Science.gov

Sample records for accessible oxidation states

  1. Diiron Oxidation State Control of Substrate Access to the Active Site of Soluble Methane Monooxygenase Mediated by the Regulatory Component

    PubMed Central

    2015-01-01

    The regulatory component (MMOB) of soluble methane monooxygenase (sMMO) has a unique N-terminal tail not found in regulatory proteins of other bacterial multicomponent monooxygenases. This N-terminal tail is indispensable for proper function, yet its solution structure and role in catalysis remain elusive. Here, by using double electron–electron resonance (DEER) spectroscopy, we show that the oxidation state of the hydroxylase component, MMOH, modulates the conformation of the N-terminal tail in the MMOH–2MMOB complex, which in turn facilitates catalysis. The results reveal that the N-terminal tail switches from a relaxed, flexible conformational state to an ordered state upon MMOH reduction from the diiron(III) to the diiron(II) state. This observation suggests that some of the crystallographically observed allosteric effects that result in the connection of substrate ingress cavities in the MMOH–2MMOB complex may not occur in solution in the diiron(III) state. Thus, O2 may not have easy access to the active site until after reduction of the diiron center. The observed conformational change is also consistent with a higher binding affinity of MMOB to MMOH in the diiron(II) state, which may allow MMOB to displace more readily the reductase component (MMOR) from MMOH following reduction. PMID:24476336

  2. United States Access Board

    MedlinePlus

    ... Communications & IT Access to information and communication technology (ICT) is addressed by Board standards and guidelines issued ... Engineer (November 3) Access Board Approves Rules on ICT Refresh and Medical Diagnostic Equipment (September 14) Access ...

  3. Oxidation State 10 Exists.

    PubMed

    Yu, Haoyu S; Truhlar, Donald G

    2016-07-25

    In a recent paper, Wang et al. found an iridium-containing compound with a formal oxidation state of 9. This is the highest oxidation state ever found in a stable compound. To learn if this is the highest chemical oxidation state possible, Kohn-Sham density functional theory was used to study various compounds, including PdO4 (2+) , PtO4 (2+) , PtO3 F2 (2+) , PtO4 OH(+) , PtO5 , and PtO4 SH(+) , in which the metal has an oxidation state of 10. It was found that PtO4 (2+) has a metastable state that is kinetically stable with a barrier height for decomposition of 31 kcal mol(-1) and a calculated lifetime of 0.9 years. All other compounds studied would readily decompose to lower oxidation states.

  4. 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)

  5. 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

  6. Zinc in +III oxidation state

    NASA Astrophysics Data System (ADS)

    Samanta, Devleena; Jena, Puru

    2012-02-01

    The possibility of Group 12 elements, such as Zn, Cd, and Hg existing in an oxidation state of +III or higher has fascinated chemists for decades. Significant efforts have been made in the past to achieve higher oxidation states for the heavier congener mercury (since the 3^rd ionization potential of the elements decrease as we go down the periodic table). It took nearly 20 years before experiment could confirm the theoretical prediction that Hg indeed can exist in an oxidation state of +IV. While this unusual property of Hg is attributed to the relativistic effects, Zn being much lighter than Hg has not been expected to have an oxidation state higher than +II. Using density functional theory we show that an oxidation state of +III for Zn can be realized by choosing specific ligands with large electron affinities i.e. superhalogens. We demonstrate this by a systematic study of the interaction of Zn with F, BO2, and AuF6 ligands whose electron affinities are progressively higher, namely, 3.4 eV, 4.4 eV, and 8.4 eV, respectively. Discovery of higher oxidation states of elements can help in the formulation of new reactions and hence in the development of new chemistry.

  7. MOLECULAR ACCESSIBILITY IN OXIDIZED AND DRIED COALS

    SciTech Connect

    Lowell D. Kispert

    1999-07-01

    Changes in physical and chemical structure of the micropore system in eight solvent swelled Argonne Premium Coal Sample (APCS) coals upon weathering were studied using the EPR spin probe method. Spin probes, which are allowed to diffuse into the coal structure during swelling, are trapped when the swelling solvent is removed. Excess spin probes are removed from the coal surface and larger pores so that only the presence of spin probes trapped in pores which closely approximate the size of the spin probe are detected. Detailed explanations and illustrations of the experimental procedure used are given. Careful examination of the weathering process on coal as a function of rank was accomplished using the EPR spin probe method. The retention of spin probes in eight APCS coals provided valuable insight into both the loss of water and the oxidation which occur during the weathering process. The results could be explained in terms of the autoxidation process observed in other polymeric systems. It was shown that initial oxidation of coal can result in increased cross-linking in the coal structure. As the oxidation process continued, both the covalent and hydrogen bonded character of the coal were significantly altered. The retention character of some coals during oxidation was shown to change by as much as three orders of magnitude. Experiments were performed to study the effects of short term oxidation and dehydration on coal structure by exposing the coal samples to argon or oxygen for time periods up to five minutes. The results indicate that the structure of coal is extremely sensitive to environmental changes and exhibits significant changes in as little as 30 seconds. Exposure of Illinois No.6 coal to argon or oxygen for 30 seconds caused a decrease in the retention of polar spin probes by as much as an order of magnitude. The studies presented here suggest that the structure of coal is dynamic in nature, and has an intimate relationship with the nature of its

  8. Facile Access to Graphene Oxide from Ferro-Induced Oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Chao; Wang, Cai-Feng; Chen, Su

    2016-01-01

    Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers’ method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials.

  9. Molecular accessibility in oxidized and dried coals. Quarterly report

    SciTech Connect

    Kispert, L.D.

    1996-09-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using the EPR spin pore method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal as a function of sunlight for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distribution, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  10. Molecular accessibility in oxidized and dried coals. Quarterly report

    SciTech Connect

    Kispert, L.D.

    1995-06-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using the newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  11. Implementing the Equal Access Act and State Constitutional Provisions.

    ERIC Educational Resources Information Center

    Bjorklun, Eugene C.

    1992-01-01

    Examines the issue of whether implementation of the Equal Access Act would violate the constitutions of some states that require a stricter separation of church and state than the federal Constitution. (MLF)

  12. Broadband Access for Students at East Tennessee State University

    ERIC Educational Resources Information Center

    Sawyer, Thomas Scott

    2013-01-01

    The purpose of this study was to determine the availability of Internet access for students attending East Tennessee State University during the fall semester 2013. It has been unknown to what degree broadband access is available in the East Tennessee State University service area that includes counties in East Tennessee, Southwest Virginia, and…

  13. Residential Broadband Access for Students at Walters State Community College

    ERIC Educational Resources Information Center

    Hurst, Mark A.

