modulation of Protein Interactions.

    PubMed

    Perell, Gabriella T; Staebell, Rachel Lynn; Hairani, Mehrdad; Cembran, Alessandro; Pomerantz, William C K

    2017-09-19

    Thioethers, sulfoxides, and sulfonium ions, despite diverse physicochemical properties, all engage in noncovalent interactions with proteins. Thioether-containing macrocycles are also attracting attention as protein-protein interaction (PPI) inhibitors. Here, we used a model PPI between α-helical mixed lineage leukemia (MLL) protein and kinase-inducible domain interacting (KIX) domain to evaluate oxidation effects on sulfurcontaining macrocycle structure, stability, and protein affinity. Desolvation effects from various polarity states were evaluated computationally and experimentally at the side chain, amino acid, and peptide level. Sulfur-containing side chains spanned polarity ranges between all-hydrocarbon and lactam bridges for modulating solubility, cellular uptake, and affinity. Helical propensity studies showed that, although oxidized sulfur-containing side chains could be tolerated, conformational effects were sequence-dependent. In some cases, proteolytic stability, binding capacity with KIX, and increased helicity were obtained as first steps toward developing PPI inhibitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Probing local coordination and oxidation state of uranium in ThO2: U nanostructured

    NASA Astrophysics Data System (ADS)

    Gupta, Santosh K.; Pathak, N.; Kadam, R. M.

    2015-12-01

    Uranium doped thorium oxide nanoparticle (UDT) was synthesized using citric acid assisted combustion method. The concentration of uranium was varied from 0.5 to 5.0 mol % to investigate the effect of doping concentration on its optical properties. The synthesised UDT powder were characterized systematically using X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) respectively for phase purity, morphology and crystallinity. Pertaining to nuclear industry, UDT is an important material and investigating the local structure of uranium in UDT is interesting as well as challenging because of complexity involved in synthesis of such ceramic powder. We have used time resolved photoluminescence spectroscopy (TRPLS) to probe the local coordination and oxidation state of uranium in UDT. Based on PL emission spectroscopy it was confirmed that uranium stabilizes as UO22+ ion in UDT. Lifetime spectroscopy shows that uranyl ion is not homogenously distributed in UDT lattice; rather it has two different chemical environments. Effect of concentration on PL behaviour shows that, concentration quenching takes place beyond 2.0 mol %; and based on critical distance calculation multipolar interaction was found to be responsible for such non-radiative quenching. As far as application in luminescence industry is concerned PL measurement shows that UDT gives intense green emission under UV excitation.

  9. The Oxidation State of Komatiites and the Redox History of the Mantle

    NASA Astrophysics Data System (ADS)

    Nicklas, R. W.; Puchtel, I. S.; Ash, R. D.

    2015-12-01

    Oxygen fugacity (fO2) is an important intensive variable in magmatic systems. Previous studies argued that, at the level of resolution of ca. 1.0 ΔNNO log units, the mantle has been at a near-constant oxidation state since core formation [1,3]. Here, we revisit this hypothesis using the V partitioning between olivine or chromite and komatiite liquid as oxybarometers [1,2] by obtaining high-precision V abundance data for komatiite lava flows. Whole-rock samples collected across each lava flow were analyzed for V and other transition metal abundances using Standard Addition ICP-MS (SA ICP-MS); liquidus olivines and chromites were analyzed using Laser Ablation ICP-MS. Our external precision for V concentrations is 5% (2SD) for SA-ICP-MS, based on replicate analysis of standard reference materials. The V data, when plotted against wt.% MgO, define regression lines consistent with olivine control for V. Linear regressions through the V vs. MgO data for samples for each flow were used to determine V content of the emplaced lavas using known MgO contents. Calculated partition coefficients for V were used to determine the oxygen fugacity of each komatiite system using experimental calibrations of [1,2] with a precision of 0.10 - 0.05 ΔNNO log units (2SE). The calculated oxygen fugacities show a well-defined trend of increasing fO2 (>0.5 ΔNNO log units) over ~1.0 Ga of Earth's history, approaching that of modern mantle at 2.4 Ga, immediately before the Great Oxidation Event (GOE). An exception is the 3.55 Ga Schapenburg komatiite, which plots 0.5 log units above the trend, likely reflecting primordial mantle heterogeneity. Our data suggest that the mantle was becoming increasingly oxidized leading up to the GOE. A change in deep Earth buffering capacity could change the oxidation state of volcanic gases, triggering the rise in atmospheric O2 at 2.4 Ga. [1] Canil (1997) Nature 389. [2] Canil, 1999; [3] Li et al. (2004) EPSL 228. Oxygen fugacity (fO2) is an important

  10. Virtual gap states induced modifications in charge neutrality level in cadmium oxide thin films

    NASA Astrophysics Data System (ADS)

    Das, Arkaprava; Gautam, Subodh K.; Umapathy, G. R.; Ojha, S.; Singh, Fouran

    2017-04-01

    Present manuscript reports on the creation of virtual gap states (ViGS) in sol-gel spin coated cadmium oxide thin films by tin doping and irradiation at different density of electronic excitations (EEs) induced by energetic ions. Effects of ViGS on charge neutrality level (CNL), which affects the modifications in band gap (BG) of such oxide semiconductors are investigated. Studies reveal that there were insignificant changes in the structural and morphological properties of the films. Interestingly, the transmittance spectrum shows insignificant changes in the films irradiated by low density EEs but an overall decrease in transmittance for high density EEs. However, Raman spectroscopy reveals a significant change in longitudinal optical (LO) modes with tin doping which get intensified and they exhibit an insignificant influence upon irradiation. The BG with respect to bulk is observed to be increased by 0.57 eV and 0.83 eV upon tin doping and irradiation, respectively. These variations are attributed to the combined effect of Burstein-Moss shift (BMS) and ViGS, which were created by tin doping and EEs. It is observed that density of ViGS strongly depends on the density of EEs. A schematic band diagram is also developed for demonstrating the observed influence of ViGS on band gap modifications. Thus the reported investigations are very interesting for the in-depth understanding of fundamental interactions and besides their possible potential applications in the development of optoelectronic devices.

  11. Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program

    SciTech Connect

    Nguyen Minh

    2006-07-31

    This report summarizes the work performed for Phase I (October 2001 - August 2006) under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled 'Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program'. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. During Phase I of the program significant progress has been made in the area of SOFC technology. A high-efficiency low-cost system was designed and supporting technology developed such as fuel processing, controls, thermal management, and power electronics. Phase I culminated in the successful demonstration of a prototype system that achieved a peak efficiency of 41%, a high-volume cost of $724/kW, a peak power of 5.4 kW, and a degradation rate of 1.8% per 500 hours. . An improved prototype system was designed, assembled, and delivered to DOE/NETL at the end of the program. This prototype achieved an extraordinary peak efficiency of 49.6%.

  12. New strain states and radical property tuning of metal oxides using a nanocomposite thin film approach

    NASA Astrophysics Data System (ADS)

    MacManus-Driscoll, Judith; Suwardi, Ady; Kursumovic, Ahmed; Bi, Zhenxing; Tsai, Chen-Fong; Wang, Haiyan; Jia, Quanxi; Lee, Oon Jew

    2015-06-01

    Auxetic-like strain states were generated in self-assembled nanocomposite thin films of (Ba0.6Sr0.4TiO3)1-x - (Sm2O3)x(BSTO - SmO). A switch from auxetic-like to elastic-like strain behavior was observed for x > 0.50, when the SmO switched from being nanopillars in the BSTO matrix to being the matrix with BSTO nanopillars embedded in it. A simple model was adopted to explain how in-plane strain varies with x. At high x (0.75), strongly enhanced ferroelectric properties were obtained compared to pure BSTO films. The nanocomposite method represents a powerful new way to tune the properties of a wide range of strongly correlated metal oxides whose properties are very sensitive to strain.

  13. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica

    PubMed Central

    Olguin, Gianni; Yacou, Christelle; Smart, Simon; Diniz da Costa, João C.

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications. PMID:24022785

  14. Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide.

    PubMed

    Cai, Weiwei; Piner, Richard D; Stadermann, Frank J; Park, Sungjin; Shaibat, Medhat A; Ishii, Yoshitaka; Yang, Dongxing; Velamakanni, Aruna; An, Sung Jin; Stoller, Meryl; An, Jinho; Chen, Dongmin; Ruoff, Rodney S

    2008-09-26

    The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13-labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.

  15. On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

    PubMed

    Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

    2017-02-08

    We demonstrate herein that Mn(3+) and not Mn(2+), as commonly accepted, is the dominant dissolved manganese cation in LiPF6-based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn(3+) fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn(3+) in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn(3+) occurs at a very slow rate.

  16. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica.

    PubMed

    Olguin, Gianni; Yacou, Christelle; Smart, Simon; da Costa, João C Diniz

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications.

  17. State-of-the-art technologies of gallium oxide power devices

    NASA Astrophysics Data System (ADS)

    Higashiwaki, Masataka; Kuramata, Akito; Murakami, Hisashi; Kumagai, Yoshinao

    2017-08-01

    Gallium oxide (Ga2 O3 ) has gained increased attention for power devices due to its superior material properties and the availability of economical device-quality native substrates. This review illustrates recent advances in Ga2 O3 device technologies, beginning with an overview of the social circumstances that motivate the development of new-generation switching devices. Following an introduction to the material properties of Ga2 O3 from the viewpoint of power electronics, growth technologies of Ga2 O3 bulk single crystals and epitaxial thin films are discussed. The fabrication and performance of state-of-the-art Ga2 O3 transistors and diodes are then described. We conclude by identifying the directions and challenges of Ga2 O3 power device development in the near future.

  18. Unsupervised learning in probabilistic neural networks with multi-state metal-oxide memristive synapses

    NASA Astrophysics Data System (ADS)

    Serb, Alexander; Bill, Johannes; Khiat, Ali; Berdan, Radu; Legenstein, Robert; Prodromakis, Themis

    2016-09-01

    In an increasingly data-rich world the need for developing computing systems that cannot only process, but ideally also interpret big data is becoming continuously more pressing. Brain-inspired concepts have shown great promise towards addressing this need. Here we demonstrate unsupervised learning in a probabilistic neural network that utilizes metal-oxide memristive devices as multi-state synapses. Our approach can be exploited for processing unlabelled data and can adapt to time-varying clusters that underlie incoming data by supporting the capability of reversible unsupervised learning. The potential of this work is showcased through the demonstration of successful learning in the presence of corrupted input data and probabilistic neurons, thus paving the way towards robust big-data processors.

  19. New strain states and radical property tuning of metal oxides using a nanocomposite thin film approach

    DOE PAGES

    MacManus-Driscoll, Judith; Suwardi, Ady; Kursumovic, Ahmed; ...

    2015-05-05

    Auxetic-like strain states were generated in self-assembled nanocomposite thin films of (Ba0.6Sr0.4TiO3)1–x – (Sm2O3)x(BSTO – SmO). A switch from auxetic-like to elastic-like strain behavior was observed for x > 0.50, when the SmO switched from being nanopillars in the BSTO matrix to being the matrix with BSTO nanopillars embedded in it. A simple model was adopted to explain how in-plane strain varies with x. At high x (0.75), strongly enhanced ferroelectric properties were obtained compared to pure BSTO films. Furthermore, the nanocomposite method represents a powerful new way to tune the properties of a wide range of strongly correlated metalmore » oxides whose properties are very sensitive to strain.« less

  20. Unsupervised learning in probabilistic neural networks with multi-state metal-oxide memristive synapses

    PubMed Central

    Serb, Alexander; Bill, Johannes; Khiat, Ali; Berdan, Radu; Legenstein, Robert; Prodromakis, Themis

    2016-01-01

    In an increasingly data-rich world the need for developing computing systems that cannot only process, but ideally also interpret big data is becoming continuously more pressing. Brain-inspired concepts have shown great promise towards addressing this need. Here we demonstrate unsupervised learning in a probabilistic neural network that utilizes metal-oxide memristive devices as multi-state synapses. Our approach can be exploited for processing unlabelled data and can adapt to time-varying clusters that underlie incoming data by supporting the capability of reversible unsupervised learning. The potential of this work is showcased through the demonstration of successful learning in the presence of corrupted input data and probabilistic neurons, thus paving the way towards robust big-data processors. PMID:27681181

  1. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt–Copper Complexes

    SciTech Connect

    Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.; Young, Victor G.; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

    2015-12-07

    Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

  2. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

    SciTech Connect

    Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.; Victor G. Young Jr.; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

    2016-03-04

    Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

  3. Oxidation photochemistry in the Southern Atlantic boundary layer: Unexpected deviations of photochemical steady state

    NASA Astrophysics Data System (ADS)

    Hosaynali Beygi, Z.; Fischer, H.; Martinez, M.; Harder, H. D.; Joeckel, P.; Parchatka, U.; Gurk, C.; Koenigstedt, R.; Brookes, D.; Monks, P. S.; Lelieveld, J.

    2009-12-01

    Ozone (O3) is a photochemical oxidant and a green house gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote MBL is considered an important region in terms of chemical O3 loss; however surface atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry of O3 and its precursors in the clean background conditions of the Southern Atlantic Ocean, accurate and precise measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel, Marion-Dufresne, crossing the Southern Atlantic (28°S-57°S, 46°W-34°E) in March 2007 are among the lowest amounts yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions and the calculations indicate deviations from PSS (Φ>1). The deviations observed under low NOx, conditions (5 to 25 pptv) demonstrate a remarkable and unexpected trend in the Leighton ratio (a ratio used to characterize PSS) dependant on the NO2 mixing ratio and JNO2 intensity. Further, a direct comparison of the measured species with model output of an atmospheric chemistry general circulation model (EMAC) is performed along the exact cruise track. To further investigate the consistency of the measurements and our current understanding of atmospheric radical chemistry a steady-state box model is constrained using data obtained during the cruise. The comparison between measured and model calculated ROx concentrations in the low NOx, regime shows that conventional theory fails to reproduce the observations. The possible causes and implications are discussed.

  4. Effect of MgO/Fe Interface Oxidation State on Electric-Field Modulation of Interfacial Magnetic Anisotropy

    NASA Astrophysics Data System (ADS)

    Guan, X. W.; Cheng, X. M.; Wang, S.; Huang, T.; Xue, K. H.; Miao, X. S.

    2016-06-01

    The impact of the MgO/Fe interface oxidation state on the electric-field-modified magnetic anisotropy in MgO/Fe has been revealed by density functional calculations. It is shown that the influence of the interface oxidation is strong enough to dominate the effect of the electric field on the magnetic anisotropy of MgO/Fe-based films. The magnetoelectric coefficients are calculated to be positive for the ideal and overoxidized MgO/Fe interface, but an abnormal negative value emerges in the underoxidized case. By analyzing the interface states based on density of states and band structures, we demonstrate that the considerably different electronic structures of the three oxidized MgO/Fe interfaces lead to the strong discrepancy in the electric-field modulation of the interfacial magnetic anisotropy. These results are of considerable interest in the area of electric-field-controlled magnetic anisotropy and switching.

  5. The Oxidation State of Global Subduction Zone Basalts and its Relationship to Volatiles, Magmatic Processes, and Source Composition

    NASA Astrophysics Data System (ADS)

    Kelley, K. A.; Cottrell, E.

    2008-12-01

    Oxidation state is a central variable in magmatic systems. In subduction zones, the mantle wedge is exposed to hydrous fluids from an oxidized subducting plate, potentially driving a fundamental shift in the oxidation states of arc and back-arc basin magmas and their sources. Despite its importance, however, magmatic oxidation state and its relationship to conditions in the mantle source can be difficult to constrain. Here, we present new, in-situ μ-XANES analyses of Fe+3/ΣFe ratios, as an indicator of melt oxidation state, in natural, primitive pillow glasses from the Mariana, Lau, and Manus back-arc basins (MgO>6 wt.%; n=31) and a global suite of olivine-hosted arc melt inclusions (MI; MgO>4 wt.%; n=16). These new data show that back-arc basin basalts preserve Fe+3/ΣFe ratios of 0.14-0.21, more oxidized than MORB (Fe+3/ΣFe=0.11-0.17), and arc basalts range to even higher ratios of 0.17-0.36. Analysis of MI equilibrium with host olivine compositions indicates that either post-entrapment crystallization or outward Fe+2 diffusion may have occurred in the MI's studied, but the magnitude of these effects is small (9±5% change in FeO; see also Cottrell & Kelley, this mtg.). Coupled with new and existing major element, volatile (H2O±CO2, S, Cl, F), and trace element data, we also test the variation of melt oxidation state with indicators of extent of crystal fractionation and of mantle source composition. The arc and back-arc glasses capture a full range of natural, undegassed magmatic H2O concentrations (0.1-5.3 wt.%), and show a general, global increase in Fe+3/ΣFe with increasing H2O content, although the Mariana trough defines a trend distinct from the Manus and Lau basins. The Fe+3/ΣFe ratio does not correlate with Mg#, suggesting that the melt oxidation states are not controlled by the extent of crystal fractionation. In the Mariana trough, Fe+3/ΣFe does increase with increasing Ba and Sr concentrations, suggesting a direct link between melt oxidation

  6. Accessibility of Myofilament Cysteines and Effects on ATPase Depend on the Activation State during Exposure to Oxidants

    PubMed Central

    Gross, Sean M.; Lehman, Steven L.

    2013-01-01

    Signaling by reactive oxygen species has emerged as a major physiological process. Due to its high metabolic rate, striated muscle is especially subject to oxidative stress, and there are multiple examples in cardiac and skeletal muscle where oxidative stress modulates contractile function. Here we assessed the potential of cysteine oxidation as a mechanism for modulating contractile function in skeletal and cardiac muscle. Analyzing the cysteine content of the myofilament proteins in striated muscle, we found that cysteine residues are relatively rare, but are very similar between different muscle types and different vertebrate species. To refine this list of cysteines to those that may modulate function, we estimated the accessibility of oxidants to cysteine residues using protein crystal structures, and then sharpened these estimates using fluorescent labeling of cysteines in cardiac and skeletal myofibrils. We demonstrate that cysteine accessibility to oxidants and ATPase rates depend on the contractile state in which preparations are exposed. Oxidant exposure of skeletal and cardiac myofibrils in relaxing solution exposes myosin cysteines not accessible in rigor solution, and these modifications correspond to a decrease in maximum ATPase. Oxidant exposure under rigor conditions produces modifications that increase basal ATPase and calcium sensitivity in ventricular myofibrils, but these effects were muted in fast twitch muscle. These experiments reveal how structural and sequence variations can lead to divergent effects from oxidants in different muscle types. PMID:23894416

  7. The Oxidative and Inflammatory State in Patients with Acute Renal Graft Dysfunction Treated with Tacrolimus

    PubMed Central

    Carrillo-Ibarra, Sandra; Cerrillos-Gutiérrez, José Ignacio; Escalante-Núñez, Ariadna; Rojas-Campos, Enrique; Gómez-Navarro, Benjamín; Sifuentes-Franco, Sonia

    2016-01-01

    Objective. To determine the oxidative stress/inflammation behavior in patients with/without acute graft dysfunction (AGD) with Tacrolimus. Methods. Cross-sectional study, in renal transplant (RT) recipients (1-yr follow-up). Patients with AGD and without AGD were included. Serum IL-6, TNF-α, 8-isoprostanes (8-IP), and Nitric Oxide (NO) were determined by ELISA; C-reactive protein (CRP) was determined by nephelometry; lipid peroxidation products (LPO) and superoxide dismutase (SOD) were determined by colorimetry. Results. The AGD presentation was at 5.09 ± 3.07 versus 8.27 ± 3.78 months (p < 0.001); CRP >3.19 mg/L was found in 21 versus 19 in the N-AGD group (p = 0.83); TNF-α 145.53 ± 18.87 pg/mL versus 125.54 ± 15.92 pg/mL in N-AGD (p = 0.64); IL-6 2110.69 ± 350.97 pg/mL versus 1933.42 ± 235.38 pg/mL in N-AGD (p = 0.13). The LPO were higher in AGD (p = 0.014): 4.10 ± 0.69 µM versus 2.41 ± 0.29 µM; also levels of 8-IP were higher in AGD 27.47 ± 9.28 pg/mL versus 8.64 ± 1.54 pg/mL (p = 0.01). Serum levels of NO in AGD were lower 138.44 ± 19.20 µmol/L versus 190.57 ± 22.04 µmol/L in N-AGD (p = 0.042); antioxidant enzyme SOD activity was significantly diminished in AGD with 9.75 ± 0.52 U/mL versus 11.69 ± 0.55 U/mL in N-AGD (p = 0.012). Discussion. Patients with RT present with a similar state of the proinflammatory cytokines whether or not they have AGD. The patients with AGD showed deregulation of the oxidative state with increased LPO and 8-IP and decreased NO and SOD. PMID:27872679

  8. Interface states in cycled hot electron injection program/hot hole erase silicon-oxide-nitride-oxide-silicon memories

    NASA Astrophysics Data System (ADS)

    Daniel, Ramiz; Shaham-Diamand, Yossi; Roizin, Yakov

    2004-12-01

    Charge pumping measurements were performed to characterize the interface between silicon and bottom oxide in silicon-oxide-nitride-oxide-silicon memory transistors, where information is stored as charges in nitride at the edges of the channel. The charge pumping signal was found to strongly increase with the number of performed program/erase cycles, thus indicating the creation of traps with a density on the order of 1012cm-2 (after 100 000 cycles). To estimate the length of the degraded region, the charge pumping signal dependence on the drain voltage was compared with the simulated drain depletion length using TSUPREM/Medici software. The damaged length calculated from the metallurgical junction is about 200Å at the beginning of the endurance test and increases to 500Å after 100 000 cycles.

  9. Oxidation state of iron and extensive redistribution of sulfur in thermally modified Stardust particles

    NASA Astrophysics Data System (ADS)

    Leroux, Hugues; Roskosz, Mathieu; Jacob, Damien

    2009-02-01

    Two representative thermally modified Stardust samples were investigated by analytical transmission electron microscopy in order to decipher their iron oxidation state after the strong thermal episode due to the capture in aerogel. Their dominant microstructure consists of evenly distributed rounded Fe-Ni-S nano-droplets within a silica-rich glassy matrix. The mineralogy and associated redox state of iron is assessed using a Fe-Mg-S ternary diagram on which ferromagnesian silicates, sulfides and metal can be represented and potentially compared with any other extraterrestrial material. In this diagram, all the data (bulk and local analysis of silicates, sulfide + metal) scatter along a mixing line between the Mg corner and the average composition of the iron-sulfide. There is an obvious genetic relationship between the different phases observed in such samples, further supported by the very low concentration of iron in the glassy matrix. Silicate glasses contain a significant concentration of dissolved sulfur probably present as MgS complexes. This chemical signature is typical of highly reduced environments. These secondary microstructures were established during the high temperature stage of the capture. A significant part of the Fe-droplets formed in situ by reduction at high temperature of ferromagnesian silicates (olivine and pyroxenes) during the impact. At this stage, the indigenous sulfides destabilized and sulfur readily volatilized as S 2, diffused into molten materials and condensed later onto the Fe-precipitates that formed in the silicate melt. This scenario is supported by the structure of Fe-Ni-S beads with a metal core and a sulfide rim. It will be difficult to derive reliable information on the redox state of 81P/Wild 2 particles based on bulk analyses of whole tracks because particles found along the walls of tracks suffered strong reduction reactions, contrary to terminal particles that may have preserved their pristine redox state. The capture

  10. Effect of dielectric stoichiometry and interface chemical state on band alignment between tantalum oxide and platinum

    SciTech Connect

    Lebedinskii, Yu. Yu.; Chernikova, A. G.; Markeev, A. M.; Kuzmichev, D. S.

    2015-10-05

    The tantalum oxide–platinum interface electronic properties determined by X-ray photoelectron spectroscopy are found to depend on the dielectric stoichiometry and platinum chemical state. We demonstrate the slow charging of the tantalum oxide in cases of Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt interfaces under the X-ray irradiation. This behavior is proposed to be related to the charge accumulation at oxygen vacancies induced traps. Based on the proposed methodology, we define the intrinsic conductive band offset (CBO) ∼1.3 eV (both for Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt) and CBO after the full saturation of the traps charging ∼0.5 eV, while the last one defines the energy position of charged traps below the bottom of conduction band. We demonstrate also the pining at the both Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt interfaces even in the “intrinsic” state, apparently induced by the presence of additional interfacial states. No shifts of Ta4f line and band alignment in over stoichiometric Ta{sub 2}O{sub 5+x}/Pt structure during X-ray irradiation, as well as the absence of pinning, resulting in increase of CBO up to 2.3 eV are found. This behavior is related to the PtO{sub 2} interfacing layer formation at Ta{sub 2}O{sub 5+x}/Pt, blocking the charging of the surface states and associated dipole formation.

  11. Low oxidation state aluminum-containing cluster anions: Cp(∗)AlnH(-), n = 1-3.

    PubMed

    Zhang, Xinxing; Ganteför, Gerd; Eichhorn, Bryan; Mayo, Dennis; Sawyer, William H; Gill, Ann F; Kandalam, Anil K; Schnöckel, Hansgeorg; Bowen, Kit

    2016-08-21

    Three new, low oxidation state, aluminum-containing cluster anions, Cp*AlnH(-), n = 1-3, were prepared via reactions between aluminum hydride cluster anions, AlnHm (-), and Cp*H ligands. These were characterized by mass spectrometry, anion photoelectron spectroscopy, and density functional theory based calculations. Agreement between the experimentally and theoretically determined vertical detachment energies and adiabatic detachment energies validated the computed geometrical structures. Reactions between aluminum hydride cluster anions and ligands provide a new avenue for discovering low oxidation state, ligated aluminum clusters.

  12. Use of XPS to identify the oxidation state of Mn in solid surfaces of filtration media oxide samples from drinking water treatment plants.

    PubMed

    Cerrato, José M; Hochella, Michael F; Knocke, William R; Dietrich, Andrea M; Cromer, Thomas F

    2010-08-01

    X-ray photoelectron spectroscopy (XPS) was used to identify Mn(II), Mn(III), and Mn(IV) in the surfaces of pure oxide standards and filtration media samples from drinking water treatment plants through the determination of the magnitude of the Mn 3s multiplet splitting and the position and shape of the Mn 3p photo-line. The Mn 3p region has been widely studied by applied physicists and surface scientists, but its application to identify the oxidation state of Mn in heterogeneous oxide samples has been limited. This study shows that the use of both the Mn 3s multiplet splitting and the position and shape of the Mn 3p photo-line provides a feasible means of determining the oxidation state of manganese in complex heterogeneous, environmentally important samples. Surface analysis of filtration media samples from several drinking water treatment plants was conducted. While Mn(IV) was predominant in most samples, a mixture of Mn(III) and Mn(IV) was also identified in some of the filtration media samples studied. The predominance of Mn(IV) in the media samples was felt to be related to the maintenance of free chlorine (HOCl) at substantial concentrations (2-5 mg*L(-1) as Cl2) across these filters. XPS could be a useful tool to further understand the specific mechanisms affecting soluble Mn removal using MnOx-coated filtration media.

  13. Design of Amorphous Manganese Oxide@Multiwalled Carbon Nanotube Fiber for Robust Solid-State Supercapacitor.

    PubMed

    Shi, Peipei; Li, Li; Hua, Li; Qian, Qianqian; Wang, Pengfei; Zhou, Jinyuan; Sun, Gengzhi; Huang, Wei

    2017-01-24

    Solid-state fiber-based supercapacitors have been considered promising energy storage devices for wearable electronics due to their lightweight and amenability to be woven into textiles. Efforts have been made to fabricate a high performance fiber electrode by depositing pseudocapacitive materials on the outer surface of carbonaceous fiber, for example, crystalline manganese oxide/multiwalled carbon nanotubes (MnO2/MWCNTs). However, a key challenge remaining is to achieve high specific capacitance and energy density without compromising the high rate capability and cycling stability. In addition, amorphous MnO2 is actually preferred due to its disordered structure and has been proven to exhibit superior electrochemical performance over the crystalline one. Herein, by incorporating amorphous MnO2 onto a well-aligned MWCNT sheet followed by twisting, we design an amorphous MnO2@MWCNT fiber, in which amorphous MnO2 nanoparticles are distributed in MWCNT fiber uniformly. The proposed structure gives the amorphous MnO2@MWCNT fiber good mechanical reliability, high electrical conductivity, and fast ion-diffusion. Solid-state supercapacitor based on amorphous MnO2@MWCNT fibers exhibits improved energy density, superior rate capability, exceptional cycling stability, and excellent flexibility. This study provides a strategy to design a high performance fiber electrode with microstructure control for wearable energy storage devices.

  14. Engineering the metathesis and oxidation-reduction reaction in solid state at room temperature for nanosynthesis

    NASA Astrophysics Data System (ADS)

    Hu, Pengfei; Cao, Yali; Jia, Dianzeng; Li, Qiang; Liu, Ruili

    2014-03-01

    It is a long-standing goal to explore convenient synthesis methodology for functional materials. Recently, several multiple-step approaches have been designed for photocatalysts AgnX@Ag (X = Cl-, PO43-, etc.), mainly containing the ion-exchange (metathesis) reaction followed by photoreduction in solution. But they were obsessed by complicated process, the uncontrollability of composition and larger sizes of Ag particles. Here we show a general solid-state route for the synthesis of AgnX@Ag catalysts with hierarchical structures. Due to strong surface plasmon resonance of silver nanoparticles with broad shape and size, the AgnX@Ag showed high photocatalytic activity in visible region. Especially, the composition of AgnX@Ag composites could be accurately controlled by regulating the feed ratio of (NH2OH)2.H2SO4 to anions, by which the performance were easily optimized. Results demonstrate that the metathesis and oxidation-reduction reactions can be performed in solid state at room temperature for nanosynthesis, greatly reducing the time/energy consumption and pollution.