    2010-01-01

    The purpose of this study was to determine the availability of internet access for students attending Walters State Community College during the spring semester 2010. In particular, it is unknown to what degree broadband internet access is available in the counties that Walters State considers the service area of the college. The research was…

  14. A Random Walk among Accessible States.

    ERIC Educational Resources Information Center

    Bauer, S. H.

    1986-01-01

    Proposes a model for kinetic processes said to be similar in computational effort and yielding similar results to conventional transition state theory (TST), while maintaining parsimony and credulity. Argues that partitioning of states into groups be limited to energy space in contrast to TST. (JM)

  15. Molecular accessibility in oxidized and dried coals. Quarterly report, 1996

    SciTech Connect

    Kispert, L.D.

    1996-06-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes. It appears that the observed binary swelling data for the APCS coals studied to date can be explained in terms of four different processes: one, disruption of weak hydrogen bonds which protect or isolate the interconnected micropore system; two, disruption of weak hydrogen bonds which protect individual micropores; three, the competition of pyridine for the active sites capable of establishing hydrogen bonds or the `poisoning` of active sites; four, disruption of stronger hydrogen bonds within the macromolecular structure which cause an opening of the structure. The contributions of each of these factors to the spin probe retention with increasing concentrations of pyridine vary up to 5% pyridine. At concentrations above 5% pyridine, the first factor becomes less significant, and variations in the others require greater changes in pyridine concentration.

  16. State Medicaid Coverage, ESRD Incidence, and Access to Care

    PubMed Central

    Goldstein, Benjamin A.; Hall, Yoshio N.; Mitani, Aya A.; Winkelmayer, Wolfgang C.

    2014-01-01

    The proportion of low-income nonelderly adults covered by Medicaid varies widely by state. We sought to determine whether broader state Medicaid coverage, defined as the proportion of each state’s low-income nonelderly adult population covered by Medicaid, associates with lower state-level incidence of ESRD and greater access to care. The main outcomes were incidence of ESRD and five indicators of access to care. We identified 408,535 adults aged 20–64 years, who developed ESRD between January 1, 2001, and December 31, 2008. Medicaid coverage among low-income nonelderly adults ranged from 12.2% to 66.0% (median 32.5%). For each additional 10% of the low-income nonelderly population covered by Medicaid, there was a 1.8% (95% confidence interval, 1.0% to 2.6%) decrease in ESRD incidence. Among nonelderly adults with ESRD, gaps in access to care between those with private insurance and those with Medicaid were narrower in states with broader coverage. For a 50-year-old white woman, the access gap to the kidney transplant waiting list between Medicaid and private insurance decreased by 7.7 percentage points in high (>45%) versus low (<25%) Medicaid coverage states. Similarly, the access gap to transplantation decreased by 4.0 percentage points and the access gap to peritoneal dialysis decreased by 3.8 percentage points in high Medicaid coverage states. In conclusion, states with broader Medicaid coverage had a lower incidence of ESRD and smaller insurance-related access gaps. PMID:24652791

  17. 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.

  18. State Lotteries: Their Effect on Equal Access to Higher Education

    ERIC Educational Resources Information Center

    Bowden, Randall G.; Elrod, Henry E.

    2004-01-01

    Many states (18 of 39) use revenue generated by lotteries to help fund higher education. The revenue is generated as a regressive tax disproportionately collected. As such, do state lotteries contribute toward facilitation of equal access to higher education for low-income and minority citizens? Given population trends, college enrollment, and…

  19. Materials selection for oxide-based resistive random access memories

    SciTech Connect

    Guo, Yuzheng; Robertson, John

    2014-12-01

    The energies of atomic processes in resistive random access memories (RRAMs) are calculated for four typical oxides, HfO{sub 2}, TiO{sub 2}, Ta{sub 2}O{sub 5}, and Al{sub 2}O{sub 3}, to define a materials selection process. O vacancies have the lowest defect formation energy in the O-poor limit and dominate the processes. A band diagram defines the operating Fermi energy and O chemical potential range. It is shown how the scavenger metal can be used to vary the O vacancy formation energy, via controlling the O chemical potential, and the mean Fermi energy. The high endurance of Ta{sub 2}O{sub 5} RRAM is related to its more stable amorphous phase and the adaptive lattice rearrangements of its O vacancy.

  20. Current state of web accessibility of Malaysian ministries websites

    NASA Astrophysics Data System (ADS)

    Ahmi, Aidi; Mohamad, Rosli

    2016-08-01

    Despite the fact that Malaysian public institutions have progressed considerably on website and portal usage, web accessibility has been reported as one of the issues deserves special attention. Consistent with the government moves to promote an effective use of web and portal, it is essential for the government institutions to ensure compliance with established standards and guidelines on web accessibility. This paper evaluates accessibility of 25 Malaysian ministries websites using automated tools i.e. WAVE and Achecker. Both tools are designed to objectively evaluate web accessibility in conformance with Web Content Accessibility Guidelines 2.0 (WCAG 2.0) and United States Rehabilitation Act 1973 (Section 508). The findings reported somewhat low compliance to web accessibility standard amongst the ministries. Further enhancement is needed in the aspect of input elements such as label and checkbox to be associated with text as well as image-related elements. This findings could be used as a mechanism for webmasters to locate and rectify errors pertaining to the web accessibility and to ensure equal access of the web information and services to all citizen.

  1. Molecular accessibility in oxidized and dried coals. Quarterly report

    SciTech Connect

    Kispert, L.D.

    1995-12-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture los both in the presence and absence of light using our newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution swelled, {ital oxidized} APCS coal for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering process. This quarter we have continued to examine the effect of exposure of light before alkylation versus after O-alkylation of the coal structure. The variation in uptake of spin probe VII (amine group) is depicted in figure 1 for Wyodak-Anderson. Before O-alkylation, a significant decrease occurred in the uptake of VII with increasing exposure to ambient light. This suggests that partial break-up of the hydrogen bond network occurs, making it possible to wash out more of the spin probes. This effect was eliminated if the coal was O-alkylated after exposure to sunlight (Figure 2). The removal of the source of hydrogen bonding is responsible for the lack of spin probe up-take variation with time of exposure to light. Further experiments have shown that the data in Figures 1 and 2 is reproducible with a deviation of less than {+-} 10%. It has also been observed that if Wyodak-Anderson coal is exposed to sunlight before swelling, the oscillatory up-take of spin probe VII as a function of percent pyridine is essentially removed.