  15. Risk assessment for children exposed to decabromodiphenyl (oxide) ether (Deca) in the United States.

    PubMed

    Hays, Sean M; Pyatt, David W

    2006-01-01

    Decabromodiphenyl (oxide) ether (Deca) is a widely used brominated flame retardant in the United States predominantly in the hard-plastic housings of consumer electronics and in flame-retarded backing on textiles used in furniture. A child-specific exposure assessment of Deca was performed for the US Environmental Protection Agency's Voluntary Children's Chemical Evaluation Program (VCCEP). The VCCEP guidance for a tier 1 exposure assessment requires that a screening-level assessment be conducted using currently available data and conservative assumptions. For Deca, relevant exposure pathways considered were general environmental exposures (e.g., exposures to contaminated soil, dust, air, and food), breast milk exposures, inhalation of Deca-containing particulates in air, and mouthing Deca-containing consumer products. For each of these scenarios, a mid-range and upper estimate of age-appropriate intakes were calculated. The calculated intakes indicate that, despite the uncertainties, children appear to be exposed to Deca at levels at least 1 order of magnitude, with most being several orders of magnitude, below the National Academy of Sciences reference dose for Deca of 4 mg/kg/d. This analysis indicates that, using the available data, current levels of Deca in the United States are unlikely to represent an adverse health risk for children.

  16. Inactivation of nitric oxide by cytochrome c oxidase under steady-state oxygen conditions.

    PubMed

    Unitt, David C; Hollis, Veronica S; Palacios-Callender, Miriam; Frakich, Nanci; Moncada, Salvador

    2010-03-01

    We have developed a respiration chamber that allows intact cells to be studied under controlled oxygen (O(2)) conditions. The system measures the concentrations of O(2) and nitric oxide (NO) in the cell suspension, while the redox state of cytochrome c oxidase is continuously monitored optically. Using human embryonic kidney cells transfected with a tetracycline-inducible NO synthase we show that the inactivation of NO by cytochrome c oxidase is dependent on both O(2) concentration and electron turnover of the enzyme. At a high O(2) concentration (70 microM), and while the enzyme is in turnover, NO generated by the NO synthase upon addition of a given concentration of l-arginine is partially inactivated by cytochrome c oxidase and does not affect the redox state of the enzyme or consumption of O(2). At low O(2) (15 microM), when the cytochrome c oxidase is more reduced, inactivation of NO is decreased. In addition, the NO that is not inactivated inhibits the cytochrome c oxidase, further reducing the enzyme and lowering O(2) consumption. At both high and low O(2) concentrations the inactivation of NO is decreased when sodium azide is used to inhibit cytochrome c oxidase and decrease electron turnover.

  17. Electronic State of Fe in Double Perovskite Oxide Sr 2FeWO 6

    NASA Astrophysics Data System (ADS)

    Kawanaka, Hirofumi; Hase, Izumi; Toyama, Shunichiro; Nishihara, Yoshikazu

    1999-09-01

    The magnetic properties of double perovskite oxide Sr2FeWO6 have been reported. The magnetic susceptibility and Mössbauer effect of 57Fe show that this compound is an antiferromagnet with T N=37 K. The Mössbauer parameters below ˜20 K are the center shift of +1.2 mm/s relative to metallic iron, the quadrupole splitting of 1.9 mm/s and the hyperfine field of ˜110 kOe. The quadrupole splitting has a strong temperature dependence. From these data, we conclude that Fe in Sr2FeWO6 is in the Fe2+ high-spin state, while the hyperfine field seems to be quite small. The cell volume shows a large increase compared to other Sr2FeTO6 ( T= Mo, Re, etc.), which is in the Fe3+ high-spin state. These results suggest that these compounds have a strongly coupled charge and lattice systems.

  18. Engineering the metathesis and oxidation-reduction reaction in solid state at room temperature for nanosynthesis

    PubMed Central

    Hu, Pengfei; Cao, Yali; Jia, Dianzeng; Li, Qiang; Liu, Ruili

    2014-01-01

    It is a long-standing goal to explore convenient synthesis methodology for functional materials. Recently, several multiple-step approaches have been designed for photocatalysts AgnX@Ag (X = Cl−, PO43−, etc.), mainly containing the ion-exchange (metathesis) reaction followed by photoreduction in solution. But they were obsessed by complicated process, the uncontrollability of composition and larger sizes of Ag particles. Here we show a general solid-state route for the synthesis of AgnX@Ag catalysts with hierarchical structures. Due to strong surface plasmon resonance of silver nanoparticles with broad shape and size, the AgnX@Ag showed high photocatalytic activity in visible region. Especially, the composition of AgnX@Ag composites could be accurately controlled by regulating the feed ratio of (NH2OH)2·H2SO4 to anions, by which the performance were easily optimized. Results demonstrate that the metathesis and oxidation-reduction reactions can be performed in solid state at room temperature for nanosynthesis, greatly reducing the time/energy consumption and pollution. PMID:24614918

  19. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    SciTech Connect

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  20. Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

    NASA Astrophysics Data System (ADS)

    Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

    2016-08-01

    We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

  1. DFT study on the electronic structure and chemical state of Americium in an (Am,U) mixed oxide

    NASA Astrophysics Data System (ADS)

    Suzuki, Chikashi; Nishi, Tsuyoshi; Nakada, Masami; Tsuru, Tomohito; Akabori, Mitsuo; Hirata, Masaru; Kaji, Yoshiyuki

    2013-12-01

    We investigated the electronic state of an (Am,U) mixed oxide with the fluorite structure using the all-electron full potential linear augmented plane wave method and compared it with those of Am2O3, AmO2, UO2, and La0.5U0.5O2. The valence of Am in the mixed oxide was close to that of Am2O3 and the valence of U in the mixed oxide was pentavalent. The electronic structure of AmO2 was different from that of Am2O3, particularly just above the Fermi level. In addition, the electronic states of Am and U in the mixed oxide were similar to those of trivalent Am and pentavalent U oxides. These electronic states reflected the high oxygen potential of AmO2 and the heightened oxygen potential resulting from the addition of Am to UO2 and also suggested the occurrence of charge transfer from Am to U in the solid solution process.

  2. Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

    2010-01-01

    Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re

  3. Oxidation state of iron in komatiitic melt inclusions indicates hot Archaean mantle

    SciTech Connect

    Berry, A.J.; Danyushevsky, L.; O'Neill, H.C.; Newville, M.; Sutton, S.R.

    2008-10-16

    Komatiites are volcanic rocks mainly of Archaean age that formed by unusually high degrees of melting of mantle peridotite. Their origin is controversial and has been attributed to either anhydrous melting of anomalously hot mantle or hydrous melting at temperatures only modestly greater than those found today. Here we determine the original Fe{sup 3+}/{Sigma}Fe ratio of 2.7-Gyr-old komatiitic magma from Belingwe, Zimbabwe, preserved as melt inclusions in olivine, to be 0.10 {+-} 0.02, using iron K-edge X-ray absorption near-edge structure spectroscopy. This value is consistent with near-anhydrous melting of a source with a similar oxidation state to the source of present-day mid-ocean-ridge basalt. Furthermore, this low Fe{sup 3+}/{Sigma}Fe value, together with a water content of only 0.2--0.3 wt%, excludes the possibility that the trapped melt contained significantly more water that was subsequently lost from the inclusions by reduction to H{sub 2} and diffusion. Loss of only 1.5 wt% water by this mechanism would have resulted in complete oxidation of iron (that is, the Fe{sup 3+}/{Sigma}Fe ratio would be {approx}1). There is also no petrographic evidence for the loss of molecular water. Our results support the identification of the Belingwe komatiite as a product of high mantle temperatures ({approx}1,700 C), rather than melting under hydrous conditions (3--5-wt% water), confirming the existence of anomalously hot mantle in the Archaean era.

  4. Electrochemical and spectroscopic studies of some less stable oxidation states of selected lanthanide and actinide elements

    SciTech Connect

    Hobart, D. E.

    1981-06-01

    Simultaneous observation of electrochemical and spectroscopic properties (spectroelectrochemistry) at optically transparent electrodes (OTE's) was used to study some less stable oxidation states of selected lanthanide and actinide elements. Cyclic voltammetry at microelectrodes was used in conjunction with spectroelectrochemistry for the study of redox couples. Additional analytical techniques were used. The formal reduction potential (E/sup 0/') values of the M(III)/M(II) redox couples in 1 M KCl at pH 6 were -0.34 +- 0.01 V for Eu, -1.18 +- 0.01 V for Yb, and -1.50 +- 0.01 V for Sm. Spectropotentiostatic determination of E/sup 0/' for the Eu(III)/Eu(II) redox couple yielded a value of -0.391 +- 0.005 V. Spectropotentiostatic measurement of the Ce(IV)/Ce(III) redox couple in concentrated carbonate solution gave E/sup 0/' equal to 0.051 +- 0.005 V, which is about 1.7 V less positive than the E/sup 0/' value in noncomplexing solution. This same difference in potential was observed for the E/sup 0/' values of the Pr(IV)/Pr(III) and Tb(IV)/Tb(III) redox couples in carbonate solution, and thus Pr(IV) and Tb(IV) were stabilized in this medium. The U(VI)/U(V)/U(IV) and U(IV)/U(III) redox couples were studied in 1 M KCl at OTE's. Spectropotentiostatic measurement of the Np(VI)/Np(V) redox couple in 1 M HClO/sub 4/ gave an E/sup 0/' value of 1.140 +- 0.005 V. An E/sup 0/' value of 0.46 +- 0.01 V for the Np(VII)/Np(VI) couple was found by voltammetry. Oxidation of Am(III) was studied in concentrated carbonate solution, and a reversible cyclic voltammogram for the Am(IV)/Am(III) couple yielded E/sup 0/' = 0.92 +- 0.01 V in this medium; this value was used to estimate the standard reduction potential (E/sup 0/) of the couple as 2.62 +- 0.01 V. Attempts to oxidize Cm(III) in concentrated carbonate solution were not successful which suggests that the predicted E/sup 0/ value for the Cm(IV)/Cm(III) redox couple may be in error.

  5. Geochemical Constraints on the Oxidation States of the Europan Ocean and Mantle

    NASA Technical Reports Server (NTRS)

    Zolotov, M. Yu.; Shock, E. L.

    2001-01-01

    We present observational, meteoritic, and physical-chemical arguments for an oxidized Fe-metal free mantle and an oxidized sulfate-carbonate rich ocean on Europa. The ocean should be out of equilibrium even with oxidized igneous rocks at the oceanic floor. Additional information is contained in the original extended abstract.

  6. Investigation of the oxidation states of Cu additive in colored borosilicate glasses by electron energy loss spectroscopy

    SciTech Connect

    Yang, Guang Cheng, Shaodong; Li, Chao; Ma, Chuansheng; Zhong, Jiasong; Xiang, Weidong; Wang, Zhao

    2014-12-14

    Three optically transparent colorful (red, green, and blue) glasses were synthesized by the sol-gel method. Nano-sized precipitates were found in scanning electron microscopy images. The precipitates were analyzed by transmission electron microscopy (TEM) and high resolution TEM. The measured lattice parameters of these precipitates were found to fit the metallic copper in red glass but deviate from single valenced Cu oxides in green and blue glasses. The chemistry of these nano-sized particles was confirmed by electron energy loss spectroscopy (EELS). By fitting the EELS spectra obtained from the precipitates with the linear combination of reference spectra from Cu reference compounds, the oxidation states of Cu in the precipitates have been derived. First principle calculations suggested that the Cu nano-particles, which are in the similar oxidation states as our measurement, would show green color in the visible light range.

  7. Oxidation state of the lithospheric mantle beneath the Massif Central,France

    NASA Astrophysics Data System (ADS)

    Uenver-Thiele, L.; Woodland, A. B.; Downes, H.; Altherr, R.

    2012-04-01

    The Tertiary and Quaternary volcanism of the French Massif Central sampled the underlying subcontinental lithospheric mantle (SCLM) in the form of xenoliths over a wide geographic area of ~20.000km2. Such an extensive distribution of xenoliths provides an unique opportunity to investigate regional variations in mantle structure and composition. On the basis of textural and geochemical differences, Lenoir et al. (2000) and later Downes et al. (2003) identified two distinct domains in the SCLM lying north and south of latitude 45° 30' N, respectively. The northern domain is relatively refractory, but has experienced pervasive enrichment of LREE. The southern domain is generally more fertile, exhibiting depletion in LREE. A metasomatic overprint has developed to variable extents in many xenolith suites. The different histories of these two juxtaposed blocks of SCLM should also be reflected in their oxidation state, with local variations also to be expected due to metasomatic interactions. For example, if carbonate-melt metasomatism played a role in the LREE enrichment of the northern domain (Lenoir et al. 2000; Downes et al. 2003), then such mantle should be relatively oxidised. Since surprisingly little redox data are currently available, we are undertaking a study to determine the oxidation state of the SCLM beneath the Massif Central over the largest geographical area possible. All xenoliths investigated are spinel peridotites, mostly with protogranular textures (although some samples are porphyroclastic or equigranular). Most samples are nominally anhydrous although minor amphibole is present in some xenolith suites. Major element compositions of the individual minerals were determined by microprobe. Two-pyroxene temperatures (BKN) range from 750° to ~1200° C. Ferric iron contents of spinel were determined by Mössbauer spectroscopy and gave a range of Fe3+/ Fetot from 0.191 to 0.418, with a conservative uncertainty of ±0.02. These data were used to calculate

  8. Quantifying X-Ray Pleochroism Effects in Synchrotron Micro-XANES Microanalyses of Elemental Oxidation States: Feldspar and Biotite

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.; Dyar, M. D.; Sutton, S. R.

    2001-01-01

    X-ray pleochroism is a predictable source of scatter in synchrotron microXANES analyses of elemental oxidation states. The magnitude of the effect is illustrated and a procedure to compensate for it has been implemented, reducing errors significantly. Additional information is contained in the original extended abstract.

  9. Comparative Distribution and Retention of Arsenic in Arsenic (+3 Oxidation State) Methyltransferase Knockout and Wild Type Mice

    EPA Science Inventory

    The mouse arsenic (+3 oxidation state) methyltransferase (As3mt) gene encodes a ~ 43 kDa protein that catalyzes conversion of inorganic arsenic into methylated products. Heterologous expression of AS3MT or its silencing by RNA interference controls arsenic methylation phenotypes...

  10. METABOLISM AND TOXICITY OF AS IN HUMAN UROTHELIAL CELLS EXPRESSING RAT ARSENIC (+3 OXIDATION STATE)-METHYLTRANSFERASE

    EPA Science Inventory

    The enzymatic methylation of inorganic As (iAs) is catalyzed by As(+3 oxidation state)-methyltransferase (AS3MT). AS3MT is expressed in rat liver and in human hepatocytes However, AS3MT is not expressed in UROtsa, human urothelial cells that do not methylate iAs. Thus, UROtsa ce...