  2. A molecular placeholder strategy to access a family of transition-metal-functionalized vanadium oxide clusters.

    PubMed

    Kastner, Katharina; Margraf, Johannes T; Clark, Timothy; Streb, Carsten

    2014-09-15

    Systematic access to metal-functionalized polyoxometalates has thus far been limited to lacunary tungsten oxide and molybdenum oxide clusters. The first controlled, stepwise bottom-up assembly route to metal-functionalized molecular vanadium oxides is now presented. A di-vacant vanadate cluster with two metal binding sites, (DMA)2[V12O32Cl](3-) (DMA = dimethylammonium) is formed spontaneously in solution and characterized by single-crystal X-ray diffraction, ESI mass spectrometry, (51)V NMR spectroscopy, and elemental analyses. In the cluster, the metal binding sites are selectively blocked by hydrogen-bonded DMA placeholder cations. Reaction of the cluster with transition metals TM (Fe(3+), Co(2+), Cu(2+), Zn(2+)) gives access to mono-functionalized vanadate clusters (DMA)[{TM(L)}V12O32Cl](n-) (L = ligand). Metal binding is accomplished by significant distortions of the vanadium oxide framework reminiscent of a pincer movement. Cluster stability under technologically relevant conditions in the solid-state and solution is demonstrated.

  3. Improving Immigrants' Access to Public Services in the United States: Language Access Policy and Policy Implementation

    ERIC Educational Resources Information Center

    Sperling, Jessica

    2009-01-01

    Language access mandates in the USA, which require that governmental services be provided in any needed language, have been largely ignored since their first enacting. However, the past decade has seen an increase in the number of national, state, and local efforts to accommodate limited English-proficient individuals. This article provides an…

  4. State Centralization and Equal Access to Educational Opportunity.

    ERIC Educational Resources Information Center

    Hendrix, Vernon L.; Sederberg, Charles H.

    This study's purpose was to explore the premise that increasing state support for elementary/secondary schools increases equal student access to educational opportunity. Following a brief overview of the background of the problem, including a description of the so-called "Minnesota Miracle" or Omnibus Tax Law of 1971 with its provisions for…

  5. Anomalous oxidation states in oxide multilayers for fuel cell applications

    SciTech Connect

    Perkins, James; Fearn, Sarah; Cook, S. N.; Srinivasan, R.; Rouleau, Christopher M; Christen, Hans M; West, G. D.; Morris, R. J. H.; Fraser, H. L.; Skinner, Stephen; Kilner, John; McComb, David

    2010-01-01

    Significant interest has been directed towards interface enhanced ionic conductivity. Advanced analytical techniques including electron microscopy (TEM/STEM), electron energy loss spectroscopy (EELS), and secondary ion mass spectrometry (SIMS) have been used to characterize CeO2/Ce0.85Sm0.15O2 multilayer thin films grown by pulsed laser deposition. High quality growth is observed, but ionic conductivity measured by impedance spectroscopy and 18O tracer experiments is consistent with bulk materials. EELS analysis reveals the unusual situation of layers containing only Ce(IV) adjacent to layers containing both Ce(III) and Ce(IV). Post oxygen annealing induced oxygen diffusion and mixed oxidation states in both layers, but only in the vicinity of low angle grain boundaries perpendicular to the layers. The implications of this remarkable metastability of Ce oxidation states on the design of novel electrolytes for solid oxide fuel cells is discussed.

  6. Iron oxidation state in hydrous rhyolites

    NASA Astrophysics Data System (ADS)

    Humphreys, M.; Brooker, R.; Fraser, D.; Smith, V. C.

    2012-12-01

    Recent studies have suggested that the Earth's mantle at subduction zones is oxidized relative to that at mid-ocean ridges. One possible origin of the oxidation is thought to be hydrous fluids, which are released into the mantle from the down-going slab during subduction. However, this is controversial; other studies have concluded that there is no intrinsic difference in oxidation state. One potential problem in determining primary oxidation states is that magmas produced by partial melting of the sub-arc mantle undergo significant degassing and crystallisation near the earth's surface, which may overprint the oxidation state of the primary melt. H2O contents of melt inclusions may be affected by partial re-equilibration. The effect of H2O on Fe oxidation state is unclear, although theoretical arguments typically predict increasing Fe3+/ΣFe during shallow degassing as a result of preferential diffusion of H2 out of the melt: FeO (m) + H2O (m) = Fe2O3 (m) + H2 (g) [1] We used XANES to measure Fe3+/Fe2+ in cylinders of rhyolitic obsidian that had been hydrated in gold capsules in cold-seal apparatus. Runs were performed at 850-900 °C under H2O-saturated conditions for short run times (20-80 minutes). Surprisingly, we find a positive correlation between Fe3+/ΣFe and H2O content of the glass. This is inconsistent with the effects of reaction [1], but can be explained by considering the acid-base properties of the hydrous melt. In particular, basic behaviour of FeO but amphoteric behaviour of Fe2O3, and changes in melt basicity relating to dissolution of H2O, can explain increasing Fe3+/Fe2+ with increasing H2O. We discuss the implications of these results for using melt compositions to infer the oxidation state of the earth's mantle.

  7. Physical and chemical mechanisms in oxide-based resistance random access memory.

    PubMed

    Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Zhang, Rui; Hung, Ya-Chi; Syu, Yong-En; Chang, Yao-Feng; Chen, Min-Chen; Chu, Tian-Jian; Chen, Hsin-Lu; Pan, Chih-Hung; Shih, Chih-Cheng; Zheng, Jin-Cheng; Sze, Simon M

    2015-01-01

    In this review, we provide an overview of our work in resistive switching mechanisms on oxide-based resistance random access memory (RRAM) devices. Based on the investigation of physical and chemical mechanisms, we focus on its materials, device structures, and treatment methods so as to provide an in-depth perspective of state-of-the-art oxide-based RRAM. The critical voltage and constant reaction energy properties were found, which can be used to prospectively modulate voltage and operation time to control RRAM device working performance and forecast material composition. The quantized switching phenomena in RRAM devices were demonstrated at ultra-cryogenic temperature (4K), which is attributed to the atomic-level reaction in metallic filament. In the aspect of chemical mechanisms, we use the Coulomb Faraday theorem to investigate the chemical reaction equations of RRAM for the first time. We can clearly observe that the first-order reaction series is the basis for chemical reaction during reset process in the study. Furthermore, the activation energy of chemical reactions can be extracted by changing temperature during the reset process, from which the oxygen ion reaction process can be found in the RRAM device. As for its materials, silicon oxide is compatible to semiconductor fabrication lines. It is especially promising for the silicon oxide-doped metal technology to be introduced into the industry. Based on that, double-ended graphene oxide-doped silicon oxide based via-structure RRAM with filament self-aligning formation, and self-current limiting operation ability is demonstrated. The outstanding device characteristics are attributed to the oxidation and reduction of graphene oxide flakes formed during the sputter process. Besides, we have also adopted a new concept of supercritical CO2 fluid treatment to efficiently reduce the operation current of RRAM devices for portable electronic applications.