  11. Comparative Distribution and Retention of Arsenic in Arsenic (+3 Oxidation State) Methyltransferase Knockout and Wild Type Mice

    EPA Science Inventory

    The mouse arsenic (+3 oxidation state) methyltransferase (As3mt) gene encodes a ~ 43 kDa protein that catalyzes conversion of inorganic arsenic into methylated products. Heterologous expression of AS3MT or its silencing by RNA interference controls arsenic methylation phenotypes...

  12. Size scales over which ordinary chondrites and their parent asteroids are homogeneous in oxidation state and oxygen-isotopic composition

    NASA Astrophysics Data System (ADS)

    Rubin, Alan E.; Ziegler, Karen; Young, Edward D.

    2008-02-01

    Literature data demonstrate that on a global, asteroid-wide scale (plausibly on the order of 100 km), ordinary chondrites (OC) have heterogeneous oxidation states and O-isotopic compositions (represented, respectively, by the mean olivine Fa and bulk Δ 17O compositions of equilibrated samples). Samples analyzed here include: (a) two H5 chondrite Antarctic finds (ALHA79046 and TIL 82415) that have the same cosmic-ray exposure age (7.6 Ma) and were probably within ˜1 km of each other when they were excavated from the H-chondrite parent body, (b) different individual stones from the Holbrook L/LL6 fall that were probably within ˜1 m of each other when their parent meteoroid penetrated the Earth's atmosphere, and (c) drill cores from a large slab of the Estacado H6 find located within a few tens of centimeters of each other. Our results indicate that OC are heterogeneous in their bulk oxidation state and O-isotopic composition on 100-km-size scales, but homogeneous on meter-, decimeter- and centimeter-size scales. (On kilometer size scales, oxidation state is heterogeneous, but O isotopes appear to be homogeneous.) The asteroid-wide heterogeneity in oxidation state and O-isotopic composition was inherited from the solar nebula. The homogeneity on small size scales was probably caused in part by fluid-assisted metamorphism and mainly by impact-gardening processes (which are most effective at mixing target materials on scales of ⩽1 m).

  13. METABOLISM AND TOXICITY OF AS IN HUMAN UROTHELIAL CELLS EXPRESSING RAT ARSENIC (+3 OXIDATION STATE)-METHYLTRANSFERASE

    EPA Science Inventory

    The enzymatic methylation of inorganic As (iAs) is catalyzed by As(+3 oxidation state)-methyltransferase (AS3MT). AS3MT is expressed in rat liver and in human hepatocytes However, AS3MT is not expressed in UROtsa, human urothelial cells that do not methylate iAs. Thus, UROtsa ce...

  14. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    SciTech Connect

    Yamaura, Kazunari

    2016-04-15

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

  15. Summertime state-level source-receptor relationships between nitrogen oxides emissions and surface ozone concentrations over the continental United States.

    PubMed

    Tong, Daniel Q; Mauzerall, Denise L

    2008-11-01

    Interstate transport of ozone (O3) and its precursors can contribute substantially to state-level surface o3 concentrations, making it difficult for some states to meet the National Ambient Air Quality Standards (NAAQS) for O3 by limiting only their own emissions. We analyze the effect of interstate transport on surface O3 in each continental U.S. state in July 1996 using the community multiscale air quality (CMAQ) model. By examining the difference between a baseline simulation and perturbation simulations in which each state's nitrogen oxides (NOx) emissions are removed, we establish for the first time a summertime source-receptor matrix for all 48 continental states. We find that for 16 (20) states at least one neighboring state's NOx emissions are responsible for a larger increase in monthly mean peak 8 h (all-hour) O3 concentrations than the state's own emissions. For over 80% of the contiguous states, interstate transport is more importantthan local emissions for summertime peak O3 concentrations. Our source-receptor matrices indicate that the geographic range of the clean air interstate rule (CAIR) was sufficient to address interstate transport of O3 in most of the states included in the program. However, the exclusion of Texas, which has particularly large NOx emissions, from the CAIR O3 program left emission sources uncontrolled that contribute more than 1 ppbv to the July mean of peak 8 h O3 concentrations in over a dozen states.

  16. Contribution of the First Electronically Excited State of Molecular Nitrogen to Thermospheric Nitric Oxide

    NASA Astrophysics Data System (ADS)

    Yonker, Justin D.

    The chemical reaction of the first excited electronic state of molecular nitrogen, N2(A3 S+u ) or N2(A), with ground state atomic oxygen, O(3 P), is an important contributor to thermospheric nitric oxide (NO). The importance is assessed by including this reaction in a one-dimensional photochemical model. The method is to scale the photoelectron impact ionization rate of N2 by a Gaussian centered near 100 km. Large uncertainties remain in the temperature dependence and branching ratios of many reactions important to NO production and loss. Similarly large uncertainties are present in the solar soft x-ray irradiance, known to be the fundamental driver of the low-latitude NO. To illustrate, it is shown that the equatorial, midday NO density measured by the Student Nitric Oxide Explorer (SNOE) satellite near the Solar Cycle 23 maximum can be recovered by the model to within the 20% measurement uncertainties using two rather different but equally reasonable chemical schemes, each with their own solar soft-xray irradiance parameterizations. Including the N2(A) changes the NO production rate by an average of 11%, but the NO density changes by a much larger 44%. This is explained by tracing the direct, indirect, and catalytic contributions of N2(A) to NO, finding them to contribute 40%, 33%, and 27 % respectively. The contribution of N2(A) relative to the total NO production and loss is assessed by tracing both back to their origins in the primary photoabsorption and photoelectron impact processes. The photoelectron impact ionization of N2 (PEI N2) is shown to be the main driver of the midday NO production while the photoelectron impact dissociation of N2 (PED N2) is the main NO destroyer. The net photoelectron impact excitation rate of N2 (PEE N2), which is responsible for the N2(A) production, is larger than either PEI N2 or PED N2 and thus potentially very important. Although the conservative assumptions regarding the level-specific NO yield from the N2(A)+O reaction

  17. High-precision determination of iron oxidation state in silicate glasses using XANES

    SciTech Connect

    Cottrell, Elizabeth; Kelley, Katherine A.; Lanzirotti, Antonio; Fischer, Rebecca A.

    2009-11-04

    Fe K-edge X-ray absorption near-edge structure (XANES) and Moessbauer spectra were collected on natural basaltic glasses equilibrated over a range of oxygen fugacity (QFM - 3.5 to QFM + 4.5). The basalt compositions and fO{sub 2} conditions were chosen to bracket the natural range of redox conditions expected for basalts from mid-ocean ridge, ocean island, back-arc basin, and arc settings, in order to develop a high-precision calibration for the determination of Fe{sup 3+}/{Sigma}Fe in natural basalts. The pre-edge centroid energy, corresponding to the 1s {yields} 3d transition, was determined to be the most robust proxy for Fe oxidation state, affording significant advantages compared to the use of other spectral features. A second-order polynomial models the correlation between the centroid and Fe{sup 3+}/{Sigma}Fe, yielding a precision of {+-} 0.0045 in Fe{sup 3+}/{Sigma}Fe for glasses with Fe{sup 3+}/{Sigma}Fe > 8%, which is comparable to the precision of wet chemistry. This high precision relies on a Si (311) monochromator to better define the Fe{sup 2+} and Fe{sup 3+} transitions, accurate and robust modeling of the pre-edge feature, dense fO{sub 2}-coverage and compositional appropriateness of reference glasses, and application of a non-linear drift correction. Through re-analysis of the reference glasses across three synchrotron beam sessions, we show that the quoted precision can be achieved (i.e., analyses are reproducible) across multiple synchrotron beam sessions, even when spectral collection conditions (detector parameters or sample geometry) change. Rhyolitic glasses were also analyzed and yield a higher centroid energy at a given Fe{sup 3+}/{Sigma}Fe than basalts, implying that major variations in melt structure affect the relationship between centroid position and Fe{sup 3+}/{Sigma}Fe, and that separate calibrations are needed for the determination of oxidation state in basalts and rhyolites.

  18. Titanium oxidation state and coordination in the lunar high-titanium glass source mantle

    SciTech Connect

    Krawczynski, M.J.; Sutton, S.R.; Grove, T.L.; Newville, M.

    2009-03-20

    XANES and EXAFS spectra from synthetic HiTi lunar glasses determine coordination of Ti in the HiTi source region. The amount of Ti{sup 3+} present affects the olivine-opx equilibrium, and the total amount of Ti{sup 3+} present requires a pyx bearing source. Lunar high-titanium (HiTi) ultramafic glasses provide us with evidence of the mantle processes that led to the melting of the lunar magma ocean cumulates nearly one billion years after the magma ocean solidified. Constraints on the depth, temperature and melting processes that formed the HiTi glasses are crucial for understanding the melting history of LMO products. The Apollo 17 orange glass (A17O) and Apollo 15 red glass (A15R) represent two of the HiTi compositions in the spectrum of pristine ultramafic glasses returned from the moon. The difference between these two compositions is that the A15R contains {approx}40% more TiO{sub 2} than the A17O. The low f{sub O2} of the ultramafic glass source regions allows for a certain amount of Ti{sup 3+} in the source mineralogy; however the amount of Ti{sup 3+} in the source and the host mineral for this element remain relatively unconstrained. In addition to the unknown mineralogy of the source region, the high amount of TiO*{sub 2} and FeO* in the HiTi magmas makes the phase relations extremely sensitive to changes in the oxidation state of the source region. We have previously investigated the oxidation state effect on the olivine-orthopyroxene multiple saturations points of the A15R and A17O and shown that the magnitude of the effect is proportional to the amount of Ti in the system. X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure (EXAFS) measurements have been made on minerals and glasses in experiments on synthetic analogues to the A17O and A15R. Our results show that Ti{sup 3+} concentration does indeed affect the multiple saturation points, and is an important constituent in the lunar interior.

  19. Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR

    NASA Astrophysics Data System (ADS)

    Vacchi, Isabella A.; Spinato, Cinzia; Raya, Jésus; Bianco, Alberto; Ménard-Moyon, Cécilia

    2016-07-01

    Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by amidation. We also prove that there is a negligible amount of carboxylic acid groups in two GO samples obtained by a different synthesis process, hence eliminating the possibility of amidation reactions with amine derivatives. This work brings additional insights into the chemical reactivity of GO, which is fundamental to control its functionalization, and highlights the major role of MAS NMR spectroscopy for a comprehensive characterization of derivatized GO.Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by

  20. Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

    PubMed

    Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

    2015-10-20

    This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

  1. Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy

    PubMed Central

    Wang, Y. F.; Singh, Shashi B.; Limaye, Mukta V.; Shao, Y. C.; Hsieh, S. H.; Chen, L. Y.; Hsueh, H. C.; Wang, H. T.; Chiou, J. W.; Yeh, Y. C.; Chen, C. W.; Chen, C. H.; Ray, Sekhar C.; Wang, J.; Pong, W. F.; Takagi, Y.; Ohigashi, T.; Yokoyama, T.; Kosugi, N.

    2015-01-01

    This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets. PMID:26481557

  2. Influence of stoichiometry and charge state on the structure and reactivity of cobalt oxide clusters with CO.

    PubMed

    Johnson, Grant E; Reveles, J Ulises; Reilly, Nelly M; Tyo, Eric C; Khanna, Shiv N; Castleman, A W

    2008-11-13

    Cationic and anionic cobalt oxide clusters, generated by laser vaporization, were studied using guided-ion-beam mass spectrometry to obtain insight into their structure and reactivity with carbon monoxide. Anionic clusters having the stoichiometries Co2O3(-), Co2O5(-), Co3O5(-) and Co3O6(-) were found to exhibit dominant products corresponding to the transfer of a single oxygen atom to CO, indicating the formation of CO 2. Cationic clusters, in contrast, displayed products resulting from the adsorption of CO onto the cluster accompanied by the loss of either molecular O 2 or cobalt oxide units. In addition, collision induced dissociation experiments were conducted with N 2 and inert xenon gas for the anionic clusters, and xenon gas for the cationic clusters. It was found that cationic clusters fragment preferentially through the loss of molecular O 2 whereas anionic clusters tend to lose both atomic oxygen and cobalt oxide units. To further analyze how stoichiometry and ionic charge state influence the structure of cobalt oxide clusters and their reactivity with CO, first principles theoretical electronic structure studies within the density functional theory framework were performed. The calculations show that the enhanced reactivity of specific anionic cobalt oxides with CO is due to their relatively low atomic oxygen dissociation energy which makes the oxidation of CO energetically favorable. For cationic cobalt oxide clusters, in contrast, the oxygen dissociation energies are calculated to be even lower than for the anionic species. However, in the cationic clusters, oxygen is calculated to bind preferentially in a less activated molecular O 2 form. Furthermore, the CO adsorption energy is calculated to be larger for cationic clusters than for anionic species. Therefore, the experimentally observed displacement of weakly bound O 2 units through the exothermic adsorption of CO onto positively charged cobalt oxides is energetically favorable. Our joint

  3. Passivation of oxide traps and interface states in GaAs metal-oxide-semiconductor capacitor by LaTaON passivation layer and fluorine incorporation

    SciTech Connect

    Liu, L. N.; Choi, H. W.; Lai, P. T.; Xu, J. P.

    2015-11-23

    GaAs metal-oxide-semiconductor capacitor with TaYON/LaTaON gate-oxide stack and fluorine-plasma treatment is fabricated and compared with its counterparts without the LaTaON passivation interlayer or the fluorine treatment. Experimental results show that the sample exhibits better characteristics: low interface-state density (8 × 10{sup 11 }cm{sup −2}/eV), small flatband voltage (0.69 V), good capacitance-voltage behavior, small frequency dispersion, and small gate leakage current (6.35 × 10{sup −6} A/cm{sup 2} at V{sub fb} + 1 V). These should be attributed to the suppressed growth of unstable Ga and As oxides on the GaAs surface during gate-oxide annealing by the LaTaON interlayer and fluorine incorporation, and the passivating effects of fluorine atoms on the acceptor-like interface and near-interface traps.