  8. Characteristics and mechanism study of cerium oxide based random access memories

    SciTech Connect

    Hsieh, Cheng-Chih; Roy, Anupam; Rai, Amritesh; Chang, Yao-Feng; Banerjee, Sanjay K.

    2015-04-27

    In this work, low operating voltage and high resistance ratio of different resistance states of binary transition metal oxide based resistive random access memories (RRAMs) are demonstrated. Binary transition metal oxides with high dielectric constant have been explored for RRAM application for years. However, CeO{sub x} is considered as a relatively new material to other dielectrics. Since research on CeO{sub x} based RRAM is still at preliminary stage, fundamental characteristics of RRAM such as scalability and mechanism studies need to be done before moving further. Here, we show very high operation window and low switching voltage of CeO{sub x} RRAMs and also compare electrical performance of Al/CeO{sub x}/Au system between different thin film deposition methods and discuss characteristics and resistive switching mechanism.

  9. 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.

  10. Average oxidation state of carbon in proteins.

    PubMed

    Dick, Jeffrey M

    2014-11-01

    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.

  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. Influence of mixed thiolate/thioether versus dithiolate coordination on the accessibility of the uncommon +I and +III oxidation states for the nickel ion: an experimental and computational study.

    PubMed

    Gennari, Marcello; Orio, Maylis; Pécaut, Jacques; Bothe, Eberhard; Neese, Frank; Collomb, Marie-Noëlle; Duboc, Carole

    2011-04-18

    Sulfur-rich nickel metalloenzymes are capable of stabilizing Ni(I) and Ni(III) oxidation states in catalytically relevant species. In an effort to better understand the structural and electronic features that allow the stabilization of such species, we have investigated the electrochemical properties of two mononuclear N(2)S(2) Ni(II) complexes that differ in their sulfur environment. Complex 1 features aliphatic dithiolate coordination ([NiL], 1), and complex 2I is characterized by mixed thiolate/thioether coordination ([NiL(Me)]I, 2I). The latter results from the methylation of a single sulfur of 1. The X-ray structure of 2I reveals a distorted square planar geometry around the Ni(II) ion, similar to what was previously reported by us for 1. The electrochemical investigation of 1 and 2(+) shows that the addition of a methyl group shifts the potentials of both redox Ni(II)/Ni(I) and Ni(III)/Ni(II) redox couples by about 0.7 and 0.6 V to more positive values. Through bulk electrolyses, only the mononuclear dithiolate [Ni(I)L](-) (1(-)) and the mixed thiolate/thioether [Ni(III)L(Me)](2+) (2(2+)) complexes were generated, and their electronic properties were investigated by UV-vis and EPR spectroscopy. For 1(-) (Ni(I), d(9) configuration) the EPR data are consistent with a d(x(2))(-)(y(2)) based singly occupied molecular orbitals (SOMOs). However, DFT calculations suggest that there is also pronounced radical character. This is consistent with the small g-anisotropy observed in the EPR experiments. The spin population (Mulliken analysis) analysis of 1(-) reveals that the main contribution to the SOMO (64%) is due to the bipyridine unit. Time dependent density functional theory (TD-DFT) calculations attribute the most prominent features observed in the electronic absorption spectrum of 1(-) to metal to ligand charge transfer (MLCT) transitions. Concerning 2(2+), the EPR spectrum displays a rhombic signal with g(x) = 2.236, g(y) = 2.180, and g(z) = 2.039 in CH(3)CN

  13. 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

  14. 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

  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. High performance of graphene oxide-doped silicon oxide-based resistance random access memory

    PubMed Central

    2013-01-01

    In this letter, a double active layer (Zr:SiO x /C:SiO x ) resistive switching memory device with outstanding performance is presented. Through current fitting, hopping conduction mechanism is found in both high-resistance state (HRS) and low-resistance state (LRS) of double active layer RRAM devices. By analyzing Raman and FTIR spectra, we observed that graphene oxide exists in C:SiO x layer. Compared with single Zr:SiO x layer structure, Zr:SiO x /C:SiO x structure has superior performance, including low operating current, improved uniformity in both set and reset processes, and satisfactory endurance characteristics, all of which are attributed to the double-layer structure and the existence of graphene oxide flakes formed by the sputter process. PMID:24261454

  17. The effective oxidation state of a peatland

    NASA Astrophysics Data System (ADS)

    Worrall, Fred; Clay, Gareth D.; Moody, Catherine S.; Burt, Tim P.; Rose, Rob

    2016-01-01

    The oxidative ratio (OR) of the organic matter of the terrestrial biosphere is a key parameter in the understanding of the magnitude of the carbon sink represented both by the terrestrial biosphere and by the global oceans. However, no study has considered the oxidation state of all the organic pools and fluxes within one environment. In this study all organic matter pathways (dissolved organic matter, particulate organic matter, CO2, and CH4) were measured within an upland peat ecosystem in northern England. The study showed the following: (1) The peat soil of ecosystem was accumulating oxygen at a rate of between -16 and -73 t O km-2 yr-1; (2) Although there was no significant variation in oxidation state in the peat profile, there was a significant increase in degree of unsaturation with depth; (3) The dissolved organic matter leaving the ecosystem was significantly more oxidized than the other carbon pools analyzed while the particulate organic matter was not significantly different from the peat soil profile; and (4) Assuming that all carbon flux from the site was as CO2, the OR of the ecosystem was 1.07; when the nature and speciation of the release pathways were considered, the ecosystem OR was 1.04. At the global scale, correcting for the speciation of carbon fluxes means that the annual global fluxes of carbon to land = 1.49 ± 0.003 Gt C/yr and to the oceans = 2.01 ± 0.004 Gt C/yr.

  18. Oxidation state of Mn in the Mn oxide produced by Leptothrix discophora SS-1

    NASA Astrophysics Data System (ADS)

    Adams, Lee F.; Ghiorse, William C.

    1988-08-01

    Leptothrix discophora SS-1 excretes at least one Mn 2+-oxidizing protein that, in association with acidic exopolymers, catalyzes a rapid oxidation of Mn 2+. Iodometric titration of Mn oxide product showed that the oxidation state of Mn increased with age of the oxide from 3.32 in samples 11 hours old to 3.62 in samples formed over a period of 30 days. Electron diffraction of 90-day old samples showed evidence of poorly crystalline Mn(IV) oxides. Simultaneous measurement of oxygen consumption and Mn oxide formation during 15 min reaction periods indicated that the initial Mn product possessed an average oxidation state no greater than 3.6. Results suggest that the Mn 2+-oxidizing system of Leptothrix discophora SS-1 first generates Mn oxide with an average oxidation state close to Mn(III). Aging increases this oxidation state to give the mixed Mn(III, IV) oxide product observed in older samples.

  19. Fe Oxidation State in Microtektites from the Transantarctic Mountains

    NASA Astrophysics Data System (ADS)

    Giuli, G.; Cicconi, M. R.; Eeckhout, S. G.; Paris, E.; Pratesi, G.; Folco, L.

    2012-03-01

    Fe oxidation state of microtektites from the Transantarctic mountains is consistent with that of Australasian tektites and microtektites. Despite the long distance from the presumed impact site, the Fe oxidation state does not show appreciable variation.

  20. Refugee Resettlement Patterns and State-Level Health Care Insurance Access in the United States.

    PubMed

    Agrawal, Pooja; Venkatesh, Arjun Krishna

    2016-04-01

    We sought to evaluate the relationship between state-level implementation of the Patient Protection and Affordable Care Act (ACA) and resettlement patterns among refugees. We linked federal refugee resettlement data to ACA expansion data and found that refugee resettlement rates are not significantly different according to state-level insurance expansion or cost. Forty percent of refugees have resettled to states without Medicaid expansion. The wide state-level variability in implementation of the ACA should be considered by federal agencies seeking to optimize access to health insurance coverage among refugees who have resettled to the United States. PMID:26890186

  1. 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.

  2. 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. PMID:15093111

  3. 25 CFR 30.125 - What happens if a State refuses to allow a school access to the State assessment?

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... include direct communication with the Governor of the State. A Bureau-funded school may, if necessary, pay... 25 Indians 1 2011-04-01 2011-04-01 false What happens if a State refuses to allow a school access... if a State refuses to allow a school access to the State assessment? (a) The Department will...

  4. 25 CFR 30.125 - What happens if a State refuses to allow a school access to the State assessment?

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... include direct communication with the Governor of the State. A Bureau-funded school may, if necessary, pay... 25 Indians 1 2010-04-01 2010-04-01 false What happens if a State refuses to allow a school access... if a State refuses to allow a school access to the State assessment? (a) The Department will...

  5. 25 CFR 30.125 - What happens if a State refuses to allow a school access to the State assessment?

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... include direct communication with the Governor of the State. A Bureau-funded school may, if necessary, pay... 25 Indians 1 2013-04-01 2013-04-01 false What happens if a State refuses to allow a school access... if a State refuses to allow a school access to the State assessment? (a) The Department will...

  6. 25 CFR 30.125 - What happens if a State refuses to allow a school access to the State assessment?

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... include direct communication with the Governor of the State. A Bureau-funded school may, if necessary, pay... 25 Indians 1 2014-04-01 2014-04-01 false What happens if a State refuses to allow a school access... if a State refuses to allow a school access to the State assessment? (a) The Department will...

  7. 25 CFR 30.125 - What happens if a State refuses to allow a school access to the State assessment?

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... include direct communication with the Governor of the State. A Bureau-funded school may, if necessary, pay... 25 Indians 1 2012-04-01 2011-04-01 true What happens if a State refuses to allow a school access... if a State refuses to allow a school access to the State assessment? (a) The Department will...

  8. Accessing 4f-states in single-molecule spintronics.

    PubMed

    Fahrendorf, Sarah; Atodiresei, Nicolae; Besson, Claire; Caciuc, Vasile; Matthes, Frank; Blügel, Stefan; Kögerler, Paul; Bürgler, Daniel E; Schneider, Claus M

    2013-01-01

    Magnetic molecules are potential functional units for molecular and supramolecular spintronic devices. However, their magnetic and electronic properties depend critically on their interaction with metallic electrodes. Charge transfer and hybridization modify the electronic structure and thereby influence or even quench the molecular magnetic moment. Yet, detection and manipulation of the molecular spin state by means of charge transport, that is, spintronic functionality, mandates a certain level of hybridization of the magnetic orbitals with electrode states. Here we show how a judicious choice of the molecular spin centres determines these critical molecule-electrode contact characteristics. In contrast to late lanthanide analogues, the 4f-orbitals of single bis(phthalocyaninato)-neodymium(III) molecules adsorbed on Cu(100) can be directly accessed by scanning tunnelling microscopy. Hence, they contribute to charge transport, whereas their magnetic moment is sustained as evident from comparing spectroscopic data with ab initio calculations. Our results showcase how tailoring molecular orbitals can yield all-electrically controlled spintronic device concepts.

  9. Analysis of protein solvent accessible surfaces by photochemical oxidation and mass spectrometry.

    PubMed

    Sharp, Joshua S; Becker, Jeffrey M; Hettich, Robert L

    2004-02-01

    Protein surfaces are important in most biological processes, including protein-protein interactions, enzymatic catalysis, and protein-ligand binding. We report a method in which hydroxyl radicals generated by a rapid-UV irradiation of a 15% hydrogen peroxide solution were utilized to oxidize specific amino acid side chains of two model proteins (lysozyme, beta-lactoglobulin A), according to the residues' chemical reactivities and the solvent accessibility of the reactive carbons and sulfurs in the residue. Oxidized peptides generated by tryptic digestion were identified by electrospray-Fourier transform mass spectrometry. The specific sites of the stable modification were then identified by reverse-phase liquid chromatography coupled to quadropole ion trap tandem mass spectrometry. The solvent accessibility of the residue was shown to directly affect the rate of oxidation by this method (with the exception of methionine), supporting its use as a rapid measure of the solvent accessibility of specific residues, and in some cases, individual atoms. PMID:14750862

  10. Molecular accessibility in oxidized and dried coals. Quarterly report, [January 1, 1996--March 31, 1996

    SciTech Connect

    Kispert, L.D.