  4. The solid state conversion reaction of cobalt oxide and iron fluoride thin films

    NASA Astrophysics Data System (ADS)

    Thorpe, Ryan

    Iron (II) fluoride and cobalt (II) oxide are candidate electrode materials for a new class of rechargeable lithium ion batteries known as conversion batteries. Although the energy storage capacity of these materials represents a significant improvement over that of conventional electrode materials, many challenges must be overcome before conversion batteries can become commercially viable. Chief among these challenges is a loss of energy storage capacity as a function of the number of charge-discharge cycles. In this study, FeF2 and CoO thin films have been studied as solid state analogues for lithium ion battery electrodes. These films were grown with different crystalline orientations and exposed to lithium in an ultra high vacuum chamber in order to simulate the discharge of a conversion electrode. The electronic structure and chemical phase of the films before and after exposure to lithium were characterized using x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPS). The depth and homogeneity of the conversion reaction in the thin films was measured as a function of lithium exposure using angle-resolved XPS (ARXPS). The crystalline structure and morphology were studied using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). For polycrystalline FeF2 and CoO films, the products of the solid state conversion reactions were similar to those observed in electrochemical measurements. However, parasitic reaction pathways were identified for both reactions. The products of these reaction were found to inhibit the full conversion of the thin films, and are possibly responsible for the poor reaction kinetics in electrochemical cells. Furthermore, the diffusion of lithium into the FeF2 and CoO surfaces, and the concomitant conversion reaction, was found to depend strongly on the orientation of the surface. These differences in diffusivity could partially be

  5. Quasi–solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes

    PubMed Central

    Hu, Xiaofei; Li, Zifan; Zhao, Yaran; Sun, Jianchao; Zhao, Qing; Wang, Jianbin; Tao, Zhanliang; Chen, Jun

    2017-01-01

    Na-CO2 batteries using earth-abundant Na and greenhouse gas CO2 are promising tools for mobile and stationary energy storage, but they still pose safety risks from leakage of liquid electrolyte and instability of the Na metal anode. These issues result in extremely harsh operating conditions of Na-CO2 batteries and increase the difficulty of scaling up this technology. We report the development of quasi–solid state Na-CO2 batteries with high safety using composite polymer electrolyte (CPE) and reduced graphene oxide (rGO) Na anodes. The CPE of PVDF-HFP [poly(vinylidene fluoride-co-hexafluoropropylene)]–4% SiO2/NaClO4–TEGDME (tetraethylene glycol dimethyl ether) has high ion conductivity (1.0 mS cm−1), robust toughness, a nonflammable matrix, and strong electrolyte-locking ability. In addition, the rGO-Na anode presents fast and nondendritic Na+ plating/stripping (5.7 to 16.5 mA cm−2). The improved kinetics and safety enable the constructed rGO-Na/CPE/CO2 batteries to successfully cycle in wide CO2 partial pressure window (5 to 100%, simulated car exhaust) and especially to run for 400 cycles at 500 mA g−1 with a fixed capacity of 1000 mA·hour g−1 in pure CO2. Furthermore, we scaled up the reversible capacity to 1.1 A·hour in pouch-type batteries (20 × 20 cm, 10 g, 232 Wh kg−1). This study makes quasi–solid state Na-CO2 batteries an attractive prospect. PMID:28164158

  6. Arsenic (+ 3 oxidation state) methyltransferase and the methylation of arsenicals in the invertebrate chordate Ciona intestinalis.

    PubMed

    Thomas, David J; Nava, Gerardo M; Cai, Shi-Ying; Boyer, James L; Hernández-Zavala, Araceli; Gaskins, H Rex

    2010-01-01

    Biotransformation of inorganic arsenic (iAs) involves methylation catalyzed by arsenic (+ 3 oxidation state) methyltransferase (As3mt) yielding mono-, di-, and trimethylated arsenicals. To investigate the evolution of molecular mechanisms that mediate arsenic biotransformation, a comparative genomic approach focusing on the invertebrate chordate Ciona intestinalis was used. Bioinformatic analyses identified an As3mt gene in the C. intestinalis genome. Constitutive As3mt RNA expression was observed in heart, branchial sac, and gastrointestinal tract. Adult animals were exposed to 0 or 1 ppm of iAs for 1 or 5 days. Steady-state As3mt RNA expression in the gastrointestinal tract was not modulated significantly by 5 days of exposure to iAs. Tissue levels of iAs and its methylated metabolites were determined by hydride generation-cryotrapping-gas chromatography-atomic absorption spectrometry. At either time point, exposure to iAs significantly increased concentrations of iAs and its methylated metabolites in tissues. After 5 days of exposure, total speciated arsenic concentrations were highest in branchial sac (3705 ng/g), followed by heart (1019 ng/g) and gastrointestinal tract (835 ng/g). At this time point, the sum of the speciated arsenical concentrations in gastrointestinal tract and heart equaled or exceeded that of iAs; in branchial sac, iAs was the predominant species present. Ciona intestinalis metabolizes iAs to its methylated metabolites, which are retained in tissues. This metabolic pattern is consistent with the presence of an As3mt ortholog in its genome and constitutive expression of the gene in prominent organs, making this basal chordate a useful model to examine the evolution of arsenic detoxification.

  7. All-Graphene Oxide Flexible Solid-State Supercapacitors with Enhanced Electrochemical Performance.

    PubMed

    Ogata, Chikako; Kurogi, Ruriko; Awaya, Keisuke; Hatakeyama, Kazuto; Taniguchi, Takaaki; Koinuma, Michio; Matsumoto, Yasumichi

    2017-08-09

    The rapid development of flexible and wearable electronics has led to an increase in the demand for flexible supercapacitors with enhanced electrochemical performance. Graphene oxide (GO) and reduced GO (rGO) exhibit several key properties required for supercapacitor components. Although solid-state rGO/GO/rGO supercapacitors with unique structures are promising, their moderate capacitance is inadequate for practical applications. Herein, we report a flexible solid-state rGO/GO/rGO supercapacitor comprising H2SO4-intercalated GO electrolyte/separator and pseudocapacitive rGO electrodes, which demonstrate excellent electrochemical performance. The resulting supercapacitor delivered an areal capacitance of 14.5 mF cm(-2), which is among the highest values achieved for any rGO/GO/rGO supercapacitor. High ionic concentration and fast ion conduction in the H2SO4-intercalated GO electrolyte/separator and abundant CH defects, which serve as pseudocapacitive sites on the rGO electrode, were responsible for the high capacitance of this device. The rGO electrode, well separated by the H2SO4 molecular spacer, supplied highly efficient ion transport channels, leading to excellent rate capability. The highly packed rGO electrode and high specific capacitance resulted in a high volumetric energy density (1.24 mWh cm(-3)) observed in this supercapacitor. The structure, without a clear interface between GO and rGO, provides extremely low resistance and flexibility for devices. Our device operated in air (25 °C 40%) without the use of external electrolytes, conductive additives, and binders. Furthermore, we demonstrate a simple and versatile technique for supercapacitor fabrication by combining photoreduction and electrochemical treatment. These advantages are attractive for developing novel carbon-based energy devices with high device performance and low fabrication costs.

  8. Quasi-solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes.

    PubMed

    Hu, Xiaofei; Li, Zifan; Zhao, Yaran; Sun, Jianchao; Zhao, Qing; Wang, Jianbin; Tao, Zhanliang; Chen, Jun

    2017-02-01

    Na-CO2 batteries using earth-abundant Na and greenhouse gas CO2 are promising tools for mobile and stationary energy storage, but they still pose safety risks from leakage of liquid electrolyte and instability of the Na metal anode. These issues result in extremely harsh operating conditions of Na-CO2 batteries and increase the difficulty of scaling up this technology. We report the development of quasi-solid state Na-CO2 batteries with high safety using composite polymer electrolyte (CPE) and reduced graphene oxide (rGO) Na anodes. The CPE of PVDF-HFP [poly(vinylidene fluoride-co-hexafluoropropylene)]-4% SiO2/NaClO4-TEGDME (tetraethylene glycol dimethyl ether) has high ion conductivity (1.0 mS cm(-1)), robust toughness, a nonflammable matrix, and strong electrolyte-locking ability. In addition, the rGO-Na anode presents fast and nondendritic Na(+) plating/stripping (5.7 to 16.5 mA cm(-2)). The improved kinetics and safety enable the constructed rGO-Na/CPE/CO2 batteries to successfully cycle in wide CO2 partial pressure window (5 to 100%, simulated car exhaust) and especially to run for 400 cycles at 500 mA g(-1) with a fixed capacity of 1000 mA·hour g(-1) in pure CO2. Furthermore, we scaled up the reversible capacity to 1.1 A·hour in pouch-type batteries (20 × 20 cm, 10 g, 232 Wh kg(-1)). This study makes quasi-solid state Na-CO2 batteries an attractive prospect.

  9. Direct Determination of Oxidation States of Uranium in Mixed-Valent Uranium Oxides Using Total Reflection X-ray Fluorescence X-ray Absorption Near-Edge Spectroscopy.

    PubMed

    Sanyal, Kaushik; Khooha, Ajay; Das, Gangadhar; Tiwari, M K; Misra, N L

    2017-01-03

    Total reflection X-ray fluorescence (TXRF)-based X-ray absorption near-edge spectroscopy has been used to determine the oxidation state of uranium in mixed-valent U3O8 and U3O7 uranium oxides. The TXRF spectra of the compounds were measured using variable X-ray energies in the vicinity of the U L3 edge in the TXRF excitation mode at the microfocus beamline of the Indus-2 synchrotron facility. The TXRF-based X-ray absorption near-edge spectroscopy (TXRF-XANES) spectra were deduced from the emission spectra measured using the energies below and above the U L3 edge in the XANES region. The data processing using TXRF-XANES spectra of U(IV), U(V), and U(VI) standard compounds revealed that U present in U3O8 is a mixture of U(V) and U(VI), whereas U in U3O7 is mixture of U(IV) and U(VI). The results obtained in this study are similar to that reported in literature using the U M edge. The present study has demonstrated the possibility of application of TXRF for the oxidation state determination and elemental speciation of radioactive substances in a nondestructive manner with very small amount of sample requirement.

  10. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    NASA Astrophysics Data System (ADS)

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-11-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1-xCaxAlO3-δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400-500 °C. The response current value at -300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

  11. FTIR assessment of poly(ethylene oxide) irradiated in solid state, melt and aqeuous solution

    NASA Astrophysics Data System (ADS)

    Pucić, Irina; Jurkin, Tanja

    2012-09-01

    FTIR spectroscopy was used to study poly(ethylene oxide), PEO, irradiated in solid and molten aggregate states and as aqueous solutions of various concentrations. The changes in shape and width of -C-O-C- complex absorption intensities at around 1112 cm-1 were the most prominent. On irradiation of solid samples in contact with air shrinking of -C-O-C- complex and increase in its absorption intensities indicated predominant degradation. Crosslinking prevailed on irradiation of molten PEO and of its aqueous solutions in nitrogen atmosphere and manifested itself as widening of -C-O-C- absorption and decrease of corresponding intensities. Partial or complete merging of CH2 wagging vibrations at 1342 cm-1 and 1360 cm-1 that are characteristic of crystalline PEO into a single absorption at around 1350 cm-1 indicated amorphization what was observed for samples that had reduced degree of crystallinity determined by differential scanning calorimetry. DSC could not discriminate between degradation and crosslinking while the changes in width and shape of -C-O-C- complex were independent of the changes in crystallinity. Comparison of FTIR spectra of the same PEO samples obtained as thin film and as KBr pellets revealed that pellet preparation results in a number of spectral artefacts.

  12. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

    PubMed Central

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-01-01

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden–Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure. PMID:27578622

  13. Oxidation state and local structure of plutonium reacted with magnetite, mackinawite, and chukanovite.

    PubMed

    Kirsch, Regina; Fellhauer, David; Altmaier, Marcus; Neck, Volker; Rossberg, Andre; Fanghänel, Thomas; Charlet, Laurent; Scheinost, Andreas C

    2011-09-01

    Due to their redox reactivity, surface sorption characteristics, and ubiquity as corrosion products or as minerals in natural sediments, iron(II)-bearing minerals control to a large extent the environmental fate of actinides. Pu-L(III)-edge XANES and EXAFS spectra were used to investigate reaction products of aqueous (242)Pu(III) and (242)Pu(V) reacted with magnetite, mackinawite, and chukanovite under anoxic conditions. As Pu concentrations in the liquid phase were rapidly below detection limit, oxidation state and local structure of Pu were determined for Pu associated with the solid mineral phase. Pu(V) was reduced in the presence of all three minerals. A newly identified, highly specific Pu(III)-sorption complex formed with magnetite. Solid PuO(2) phases formed in the presence of mackinawite and chukanovite; in the case of chukanovite, up to one-third of plutonium was also present as Pu(III). This highlights the necessity to consider, under reducing anoxic conditions, Pu(III) species in addition to tetravalent PuO(2) for environmental risk assessment. Our results also demonstrate the necessity to support thermodynamic calculations with spectroscopic data.

  14. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

    SciTech Connect

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-08-31

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), A n+1 B n O 3n+1 , thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Sr n+1 Ti n O 3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

  15. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

    DOE PAGES

    Stone, Greg; Ophus, Colin; Birol, Turan; ...

    2016-08-31

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), A n+1 B n O 3n+1 , thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Sr n+1 Ti n O 3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases.more » We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.« less

  16. Synthesis and spectroscopic analysis of polydiphenylamine via oxidation with bentonite clay in the solid state.

    PubMed

    Kubota, Mayara Masae; Sacco, Bruno Luis; Bento, Danielly Cristina; de Santana, Henrique

    2015-12-05

    In this study, solids of polydiphenylamine (PDPA) synthesized mechanochemically by reaction with bentonite (PDPAOB) were studied using Raman spectroscopy. It was possible to identify the chemical species in the PDPA-bentonite compound. The spectra obtained were compared to the spectra of PDPA prepared chemically by oxidation of DPA with K2S2O8 in the solid state, and PDPA produced electrochemically, with the aim of studying the characteristic frequencies of the aromatic segments (DPB), radical cation (DPB(+)) and dication (DPB(2+)) of N,N-diphenylbenzidine (DPB) in the polymer structure of the PDPA. To analyze the segments present, the band characteristic of CC asymmetric stretching of the aromatic ring in the Raman spectra was deconvoluted because of the widening of the band and shifts observed by irradiation at wavelengths of 532 and 785 nm. This procedure showed that there are three distinct contributions in the spectra which facilitate the monitoring of changes in the contributions of the segments in the materials doped with HCl (PDPAOBD) and de-doped with NH4OH, (PDPAOBR). Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs

    NASA Technical Reports Server (NTRS)

    Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.

    2006-01-01

    Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.

  18. Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR.

    PubMed

    Vacchi, Isabella A; Spinato, Cinzia; Raya, Jésus; Bianco, Alberto; Ménard-Moyon, Cécilia

    2016-07-14

    Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by amidation. We also prove that there is a negligible amount of carboxylic acid groups in two GO samples obtained by a different synthesis process, hence eliminating the possibility of amidation reactions with amine derivatives. This work brings additional insights into the chemical reactivity of GO, which is fundamental to control its functionalization, and highlights the major role of MAS NMR spectroscopy for a comprehensive characterization of derivatized GO.

  19. Structure of the sulfur K x-ray emission spectrum: influence of the oxidation state

    NASA Astrophysics Data System (ADS)

    Pérez, P. D.; Carreras, A. C.; Trincavelli, J. C.

    2012-01-01

    The sulfur K x-ray emission was studied in pure sulfur, anhydrite (CaSO4) and sphalerite (ZnS) samples. The ionizations were induced by electron impact and the spectra were recorded with a wavelength dispersive spectrometer. The spectral processing was performed through a methodology based on the optimization of atomic and experimental parameters. Energies and intensities of diagram and satellite lines were determined for a set of transitions in the Kα and Kβ groups. The lines studied include Kα22, Kα2, Kα1, Kα‧, Kα3, Kα4, Kα5, Kα6, Kβ1,3, Kβ-RAE, KβIII, KβIV, Kβx, Kβ‧ and Kβ″. The main spectral differences between the three oxidation states were analysed, considering the influence of the ligand atoms. The results were compared with data published by other authors and the origin of certain lines was discussed on the basis of data available in the literature.