    1996-03-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized Argonne Premium Coal Samples (APCS) for each rank as a function of (1) size (up to 6nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes. Results of current study on changes in molecular accessibility in APCS coal oxidized in presence of sunlight show that accessibility to spin probes upon O-alkylation of the oxidized coal depends on the percent oxygen present before alkylation. An increase in microporosity occurs upon alkylation and this increase is more pronounced in higher rank than lower ranked coals. It was also observed that the increase in microporosity depends on the structure of each coal.

  11. Oxide Defect Engineering Methods for Valence Change (VCM) Resistive Random Access Memories

    NASA Astrophysics Data System (ADS)

    Capulong, Jihan O.

    Electrical switching requirements for resistive random access memory (ReRAM) devices are multifaceted, based on device application. Thus, it is important to obtain an understanding of these switching properties and how they relate to the oxygen vacancy concentration and oxygen vacancy defects. Oxygen vacancy defects in the switching oxide of valence-change-based ReRAM (VCM ReRAM) play a significant role in device switching properties. Oxygen vacancies facilitate resistive switching as they form the conductive filament that changes the resistance state of the device. This dissertation will present two methods of modulating the defect concentration in VCM ReRAM composed of Pt/HfOx/Ti stack: 1) rapid thermal annealing (RTA) in Ar using different temperatures, and 2) doping using ion implantation under different dose levels. Metrology techniques such as x-ray diffractometry (XRD), x-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy were utilized to characterize the HfOx switching oxide, which provided insight on the material properties and oxygen vacancy concentration in the oxide that was used to explain the changes in the electrical properties of the ReRAM devices. The resulting impact on the resistive switching characteristics of the devices, such as the forming voltage, set and reset threshold voltages, ON and OFF resistances, resistance ratio, and switching dispersion or uniformity were explored and summarized. Annealing in Ar showed significant impact on the forming voltage, with as much as 45% (from 22V to 12 V) of improvement, as the annealing temperature was increased. However, drawbacks of a higher oxide leakage and worse switching uniformity were seen with increasing annealing temperature. Meanwhile, doping the oxide by ion implantation showed significant effects on the resistive switching characteristics. Ta doping modulated the following switching properties with increasing dose: a) the reduction of the forming voltage, and Vset

  12. Program Retrieval/Dissemination: A Solid State Random Access System.

    ERIC Educational Resources Information Center

    Weeks, Walter O., Jr.

    The trend toward greater flexibility in educational methods has led to a need for better and more rapid access to a variety of aural and audiovisual resource materials. This in turn has demanded the development of a flexible, reliable system of hardware designed to aid existing distribution methods in providing such access. The system must be…

  13. Accessing Ultrahigh-Pressure, Quasi-Isentropic States of Matter

    NASA Astrophysics Data System (ADS)

    Lorenz, Thomas

    2004-11-01

    A new approach to materials science at extreme pressures has been developed on the OMEGA laser, using a ramped plasma piston drive. The laser drives a shock through a solid plastic reservoir that unloads at the rear free surface, expands across a vacuum gap, and stagnates on the metal sample under study. This produces a gently increasing ram pressure, compressing the sample nearly isentropically. The peak pressure on the sample, diagnosed with VISAR measurements, can be varied by adjusting the laser energy and pulse length, gap size, and reservoir density, and obeys a simple scaling relation. [1] This has been demonstrated at OMEGA at pressures of P = 0.1-2.0 Mbar in Al foils. [2] In an important application, using in-flight x-ray radiography, the material strength of solid-state samples at high pressure can be inferred by measuring the reductions in the growth rates (stabilization) of Rayleigh-Taylor (RT) unstable interfaces. The material strength is predicted to be as much as an order of magnitude higher at P ˜ 1 Mbar than at ambient pressures. Initial RT measurements testing this prediction in foils of Al and V will be shown. We also use TEM microscopy of recovered targets to show that the samples never melted, and the presence of pressure-induced structural defects. [3,4] Experimental designs based on this drive have been developed for the NIF laser, predicting that solid-state samples can be quasi-isentropically driven to pressures an order of magnitude higher than on Omega - accessing new regimes of dense, high-pressure matter. [5] [1] J. Edwards et al., Phys. Rev. Lett., 92, 075002 (2004). [2] K.T. Lorenz et al., submitted, J. Appl. Phys. (2004). [3] J. McNaney et al., in press, Met. Mat. Trans. 35A (2004). [4] E.M. Bringa et al., to be submitted, Nature (2004). [5] B.A. Remington et al., in press, Met. Mat. Trans. 35A (2004). This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore

  14. Equalizing Access to Electronic Networked Resources: A Model for Rural Libraries in the United States.

    ERIC Educational Resources Information Center

    Senkevitch, Judith J.; Wolfram, Dietmar

    1994-01-01

    Provides an overview of the current state of networking technology in rural libraries and describes a model for educating rural librarians in accessing electronic networks. Topics discussed include information needs in rural libraries; telecommunications technology access in rural areas; and examples of services to enhance information access.…

  15. Unified Information Access for the 21st Century: A Project of The California State University.

    ERIC Educational Resources Information Center

    Davis, Doug; Pollard, Marvin; Smith, Gordon

    This paper presents the results of a three-year project of the 22 libraries of the California State University (CSU) system to create an entirely new approach to information access. The Unified Information Access System (UIAS) is designed to provide integrated, single-search access to the full range of library information resources. In addition to…

  16. Understanding Electrical Conduction States in WO3 Thin Films Applied for Resistive Random-Access Memory

    NASA Astrophysics Data System (ADS)

    Ta, Thi Kieu Hanh; Pham, Kim Ngoc; Dao, Thi Bang Tam; Tran, Dai Lam; Phan, Bach Thang

    2016-05-01

    The electrical conduction and associated resistance switching mechanism of top electrode/WO3/bottom electrode devices [top electrode (TE): Ag, Ti; bottom electrode (BE): Pt, fluorine-doped tin oxide] have been investigated. The direction of switching and switching ability depended on both the top and bottom electrode material. Multiple electrical conduction mechanisms control the leakage current of such switching devices, including trap-controlled space-charge, ballistic, Ohmic, and Fowler-Nordheim tunneling effects. The transition between electrical conduction states is also linked to the switching (SET-RESET) process. This is the first report of ballistic conduction in research into resistive random-access memory. The associated resistive switching mechanisms are also discussed.

  17. Molecular accessibility in oxidized and dried coals: Quarterly report, October 1996--December 1996

    SciTech Connect

    Kispert, L.D.

    1996-12-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal as a function of sunlight for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  18. Molecular accessibility in oxidized and dried coals. Quarterly report, July 1995--September 1995

    SciTech Connect

    Kispert, L.D.

    1996-02-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  19. Molecular accessibility in oxidized and dried coals. Quarterly report, January 1995--March 1995

    SciTech Connect

    Kispert, L.D.

    1995-03-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  20. Molecular accessibility in oxidized and dried coals. Quarterly report, October--November 1994

    SciTech Connect

    Kispert, L.D.

    1994-12-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using a newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal for each rank as a function of (1) size (up to 6 nm) and shape, (2) the relative acidic/basic reactive site distributions, and (3) the role of hydrogen bonding as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecular accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  1. 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.

  2. Performance improvement of gadolinium oxide resistive random access memory treated by hydrogen plasma immersion ion implantation

    SciTech Connect

    Wang, Jer-Chyi Hsu, Chih-Hsien; Ye, Yu-Ren; Ai, Chi-Fong; Tsai, Wen-Fa

    2014-03-15

    Characteristics improvement of gadolinium oxide (Gd{sub x}O{sub y}) resistive random access memories (RRAMs) treated by hydrogen plasma immersion ion implantation (PIII) was investigated. With the hydrogen PIII treatment, the Gd{sub x}O{sub y} RRAMs exhibited low set/reset voltages and a high resistance ratio, which were attributed to the enhanced movement of oxygen ions within the Gd{sub x}O{sub y} films and the increased Schottky barrier height at Pt/Gd{sub x}O{sub y} interface, respectively. The resistive switching mechanism of Gd{sub x}O{sub y} RRAMs was dominated by Schottky emission, as proved by the area dependence of the resistance in the low resistance state. After the hydrogen PIII treatment, a retention time of more than 10{sup 4} s was achieved at an elevated measurement temperature. In addition, a stable cycling endurance with the resistance ratio of more than three orders of magnitude of the Gd{sub x}O{sub y} RRAMs can be obtained.

  3. Oxidation state of Mn in the Mn oxide produced by Leptothrix discophora SS-1

    SciTech Connect

    Adams, L.F.; Ghiorse, W.C. )

    1988-08-01

    Leptothrix discophora SS-1 excretes at least one Mn{sup 2+}-oxidizing protein that, in association with acidic exopolymers, catalyzes a rapid oxidation of Mn{sup 2+}. Iodometric titration of Mn oxide product showed that the oxidation state of Mn increased with age of the oxide from 3.32 in samples 11 hours old to 3.62 in samples formed over a period of 30 days. Electron diffraction of 90-day old samples showed evidence of poorly crystalline Mn(IV) oxides. Simultaneous measurement of oxygen consumption and Mn oxide formation during 15 min reaction periods indicated that the initial Mn product possessed an average oxidation state no greater than 3.6. Results suggest that the Mn{sup 2+}-oxidizing system of Leptothrix discophora SS-1 first generates Mn oxide with an average oxidation state close to Mn(III). Aging increases this oxidation state to give the mixed Mn(III, IV) oxide product observed in older samples.

  4. Characterization of a transient +2 sulfur oxidation state intermediate from the oxidation of aqueous sulfide

    SciTech Connect

    Vairavmurthy, M.A.; Zhou, Weiqing

    1995-04-01

    The oxidation H{sub 2}S to sulfate involves a net transfer of eight electrons and occurs through the formation of several partially oxidized intermediates with oxidation states ranging from {minus}1 to +5. Known intermediates include elemental sulfur (oxidation state 0), polysulfides (outer sulfur: {minus}1, inner sulfur: 0), sulfite (+4) and thiosulfate (outer sulfur: {minus}1, inner sulfur: +5). A noticeable gap in this series of intermediates is that of a +2 sulfur oxidation state oxoacid/oxoanion species, which was never detected experimentally. Here, we present evidence of the transient existence of +2 oxidation state intermediate in the Ni(II)-catalyzed oxidation of aqueous sulfide. X-ray absorption near-edge structure (XANES) spectroscopy and Fourier-transform-infrared (FT-IR) spectroscopy were used to characterize this species; they suggest that it has a sulfoxylate ion (SO{sub 2}{sup 2{minus}}) structure.

  5. Geographic Access to High Capability Severe Acute Respiratory Failure Centers in the United States

    PubMed Central

    Wallace, David J.; Angus, Derek C.; Seymour, Christopher W.; Yealy, Donald M.; Carr, Brendan G.; Kurland, Kristen; Boujoukos, Arthur; Kahn, Jeremy M.

    2014-01-01

    Objective Optimal care of adults with severe acute respiratory failure requires specific resources and expertise. We sought to measure geographic access to these centers in the United States. Design Cross-sectional analysis of geographic access to high capability severe acute respiratory failure centers in the United States. We defined high capability centers using two criteria: (1) provision of adult extracorporeal membrane oxygenation (ECMO), based on either 2008–2013 Extracorporeal Life Support Organization reporting or provision of ECMO to 2010 Medicare beneficiaries; or (2) high annual hospital mechanical ventilation volume, based 2010 Medicare claims. Setting Nonfederal acute care hospitals in the United States. Measurements and Main Results We defined geographic access as the percentage of the state, region and national population with either direct or hospital-transferred access within one or two hours by air or ground transport. Of 4,822 acute care hospitals, 148 hospitals met our ECMO criteria and 447 hospitals met our mechanical ventilation criteria. Geographic access varied substantially across states and regions in the United States, depending on center criteria. Without interhospital transfer, an estimated 58.5% of the national adult population had geographic access to hospitals performing ECMO and 79.0% had geographic access to hospitals performing a high annual volume of mechanical ventilation. With interhospital transfer and under ideal circumstances, an estimated 96.4% of the national adult population had geographic access to hospitals performing ECMO and 98.6% had geographic access to hospitals performing a high annual volume of mechanical ventilation. However, this degree of geographic access required substantial interhospital transfer of patients, including up to two hours by air. Conclusions Geographic access to high capability severe acute respiratory failure centers varies widely across states and regions in the United States. Adequate

  6. Molecular accessibility in oxidized and dried coals. Quarterly report, October--December 1993

    SciTech Connect

    Kispert, L.D.