  20. Sediment Ammonia-Oxidizing Microorganisms in Two Plateau Freshwater Lakes at Different Trophic States.

    PubMed

    Yang, Yuyin; Zhang, Jingxu; Zhao, Qun; Zhou, Qiheng; Li, Ningning; Wang, Yilin; Xie, Shuguang; Liu, Yong

    2016-02-01

    Both ammonia-oxidizing archaea (AOA) and bacteria (AOB) can contribute to ammonia biotransformation in freshwater lake ecosystems. However, the factors shaping the distribution of sediment AOA and AOB in plateau freshwater lake remains unclear. The present study investigated sediment AOA and AOB communities in two freshwater lakes (hypertrophic Dianchi Lake and mesotrophic Erhai Lake) on the Yunnan Plateau (China). A remarkable difference in the abundance, diversity, and composition of sediment AOA and AOB communities was observed between Dianchi Lake and Erhai Lake. AOB usually outnumbered AOA in Dianchi Lake, but AOA showed the dominance in Erhai Lake. Organic matter (OM), total nitrogen (TN), and total phosphorus (TP) might be the key determinants of AOB abundance, while AOA abundance was likely influenced by the ration of OM to TN (C/N). AOA or AOB community structure was found to be relatively similar in the same lake. TN and TP might play important roles in shaping sediment AOA and AOB compositions in Dianchi Lake and Erhai Lake. Moreover, Nitrososphaera-like AOA were detected in Dianchi Lake. Nitrosospira- and Nitrosomonas-like AOB were dominant in Dianchi Lake and Erhai Lake, respectively. Sediment AOA and AOB communities in Dianchi Lake and Erhai Lake were generally regulated by trophic state.

  1. Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide.

    PubMed

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J; Schlom, Darrell G; Alem, Nasim; Gopalan, Venkatraman

    2016-08-31

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

  2. Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide

    NASA Astrophysics Data System (ADS)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-08-01

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

  3. Oxidation state of europium in scheelite: Tracking fluid-rock interaction in gold deposits

    SciTech Connect

    Brugger, Joël; Etschmann, Barbara; Pownceby, Mark; Liu, Weihua; Grundler, Pascal; Brewe, Dale

    2008-12-09

    We used {mu}-XANES spectroscopy to measure the oxidation state of europium in-situ at near-{mu}m resolution in hydrothermal scheelite from the giant Archean gold deposits of Kalgoorlie, Western Australia. By combining these measurements with {mu}-XRF imaging, it is possible to distinguish inhomogeneities in Eu{sup 2+}/Eu{sup 3+} ratios that developed during mineral precipitation from the effects of subsequent hydrothermal alteration and weathering. Thermodynamic analysis reveals that under the conditions typical of the formation of many Au deposits, the Eu{sup 2+}/Eu{sup 3+} ratio in the hydrothermal fluid is highly sensitive to pH. The range in pH calculated from the Eu{sup 2+}/Eu{sup 3+} ratios in the analyzed scheelite corresponds to a maximum in Au solubility under the ore-forming conditions, and suggests buffering of pH by the CO{sub 2(aq)}-rich fluid. The primary heterogeneity of the Karlgoorlie scheelite most likely results form pH oscillating between fluid- and rock-buffered conditions, and reflects the dynamics of the hydrothermal system.

  4. Mn oxidation state controllable spinel manganese-based intergrown cathode for excellent reversible lithium storage

    NASA Astrophysics Data System (ADS)

    Zhao, Quanqing; Wu, Yu; Ma, Xilan; Wang, Ran; Xu, Xingyan; Cao, Chuanbao

    2017-08-01

    Herein we report a novel hierarchical porous hollow cube-shaped 5 V spinel manganese-based intergrown cathode materials with controlling the average oxidation state of Mn. The equal proportion of LiNi0.5Mn1.5O4 and LiMn2O4 (LiMn1.75Ni0.25O4) intergrown cathode materials exhibit the most excellent electrochemical performance with the initial discharge capacity and energy density as high as 141.7 mAh g-1 and 627.8 Wh Kg-1 at 1 C. What's more, even though cells are performed at elevated temperature and encounter with intermittent high rate load, considerably superior cycle stabilities still are retained. The LMO/LNMO-1/1 yields the primal discharge capacity of 142.5 mAh g-1 and 140.8 mAh g-1, with 93.1% and 92.9% capacity retention up to 50 cycles at 55 °C and subjecting to intermittent 5 C discharge and charge load every five cycles, respectively.

  5. State-of-the-art Thin Film Electrolytes For Solid Oxide Fuel Cells

    SciTech Connect

    Thevuthasan, Suntharampillai; Nandasiri, Manjula I.

    2015-02-19

    State-of-the-Art solid oxide fuel cells (SOFC) are amongst the main candidates for clean energy technology due to their high efficiency, fuel flexibility, low air pollution, and minimal greenhouse gas emission. However, high operational temperature of SOFC is a greater challenge in commercialization these devices for low cost and portable applications. High temperature operation of SOFC degrades its performance with aging, limits the selection of materials for fuel cell components, and increases the fabrication cost. Thus, there have been enormous efforts to improve the properties of existing materials and develop new materials for SOFC components in order to lower the operating temperature of SOFC. Recent advances in thin film technology have also been utilized to develop new materials with improved properties for SOFC. One of the key components in SOFC is the electrolyte and several research groups are working on developing new electrolyte materials. In this chapter, we will discuss the recent advances in thin film SOFC electrolytes. This extensive discussion includes the evolution of doped ceria, doped zirconia, and multilayer hetero-structured thin film electrolytes. The newly developed nanoscale thin films and multi-layer hetero-structures with improved oxygen ionic conductivity will have significant impact on SOFC devices.

  6. Oxidation state of iron in mantle-derived magmas of the Icelandic rift zone

    NASA Astrophysics Data System (ADS)

    Öskarsson, N.; Helgason, Ö.; Steinthórsson, S.

    1994-12-01

    Olivine tholeiites are mantle-derived magmas that are formed by partial melting of their deep sources and which have equilibrated with mineral assemblages at slightly different subcrustal pressure-temperature conditions prior to eruption. The minimum depth of the pre-eruptive reservoirs of these magmas is in the order of 10 15 km and their liquidus temperatures fall within the range of 1180 1240 ‡C. Three types of primitive olivine tholeiites are exposed along the rift zones in Iceland. In the present study, the ferric/ferrous ratios of natural glasses (pillow crusts) of the three types of olivine tholeiites were obtained by Mössbauer spectrometry. This technique is particularly well suited for the analysis of high-Mg glasses since it resolves microcrystallites of olivine which contribute to ferrous iron in chemical analysis. All results fall within 10 15% Fe(III). At the liquidus temperature of these glasses, this ferric/ferrous ratio corresponds to fugacity close to the fayalite-magnetite-quartz-oxygen (FMQ) buffer with an uncertainty of less than one log unit in fO2. This result confirms that there is no significant difference in the oxidation state of the three magma types.

  7. Regional Sources of Nitrous Oxide over the United States: Seasonal Variation and Spatial Distribution

    SciTech Connect

    Miller, S. M.; Kort, E. A.; Hirsch, A. I.; Dlugokencky, E. J.; Andrews, A. E.; Xu, X.; Tian, H.; Nehrkorn, T.; Eluszkiewicz, J.; Michalak, A. M.; Wofsy, S. C.

    2012-01-01

    This paper presents top-down constraints on the magnitude, spatial distribution, and seasonality of nitrous oxide (N{sub 2}O) emissions over the central United States. We analyze data from tall towers in 2004 and 2008 using a high resolution Lagrangian particle dispersion model paired with both geostatistical and Bayesian inversions. Our results indicate peak N{sub 2}O emissions in June with a strong seasonal cycle. The spatial distribution of sources closely mirrors data on fertilizer application with particularly large N{sub 2}O sources over the US Cornbelt. Existing inventories for N{sub 2}O predict emissions that differ substantially from the inverse model results in both seasonal cycle and magnitude. We estimate a total annual N{sub 2}O budget over the central US of 0.9-1.2 TgN/yr and an extrapolated budget for the entire US and Canada of 2.1-2.6 TgN/yr. By this estimate, the US and Canada account for 12-15% of the total global N{sub 2}O source or 32-39% of the global anthropogenic source as reported by the Intergovernmental Panel on Climate Change in 2007.

  8. [Relationship between Arsenic (+3 Oxidation State) Methyltransferase Genetic Polymorphisms and Methylation Capacity of Inorganic Arsenic].

    PubMed

    Agusa, Tetsuro; Kunito, Takashi; Minh Tue, Nguyen; Thi Mai Lan, Vi; Binh Minh, Tu; Thi Kim Trang, Pham; Fujihara, Junko; Takeshita, Haruo; Takahashi, Shin; Hung Viet, Pham; Tanabe, Shinsuke; Iwata, Hisato

    2015-01-01

    Arsenic metabolism affects the susceptibility of humans to arsenic toxicity; therefore, clarification of the factors associated with individual variations in arsenic metabolism is an important task. Genetic polymorphisms such as single nucleotide polymorphisms (SNPs) in arsenic (+3 oxidation state) methyltransferase (AS3MT), which can methylate arsenic compounds using S-adenosyl-l-methionine (AdoMet), have been reported to modify arsenic methylation. In this review, we summarize studies conducted by us in Vietnam and by others on the association of AS3MT genetic polymorphisms with arsenic metabolism as well as human health effects. Most of the SNPs in AS3MT showed inconsistent results in terms of genotype-dependent differences in arsenic metabolism among the studies. However, AS3MT 12390 (rs3740393) and 14458 (rs11191439) were consistently related to arsenic methylation regardless of the study population: AS3MT 12390 (rs3740393) affected the second step of methylation of arsenic, whereas 14458 (rs11191439) affected the first methylation step.

  9. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    PubMed Central

    Moreno-Ruíz, Luis Antonio; Ibarra-Quevedo, David; Rodríguez-Martínez, Erika; Maldonado, Perla D.; Sarabia-Ortega, Benito; Hernández-Martínez, José Gustavo; Espinosa-Caleti, Beda; Mendoza-Pérez, Beatriz; Rivas-Arancibia, Selva

    2015-01-01

    The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS) and the left ventricular end diastolic pressure (LVEDP). Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p < 0.05) higher levels of oxidized proteins (5.03 ± 1.05 versus 4.06 ± 0.63 nmol/mg), lower levels of extracellular superoxide dismutase (EC-SOD) activity (0.045 ± 0.02 versus 0.082 ± 0.02 U/mg), higher LVEDP (16.2 ± 4.5 versus 11.3 ± 1.6 mm Hg), and lower GLS (−12% versus −16%). Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r = 0.386, p = 0.006) and LVEDP (r = 0.389, p = 0.005); we also found a negative correlation of EC-SOD activity with GLS (r = −0.404, p = 0.004) and LVEDP (r = −0.347, p = 0.014). PMID:26504504

  10. Transitions between strongly correlated and random steady-states for catalytic CO-oxidation on surfaces at high-pressure

    SciTech Connect

    Liu, Da -Jiang; Evans, James W.

    2015-04-02

    We explore simple lattice-gas reaction models for CO-oxidation on 1D and 2D periodic arrays of surface adsorption sites. The models are motivated by studies of CO-oxidation on RuO2(110) at high-pressures. Although adspecies interactions are neglected, the effective absence of adspecies diffusion results in kinetically-induced spatial correlations. A transition occurs from a random mainly CO-populated steady-state at high CO-partial pressure pCO, to a strongly-correlated near-O-covered steady-state for low pCO as noted. In addition, we identify a second transition to a random near-O-covered steady-state at very low pCO.

  11. Transitions between strongly correlated and random steady-states for catalytic CO-oxidation on surfaces at high-pressure

    DOE PAGES

    Liu, Da -Jiang; Evans, James W.

    2015-04-02

    We explore simple lattice-gas reaction models for CO-oxidation on 1D and 2D periodic arrays of surface adsorption sites. The models are motivated by studies of CO-oxidation on RuO2(110) at high-pressures. Although adspecies interactions are neglected, the effective absence of adspecies diffusion results in kinetically-induced spatial correlations. A transition occurs from a random mainly CO-populated steady-state at high CO-partial pressure pCO, to a strongly-correlated near-O-covered steady-state for low pCO as noted. In addition, we identify a second transition to a random near-O-covered steady-state at very low pCO.

  12. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    PubMed Central

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-01-01

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production. PMID:27187352

  13. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States.

    PubMed

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-05-11

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  14. Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    ERIC Educational Resources Information Center

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

    2014-01-01

    The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

  15. Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    ERIC Educational Resources Information Center

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

    2014-01-01

    The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

  16. X-ray Raman Scattering at Extreme Conditions: Insights to Local Structure, Oxidation and Spin state

    NASA Astrophysics Data System (ADS)

    Wilke, M.; Sternemann, C.; Sahle, C.; Spiekermann, G.; Nyrow, A.; Weis, C.; Cerantola, V.; Schmidt, C.; Yavas, H.

    2015-12-01

    In the last decades, X-ray spectroscopic techniques using very intense synchrotron radiation (SR) have become indispensable tools for studying geomaterials. Due to the rather low absorption of hard X-rays, SR opens up the possibility to perform measurements in high-pressure, high temperature cells. The range of elements accessible by X-ray absorption spectroscopy (XAFS) techniques in these cells is limited by the absorption of X-rays due to the sample environment, i.e. the diamond windows. The indirect measurement of XAFS spectra by inelastic X-ray Raman scattering (XRS) provides a workaround to access absorption edges at low energies (e.g. low Z elements). Therefore, XRS enables measurements that are similar to electron energy loss spectroscopy but offer to measure at in-situ conditions and not just in vacuum. Measurements of the O K-edge of H2O from ambient to supercritical PT-conditions (up to 600°C @ 134 MPa; 400°C @ 371 MPa) were used to trace structural changes of the hydrogen-bonded network, which controls many physical and chemical properties of H2O [1]. The Fe M3,2-edge measured by XRS were used to characterize the oxidation state and local structure in crystalline compounds and glasses [2]. Furthermore, the M3,2 yields detailed insight to the crystal-field splitting and electronic spin state. In a reconnaissance study, the pressure-induced high-spin to low-spin transition of Fe in FeS between 6 and 8 GPa was measured. By multiplet calculations of the spectra for octahedral Fe2+, a difference in crystal field splitting between the two states of ca. 1.7 eV was estimated [3]. Finally, we successfully assessed the electronic structure of Fe in siderite by measurements of M and L-edge up to 50 GPa, covering the spin transition between 40 and 45 GPa. [1] Sahle et al. (2013) PNAS, doi: 10.1073/pnas.1220301110.. [2] Nyrow et al. (2014) Contrib Mineral Petrol 167, 1012. [3] Nyrow et al. (2014) Appl Phys Lett 104, 262408.

  17. Solvothermal synthesis of a bimetallic thiometallate containing germanium in two oxidation states

    SciTech Connect

    Powell, Anthony V.; Mackay, Rosalyn

    2011-12-15

    A new layered germanium-antimony sulphide, [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}], has been prepared at 463 K under solvothermal conditions in the presence of ethylenediamine. The compound has been characterised by single-crystal X-ray diffraction, thermogravimetry, elemental analysis and reflectance spectroscopy. [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}] crystallises in the space group Pbca (a=13.3284(5), b=17.4801(6), c=18.5447(7) A). The structure consists of cyclic [GeSb{sub 2}S{sub 8}]{sup 6-} units that form chains which are cross-linked through Sb{sub 2}S{sub 2} rings to generate layers of stoichiometry [GeSb{sub 2}S{sub 6}]{sup 2-}, between which [Ge(en){sub 3}]{sup 2+} cations are located. [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}] contains germanium in both the divalent and tetravalent states. The optical band gap of 2.49(4) eV is in excellent agreement with the value expected on the basis of the correlation with the density of metal centres previously identified for thioantimonates, and is consistent with states at the top of the valence band being predominantly of sulphur 3p character. - Graphical abstract: [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}] is a mixed valent germanium compound that contains [GeSb{sub 2}S{sub 8}]{sup 6-} units cross linked through Sb{sub 2}S{sub 2} units to generate layers. Highlights: Black-Right-Pointing-Pointer Preparation and structural characterisation of a new mixed-metal thiometallate. Black-Right-Pointing-Pointer Germanium present in two oxidation states. Black-Right-Pointing-Pointer Optical band gap of 2.49(4) eV. Black-Right-Pointing-Pointer Band gap conforms to a correlation between band gap and density of metal centres.

  18. Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UOx(-) and UOx (x = 3-5).

    PubMed

    Su, Jing; Li, Wei-Li; Lopez, Gary V; Jian, Tian; Cao, Guo-Jin; Li, Wan-Lu; Schwarz, W H Eugen; Wang, Lai-Sheng; Li, Jun

    2016-02-25

    Uranium oxide clusters UOx(-) (x = 3-5) were produced by laser vaporization and characterized by photoelectron spectroscopy and quantum theory. Photoelectron spectra were obtained for UOx(-) at various photon energies with well-resolved detachment transitions and vibrational resolution for x = 3 and 4. The electron affinities of UOx were measured as 1.12, 3.60, and 4.02 eV for x = 3, 4, and 5, respectively. The geometric and electronic structures of both the anions and the corresponding neutrals were investigated by quasi-relativistic electron-correlation quantum theory to interpret the photoelectron spectra and to provide insight into their chemical bonding. For UOx clusters with x ≤ 3, the O atoms appear as divalent closed-shell anions around the U atom, which is in various oxidation states from U(II)(fds)(4) in UO to U(VI)(fds)(0) in UO3. For x > 3, there are no longer sufficient valence electrons from the U atom to fill the O(2p) shell, resulting in fractionally charged and multicenter delocalized valence states for the O ligands as well as η(1)- or η(2)-bonded O2 units, with unusual spin couplings and complicated electron correlations in the unfilled poly oxo shell. The present work expands our understanding of both the bonding capacities of actinide elements with extended spdf valence shells as well as the multitude of oxygen's charge and bonding states.

  19. L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

    NASA Technical Reports Server (NTRS)

    Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

    2008-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

  20. The electronic states of pyridine-N-oxide studied by VUV photoabsorption and ab initio configuration interaction computations.

    PubMed

    Palmer, Michael H; Hoffmann, Søren Vrønning; Jones, Nykola C; Smith, Elliott R; Lichtenberger, Dennis L

    2013-06-07

    The first vacuum-ultraviolet absorption spectrum of pyridine-N-oxide has been obtained, and has led to the identification of nearly 30 Rydberg states. These states were identified by use of the vibrational envelope ("footprint") of the UV-photoelectron spectrum, and are based on the first to the third ionization energies (IE). The adiabatic IE order, central to the Rydberg state symmetry identification, is confirmed by multi-configuration SCF calculations as: 1(2)B1 < 1(2)B2 < 1(2)A2 < 2(2)B1. Several excited valence state equilibrium structures were determined by multi-configuration SCF and coupled cluster procedures. Multi-reference multi-root CI was used to calculate both Rydberg and valence state vertical excitation energies and oscillator strengths, which were correlated with the experimental measurements.

  1. Interface states and internal photoemission in p-type GaAs metal-oxide-semiconductor surfaces

    NASA Technical Reports Server (NTRS)

    Kashkarov, P. K.; Kazior, T. E.; Lagowski, J.; Gatos, H. C.

    1983-01-01

    An interface photodischarge study of p-type GaAs metal-oxide-semiconductor (MOS) structures revealed the presence of deep interface states and shallow donors and acceptors which were previously observed in n-type GaAs MOS through sub-band-gap photoionization transitions. For higher photon energies, internal photoemission was observed, i.e., injection of electrons to the conduction band of the oxide from either the metal (Au) or from the GaAs valence band; the threshold energies were found to be 3.25 and 3.7 + or - 0.1 eV, respectively. The measured photoemission current exhibited a thermal activation energy of about 0.06 eV, which is consistent with a hopping mechanism of electron transport in the oxide.

  2. Fortification of CdSe quantum dots with graphene oxide. Excited state interactions and light energy conversion.

    PubMed

    Lightcap, Ian V; Kamat, Prashant V

    2012-04-25

    Graphene based 2-D carbon nanostructures provide new opportunities to fortify semiconductor based light harvesting assemblies. Electron and energy transfer rates from photoexcited CdSe colloidal quantum dots (QDs) to graphene oxide (GO) and reduced graphene oxide (RGO) were isolated by analysis of excited state deactivation lifetimes as a function of degree of oxidation and charging in (R)GO. Apparent rate constants for energy and electron transfer determined for CdSe-GO composites were 5.5 × 10(8) and 6.7 × 10(8) s(-1), respectively. Additionally, incorporation of GO in colloidal CdSe QD films deposited on conducting glass electrodes was found to enhance the charge separation and electron conduction through the QD film, thus allowing three-dimensional sensitization. Photoanodes assembled from CdSe-graphene composites in quantum dot sensitized solar cells display improved photocurrent response (~150%) over those prepared without GO.

  3. Oxidation potential and state of some vanadium ores and the relation of woody material to their deposition

    USGS Publications Warehouse

    Pommer, Alfred Michael

    1956-01-01

    Oxidation potential studies with a multiple pH-potential recorder designed and constructed for this purpose demonstrated that some uranium-vanadium ores in the Colorado Plateau were in a reduced state when deposited. Any oxidation which took place occurred after deposition. Experimental and theoretical reducing studies on fresh wood, wood degraded by burial for 450 years, and lignite, indicate that such ores may have been deposited by reduction of oxidized vanadium solutions by woody material. A vanadium (III) mineral, V2O(OH)4, was prepared synthetically by reduction of a vanadium (V) solution with wood. This is the only reported synthesis of any reduced vanadium mineral by any method. It was shown that the origin of almost all vanadium deposits currently of commercial importance involves life processes and products.

  4. Interface states and internal photoemission in p-type GaAs metal-oxide-semiconductor surfaces

    NASA Technical Reports Server (NTRS)

    Kashkarov, P. K.; Kazior, T. E.; Lagowski, J.; Gatos, H. C.

    1983-01-01

    An interface photodischarge study of p-type GaAs metal-oxide-semiconductor (MOS) structures revealed the presence of deep interface states and shallow donors and acceptors which were previously observed in n-type GaAs MOS through sub-band-gap photoionization transitions. For higher photon energies, internal photoemission was observed, i.e., injection of electrons to the conduction band of the oxide from either the metal (Au) or from the GaAs valence band; the threshold energies were found to be 3.25 and 3.7 + or - 0.1 eV, respectively. The measured photoemission current exhibited a thermal activation energy of about 0.06 eV, which is consistent with a hopping mechanism of electron transport in the oxide.

  5. Understanding the Chemistry of Uncommon Americium Oxidation States for Application to Actinide/Lanthanide Separations

    SciTech Connect

    Leigh Martin; Bruce J. Mincher; Nicholas C. Schmitt

    2007-09-01

    A spectroscopic study of the stability of Am(V) and Am(VI) produced by oxidizing Am(III) with sodium bismuthate is presented, varying the initial americium concentration, temperature and length of the oxidation was seen to have profound effects on the resultant solutions.

  6. Ethylene oxide and breast cancer incidence in a cohort study of 7576 women (United States).

    PubMed

    Steenland, Kyle; Whelan, Elizabeth; Deddens, James; Stayner, Leslie; Ward, Elizabeth

    2003-08-01

    Ethylene oxide (ETO) is a sterilant gas considered to be a human carcinogen, due primarily to excess hematopoietic cancer in exposed cohorts. ETO causes mammary tumors in mice, and has been associated with breast cancer incidence in one small epidemiologic study. We have studied breast cancer incidence in a cohort of 7576 women employed for at least one year and exposed for an average 10.7 years while working in commercial sterilization facilities. Breast cancer incidence (n = 319) was ascertained via interview, death certificates, cancer registries, and medical records. Interviews were obtained for 68% of the cohort. The standardized incidence ratio (SIR) for incident breast cancer in the whole cohort using external referent rates (SEER) was 0.87 (0.77-0.97). The SIR for those in the top quintile of cumulative exposure, with a 15 year lag, was 1.27 (0.94-1.69), with a positive trend of increasing SIR with increasing exposure (p = 0.002). SIRs are underestimated because breast cancer incidence in the whole cohort was under-ascertained, due to incomplete response and lack of complete coverage by state cancer registries. In internal nested case-control analyses of those with interviews (complete cancer ascertainment), controlling for reproductive risk factors, a positive exposure-response was found with the log of cumulative exposure with a 15-year lag (p = 0.0005). The odds ratio by quintile of cumulative exposure were 1.00 (0 exposure due to 15 year lag), 1.06, 0.99, 1.24, 1.42, and 1.87. Our data suggest that ETO is associated with breast cancer, but a causal interpretation is weakened due to some inconsistencies in exposure-response trends and possible biases due to non-response and incomplete cancer ascertainment.

  7. DAYCENT national-scale simulations of nitrous oxide emissions from cropped soils in the United States.

    PubMed

    Del Grosso, S J; Parton, W J; Mosier, A R; Walsh, M K; Ojima, D S; Thornton, P E

    2006-01-01

    Until recently, Intergovernmental Panel on Climate Change (IPCC) emission factor methodology, based on simple empirical relationships, has been used to estimate carbon (C) and nitrogen (N) fluxes for regional and national inventories. However, the 2005 USEPA greenhouse gas inventory includes estimates of N2O emissions from cultivated soils derived from simulations using DAYCENT, a process-based biogeochemical model. DAYCENT simulated major U.S. crops at county-level resolution and IPCC emission factor methodology was used to estimate emissions for the approximately 14% of cropped land not simulated by DAYCENT. The methodology used to combine DAYCENT simulations and IPCC methodology to estimate direct and indirect N2O emissions is described in detail. Nitrous oxide emissions from simulations of presettlement native vegetation were subtracted from cropped soil N2O to isolate anthropogenic emissions. Meteorological data required to drive DAYCENT were acquired from DAYMET, an algorithm that uses weather station data and accounts for topography to predict daily temperature and precipitation at 1-km2 resolution. Soils data were acquired from the State Soil Geographic Database (STATSGO). Weather data and dominant soil texture class that lie closest to the geographical center of the largest cluster of cropped land in each county were used to drive DAYCENT. Land management information was implemented at the agricultural-economic region level, as defined by the Agricultural Sector Model. Maps of model-simulated county-level crop yields were compared with yields estimated by the USDA for quality control. Combining results from DAYCENT simulations of major crops and IPCC methodology for remaining cropland yielded estimates of approximately 109 and approximately 70 Tg CO2 equivalents for direct and indirect, respectively, mean annual anthropogenic N2O emissions for 1990-2003.

  8. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    PubMed Central

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-01-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1−xCaxAlO3−δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400–500 °C. The response current value at −300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles. PMID:27886278

  9. Global analysis of genetic variation in human arsenic (+ 3 oxidation state) methyltransferase (AS3MT)

    SciTech Connect

    Fujihara, Junko; Soejima, Mikiko; Yasuda, Toshihiro; Koda, Yoshiro; Agusa, Tetsuro; Kunito, Takashi; Tongu, Miki; Yamada, Takaya; Takeshita, Haruo

    2010-03-15

    Human arsenic (+ 3 oxidation state) methyltransferase (AS3MT) is known to catalyze the methylation of arsenite. The objective of this study was to investigate the diversity of the AS3MT gene at the global level. The distribution of 18 single nucleotide polymorphisms (SNPs) in AS3MT was performed in 827 individuals from 10 populations (Japanese, Korean, Chinese, Mongolian, Tibetans, Sri Lankan Tamils, Sri Lankan Sinhalese, Nepal Tamangs, Ovambo, and Ghanaian). In the African populations, the A allele in A6144T was not observed; the allele frequencies of C35587 were much lower than those in other populations; the allele frequencies of A37616 and C37950 were relatively higher than those in other populations. Among Asian populations, Mongolians showed a different genotype distribution pattern. A lower C3963 and T6144 frequencies were observed, and, in the C37616A and T37950C polymorphism, the Mongolian population showed higher A37616 and C37950 allele frequencies than other Asian populations, similarly to the African populations. A total of 66 haplotypes were observed in the Ovambo, 48, in the Ghanaian, 99, in the Japanese, 103, in the Korean, 103, in the South Chinese, 20, in the Sri Lankan Tamil, 12, in the Sri Lankan Sinhalese, 21, in the Nepal Tamang, 50, in the Tibetan, and 45, in the Mongolian populations. The D' values between the SNP pairs were extremely high in the Sri Lankan Sinhalese population. Relatively higher D' values were observed in Mongolian and Sri Lankan Tamil populations. Network analysis showed two clusters that may have different origins, African and Asians (Chinese and/or Japanese). The present study is the first to demonstrate the existence of genetic heterogeneity in a world wide distribution of 18 SNPs in AS3MT.

  10. Metabolomic profiles of arsenic (+3 oxidation state) methyltransferase knockout mice: effect of sex and arsenic exposure.

    PubMed

    Huang, Madelyn C; Douillet, Christelle; Su, Mingming; Zhou, Kejun; Wu, Tao; Chen, Wenlian; Galanko, Joseph A; Drobná, Zuzana; Saunders, R Jesse; Martin, Elizabeth; Fry, Rebecca C; Jia, Wei; Stýblo, Miroslav

    2017-01-01

    Arsenic (+3 oxidation state) methyltransferase (As3mt) is the key enzyme in the pathway for methylation of inorganic arsenic (iAs). Altered As3mt expression and AS3MT polymorphism have been linked to changes in iAs metabolism and in susceptibility to iAs toxicity in laboratory models and in humans. As3mt-knockout mice have been used to study the association between iAs metabolism and adverse effects of iAs exposure. However, little is known about systemic changes in metabolism of these mice and how these changes lead to their increased susceptibility to iAs toxicity. Here, we compared plasma and urinary metabolomes of male and female wild-type (WT) and As3mt-KO (KO) C57BL/6 mice and examined metabolomic shifts associated with iAs exposure in drinking water. Surprisingly, exposure to 1 ppm As elicited only small changes in the metabolite profiles of either WT or KO mice. In contrast, comparisons of KO mice with WT mice revealed significant differences in plasma and urinary metabolites associated with lipid (phosphatidylcholines, cytidine, acyl-carnitine), amino acid (hippuric acid, acetylglycine, urea), and carbohydrate (L-sorbose, galactonic acid, gluconic acid) metabolism. Notably, most of these differences were sex specific. Sex-specific differences were also found between WT and KO mice in plasma triglyceride and lipoprotein cholesterol levels. Some of the differentially changed metabolites (phosphatidylcholines, carnosine, and sarcosine) are substrates or products of reactions catalyzed by other methyltransferases. These results suggest that As3mt KO alters major metabolic pathways in a sex-specific manner, independent of iAs treatment, and that As3mt may be involved in other cellular processes beyond iAs methylation.

  11. Effects of pent-4-enoate on cellular redox state, glycolysis and fatty acid oxidation in isolated perfused rat heart

    PubMed Central

    Hiltunen, J. Kalervo; Jauhonen, V. Pekka; Savolainen, Markku J.; Hassinen, Ilmo E.

    1978-01-01

    The metabolic effects of pent-4-enoate were studied in beating and potassium-arrested perfused rat hearts. The addition of 0.8mm-pent-4-enoate to the fluid used to perfuse a potassium-arrested heart resulted in a 70% increase in the O2 consumption and a 66% decrease in the glycolytic flux as measured in terms of the de-tritiation of [3-3H]glucose, although the proportion of the O2 consumption attributable to glucose oxidation decreased from an initial 30% to 10%. The pent-4-enoate-induced increase in O2 consumption was only 15% in the beating heart. In the potassium-arrested heart, pent-4-enoate stimulated palmitate oxidation by more than 100% when measured in terms of the production of 14CO2 from [1-14C]palmitate, but in the beating heart palmitate oxidation was inhibited. Perfusion of the heart with pent-4-enoate had no effect on the proportion of pyruvate dehydrogenase found in the active form, in spite of large changes in the CoASH and acetyl-CoA concentrations and changes in their concentration ratios. The effects of pent-4-enoate on the cellular redox state were dependent on the ATP consumption of the heart. In the beating heart, pent-4-enoate caused a rapid mitochondrial NAD+ reduction that subsequently faded out, so that the final state was more oxidized than the initial state. The arrested heart, however, remained in a more reduced state than initially, even after the partial re-oxidation that followed the initial rapid NAD+ reduction. The ability of pent-4-enoate to increase or decrease fatty acid oxidation can be explained on the basis of the differential effects of pent-4-enoate on the concentration of citric acid-cycle intermediates under conditions of high or low ATP consumption of the myocardial cell. The proportion of the fatty acids in the fuel consumed by the heart is probably primarily determined by the regulatory mechanisms of glycolysis. When pent-4-enoate causes an increase in the citric acid-cycle intermediates, feedback inhibition of

  12. The synthesis, characterization and reactivity of high oxidation state nickel fluorides

    SciTech Connect

    Chacon, L.C. |

    1997-12-01

    The research described in this thesis has mainly addressed the challenge of the synthesis of thermodynamically unstable nickel fluorides, which cannot be made by traditional thermal methods. A low-temperature approach towards the synthesis of such transition metal fluorides exploits the greater thermodynamic stability of high oxidation states in anions and involves the use of anhydrous hydrogen fluoride (aHF) as a solvent. The general method consists of combining an aHF soluble starting material (e.g., K{sub 2}NiF{sub 6}) with a Lewis fluoroacid (e.g., BF{sub 3}), which precipitates a neutral polymeric solid state fluoride: 2 K{sup +} + NiF{sub 6}{sup 2{minus}} + BF{sub 3} {r_arrow} NiF{sub 4} + 2 BF{sub 4}{sup {minus}} + 2 K{sup +}. At room temperature, this reaction yields a different structural phase, with composition K{sub x}NiF{sub 3} (x {approx} 0.18). This material has a pseudo-hexagonal tungsten bronze structure (H{sub 0}-K{sub x}NiF{sub 3}), and is an ionic conductor, probably due to K{sup +} ions hosted in the lattice channels. R-NiF{sub 3} is capable of fluorinating a wide range of inorganic and organic substrates. These reactions have probably shed light on the mechanism of the Simons Electrochemical Fluorination (ECF) Process, an important industrial method of fluorinating organic compounds. It has long been speculated that NiF{sub 3} plays a role in the ECF process, which uses nickel electrodes in aHF solvent. K{sub 2}NiF{sub 6} also fluorinates organic compounds in aHF, but interestingly, yields different fluorinated products. The reduction of R-NiF{sub 3} and K{sub 2}NiF{sub 6} during fluorination reactions yields NiF{sub 2}. A method has been developed to regenerate NiF{sub 6}{sup 2{minus}} from NiF{sub 2}.

  13. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    NASA Astrophysics Data System (ADS)

    Yamaura, Kazunari

    2016-04-01

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO3, LiOsO3, and Na2OsO4, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal-insulator transition in NaOsO3, a ferroelectric-like transition in LiOsO3, and high-temperature ferrimagnetism driven by a local structural distortion in Ca2FeOsO6 may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices.

  14. 3,4,5,6-tetramethylphenanthrene 9,10-oxide: a step on the way to the transition state for nucleophilic ring opening of arene oxides

    SciTech Connect

    Darnow, J.N.; Armstrong, R.N.

    1987-05-01

    Force field calculations (MM2) and studies of the parent hydrocarbons suggest that 3,4,5,6-tetramethylphenanthrene 9,10-oxide (TMPO) should exist as two kinetically stable enantiomers. Stereoelectronic considerations indicate that the axial chirality of each enantiomer should direct nucleophilic attack to the diastereotopic oxirane carbon that most closely approaches the geometry of the transition state. The two enantiomers of TMPO can be synthesized from the chiral hydrocarbons by direct oxidation. The half-life for racemization of TMPO is 30 min at 25/sup 0/C. The two enantiomers are found to be substrates for glutathione (GSH) transferase and epoxide hydrolase. Isozyme 4-4 of GSH transferase which normally catalyzes addition of GSH to oxirane carbons of R absolute configuration, catalyzes addition to the oxirane carbon of S configuration in the M-isomer of TMPO and of R configuration in the P-isomer. Analogous results are obtained with the epoxide hydrolase catalyzed addition of water. The results suggest that TMPO should be an interesting stereochemical probe of both spontaneous and enzyme catalyzed ring opening reactions of arene oxides.

  15. Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?

    NASA Astrophysics Data System (ADS)

    Jagoutz, Oliver

    2014-05-01

    A fundamental shift in the nature of granitoids occurs at approximately the Archean-Proterozoic boundary. Archean crust is dominated Na-rich tonalite-trondhjemite-granodiorites (TTGs), whereas post-Archean granitoids are characterized by K-rich granodiorite-granite (GG). Due to the HREE depletion commonly found in TTGs indicating the presence of residual garnet, many researchers have proposed that the difference in Na/K is related to the deeper melting depth of the TTG parental liquids. Here I present a compilation of the relevant experimental data, documenting that no correlation exists between the Na/K of derivative felsic liquids and the pressure of partial melting/fractional crystallization. Instead, the Na/K ratio of the felsic liquid best correlates with the Na/K ratio of the source. This implies that in Archean time the source material of TTG rocks must have been Na/K enriched relative to the modern. Modern granitoids are dominantly formed in a supra subduction zone environment, where a feedback loop exists between subducted materials (oceanic crust and sediments) and arc magmatism. Sea-floor weathering and the Na/K of the altered oceanic crust strongly depends on f(O2) conditions during alteration, which likely changed with earth history. During alteration under oxidized condition K2O is fixated due to the formation of celadonite (K-Mica), wheres during anoxic condition saponite (Na-Smectite) is the stable alteration mineral. I propose that the rise of oxygen at 2600-2400 Ma triggered associated changes in f(O2) seafloor alteration conditions. The change in the dominant seafloor alteration mineral from reduced to oxidized causes a change in the nature of the arc magma source and provides a possible explanation for the observed transition from TTGrocks in the Archean to the GG-granitoids in post-Archean times.

  16. Charge Transport Properties of P3HT-PEO block copolymers that are Electrochemically Oxidized in the Solid-State

    NASA Astrophysics Data System (ADS)

    Patel, Shrayesh; Javier, Anna; Balsara, Nitash

    2013-03-01

    We report on the relationship between morphology and electronic/ionic charge transport of Poly(3-hexylthiophene)- b-Poly(ethylene oxide) (P3HT- b-PEO) and lithium bis-(trifluoromethanesulfonyl) imide (LiTFSI) mixtures. Using ac impedance spectroscopy, we show that P3HT- b-PEO/LiTFSI mixtures can conduct electronic and ionic charges simultaneously. The electronic resistance of P3HT- b-PEO can be controlled through the electrochemical oxidation of P3HT with LiTFSI. We designed an all solid-state electrochemical cell with three terminals to measure the electronic conductivity of P3HT- b-PEO under applied potentials. The addition of a third terminal within the P3HT- b-PEO layer allows for the in-situ measurement of the electronic conductivity as a function of the P3HT electrochemical oxidation level. Our experimental setup is unique in that electrochemical oxidation occurs in the presence of solid-polymer electrolyte. Previous studies on the electrochemical oxidation of polythiophenes have been done in the presence of a liquid electrolyte. The results of the in-situ electronic conductivity measurements as a function of electrochemical doping level and block copolymer composition will be presented.

  17. Energy shifts of Si oxidation states in the system of Si nanocrystals embedded in SiO2 matrix.

    PubMed

    Chen, T P; Liu, Y; Sun, C Q; Tseng, Ampere A; Fung, S

    2007-07-01

    Energy shifts in the Si 2p levels of the five Si oxidation states Sin+ (n = 0, 1, 2, 3, 4) in the system of Si nanocrystals embedded in SiO2 matrix have been determined. The thermal annealing effect on the energy shifts has been studied. The result suggests that the Si nanocrystals and the SiO2 are thermally stable but the annealing can cause some structural deformations such as changes in the bond lengths and bond angles for the suboxides Si2O and SiO. The energy shifts generally show a linear dependence on the oxidation state n, suggesting that the energy shifts could be mainly determined by the nearest-neighbor oxygen atoms. It is shown that the chemical structures of the system are similar to those of the conventional SiO2/Si system in terms of the energy shifts.

  18. Pathway for Mn-cluster oxidation by tyrosine-Z in the S2 state of photosystem II

    PubMed Central

    Narzi, Daniele; Bovi, Daniele; Guidoni, Leonardo

    2014-01-01

    Water oxidation in photosynthetic organisms occurs through the five intermediate steps S0–S4 of the Kok cycle in the oxygen evolving complex of photosystem II (PSII). Along the catalytic cycle, four electrons are subsequently removed from the Mn4CaO5 core by the nearby tyrosine Tyr-Z, which is in turn oxidized by the chlorophyll special pair P680, the photo-induced primary donor in PSII. Recently, two Mn4CaO5 conformations, consistent with the S2 state (namely, S2A and S2B models) were suggested to exist, perhaps playing a different role within the S2-to-S3 transition. Here we report multiscale ab initio density functional theory plus U simulations revealing that upon such oxidation the relative thermodynamic stability of the two previously proposed geometries is reversed, the S2B state becoming the leading conformation. In this latter state a proton coupled electron transfer is spontaneously observed at ∼100 fs at room temperature dynamics. Upon oxidation, the Mn cluster, which is tightly electronically coupled along dynamics to the Tyr-Z tyrosyl group, releases a proton from the nearby W1 water molecule to the close Asp-61 on the femtosecond timescale, thus undergoing a conformational transition increasing the available space for the subsequent coordination of an additional water molecule. The results can help to rationalize previous spectroscopic experiments and confirm, for the first time to our knowledge, that the water-splitting reaction has to proceed through the S2B conformation, providing the basis for a structural model of the S3 state. PMID:24889635

  19. On the assignment of nickel oxidation states of the Ox1,Ox2 forms of methyl-coenzyme M reductase

    SciTech Connect

    Telser, J.; Horng, Y.C.; Becker, D.F.; Hoffman, B.M.; Ragsdale, S.W.

    2000-01-12

    Methyl-coenzyme M reductase (MCR) catalyzes the chemical step of methane formation by methanogenic organisms. The reaction involves the two-electron reduction of CH{sub 3}S-CoM by N-7-mercaptoheptanoylthreoinine phosphate (CoB-SH). The authors have employed 35 GHz EPR and ENDOR spectroscopy to resolve the oxidation state of Ni in ox1, ox2 and red1 forms of MCR, isolated from methanobacterium thermoautotrophicum strain Marburg and prepared as described previously.

  20. CoOx thin film deposited by CVD as efficient water oxidation catalyst: change of oxidation state in XPS and its correlation to electrochemical activity.

    PubMed

    Weidler, Natascha; Paulus, Sarina; Schuch, Jona; Klett, Joachim; Hoch, Sascha; Stenner, Patrick; Maljusch, Artjom; Brötz, Joachim; Wittich, Carolin; Kaiser, Bernhard; Jaegermann, Wolfram

    2016-04-28

    To reduce energy losses in water electrolysers a fundamental understanding of the water oxidation reaction steps is necessary to design efficient oxygen evolution catalysts. Here we present CoOx/Ti electrocatalytic films deposited by thermal and plasma enhanced chemical vapor deposition (CVD) onto titanium substrates. We report electrochemical (EC), photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) measurements. The electrochemical behavior of the samples was correlated with the chemical and electronic structure by recording XPS spectra before and after each electrochemical treatment (conditioning and cyclovoltammetry). The results show that the electrochemical behavior of CoOx/Ti strongly depends on the resulting electronic structure and composition. The thermal deposition leads to the formation of a pure Co(II)Ox which transforms to a mixed Co(II)Co(III)Ox during the OER. This change in oxidation state is coupled with a decrease in overpotential from η = 0.57 V to η = 0.43 V at 5 mA cm(-2). Plasma deposition in oxygen leads to a Co(III)-dominated mixed CoOx, that has a lower onset potential as deposited due to a higher Co(III) content in the initial deposited material. After the OER XPS results of the CoOx/Ti indicate a partial formation of hydroxides and oxyhydroxides on the oxide surface. Finally the plasma deposition in air, results in a CoOxOH2 surface, that is able to completely oxidizes during OER to an oxyhydroxide Co(III)OOH. With the in situ formed CoOOH we present a highly active catalyst for the OER (η = 0.34 at 5 mA cm(-2); η = 0.37 V at 10 mA cm(-2)).