    1993-12-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our newly developed EPR spin probe method. The proposed study will make it possible to deduce the molecular accessibility distribution in swelled, oxidized APCS coal for each rank as a function of (1) size (up to 6nm) and shape, (2) the relative acidic/basic reactive site distributions, (3) the role of hydrogen bonding and (4) the changes in the size and shape distribution of the accessible regions of the oxidized coal as a function of swelling solvents. The advantage of the EPR method is that it permits molecules of selected shape, size and chemical reactivity to be used as probes of molecularly accessible regions of swelled coal. From such data an optimum catalyst can be designed to convert oxidized coal into a more convenient form and methods can be devised to lessen the detrimental weathering processes.

  7. Access Guide to South Carolina State Parks for People with Special Needs.

    ERIC Educational Resources Information Center

    South Carolina State Dept. of Parks, Recreation, and Tourism, Columbia. Div. of Engineering and Planning.

    The guide was developed to assist physically handicapped persons in using South Carolina State Parks. It describes some of the accessibility problems identified in a 1986 Inventory of Handicapped Accessibility in South Carolina State Parks and Welcome Centers. It is noted that building construction since 1967 has met handicapped design criteria…

  8. Golf in the United States: an evolution of accessibility.

    PubMed

    Parziale, John R

    2014-09-01

    Golf affords physical and psychological benefits to persons who are physically challenged. Advances in adaptive technology, changes in golf course design, and rules modifications have enabled persons with neurological, musculoskeletal, and other impairments to play golf at a recreational, elite amateur, or professional level. The Americans with Disabilities Act has been cited in both federal and US Supreme Court rulings that have improved access for physically challenged golfers. Medical specialties, including physiatry, have played an important role in this process. This article reviews the history of golf's improvements in accessibility, and provides clinicians and physically challenged golfers with information that will facilitate participation in the sport.

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

    SciTech Connect

    Jernigan, G G

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu{sub 2}O), 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 > Cu{sub 2}O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu{sub 2}O, 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 N{sub 2} and CO{sub 2}. At the end of each reaction, the catalyst was found to be Cu{sub 2}O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  10. Direct Access to β-Fluorinated Aldehydes by Nitrite-Modified Wacker Oxidation.

    PubMed

    Chu, Crystal K; Ziegler, Daniel T; Carr, Brian; Wickens, Zachary K; Grubbs, Robert H

    2016-07-11

    An aldehyde-selective Wacker-type oxidation of allylic fluorides proceeds with a nitrite catalyst. The method represents a direct route to prepare β-fluorinated aldehydes. Allylic fluorides bearing a variety of functional groups are transformed in high yield and very high regioselectivity. Additionally, the unpurified aldehyde products serve as versatile intermediates, thus enabling access to a diverse array of fluorinated building blocks. Preliminary mechanistic investigations suggest that inductive effects have a strong influence on the rate and regioselectivity of the oxidation. PMID:27225538

  11. Direct Access to β-Fluorinated Aldehydes by Nitrite-Modified Wacker Oxidation.

    PubMed

    Chu, Crystal K; Ziegler, Daniel T; Carr, Brian; Wickens, Zachary K; Grubbs, Robert H

    2016-07-11

    An aldehyde-selective Wacker-type oxidation of allylic fluorides proceeds with a nitrite catalyst. The method represents a direct route to prepare β-fluorinated aldehydes. Allylic fluorides bearing a variety of functional groups are transformed in high yield and very high regioselectivity. Additionally, the unpurified aldehyde products serve as versatile intermediates, thus enabling access to a diverse array of fluorinated building blocks. Preliminary mechanistic investigations suggest that inductive effects have a strong influence on the rate and regioselectivity of the oxidation.

  12. Silicon radiation detectors with oxide charge state compensation

    SciTech Connect

    Walton, J.T.; Goulding, F.S.

    1986-10-01

    This paper discusses the use of boron implantation on high resistivity P-type silicon before oxide growth to compensate for the presence of charge states in the oxide and oxide/silicon interface. The presence of these charge states on high resistivity P-type silicon produces an inversion layer which causes high leakage currents on N/sup +/P junctions and high surface conductance. Compensating the surface region by boron implantation is shown to result in oxide passivated N/sup +/P junctions with very low leakage currents and with low surface conductance.

  13. Expanding Access and Opportunity: The Washington State Achievers Program

    ERIC Educational Resources Information Center

    Ramsey, Jennifer; Gorgol, Laura

    2010-01-01

    In 2001, the Bill & Melinda Gates Foundation launched a 10-year, multi-million dollar initiative, the Washington State Achievers Program (WSA), to increase opportunities for low-income students to attend postsecondary institutions in Washington State. The Bill & Melinda Gates Foundation granted funds to the College Success Foundation (CSF),…

  14. Expanding Access and Opportunity: The Washington State Achievers Scholarship

    ERIC Educational Resources Information Center

    O'Brien, Colleen

    2011-01-01

    In 2001, the Bill & Melinda Gates Foundation launched the multi-year, multi-million dollar Washington State Achievers Scholarship program. Concerned about disparities in college participation for low-income students in the state of Washington versus their wealthier peers, the Gates Foundation partnered with the College Success Foundation (CSF),…

  15. The Common Core State Standards: Comparisons of Access and Quality

    ERIC Educational Resources Information Center

    Wasserman, Nicholas H.

    2011-01-01

    Last year the United States unveiled the Common Core State Standards (CCSS) in English and Mathematics for grades K-12. In particular, the authors included two possible sequences of 8-12 mathematics courses that would fulfill the standards. Most notably, the courses titled "3a" and "3b" in these two sequences have become…

  16. 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)

  17. 36 CFR 212.7 - Access procurement by the United States.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 36 Parks, Forests, and Public Property 2 2012-07-01 2012-07-01 false Access procurement by the United States. 212.7 Section 212.7 Parks, Forests, and Public Property FOREST SERVICE, DEPARTMENT OF..., reconstruction, improvement, or maintenance is essential to provide safe and economical access to National...

  18. A Fiscal Analysis of Proposed Education Access Grants in Minneapolis. School Choice Issues in the State

    ERIC Educational Resources Information Center

    Maas, Ericca

    2005-01-01

    This study examines the fiscal impact of model legislation that would create Education Access Grants in Minnesota. The legislation would provide grants for low-income students to attend private schools. Specifically, this study examines the effect of implementing Education Access Grants in Minneapolis, the state's largest metropolitan area. It…

  19. Internet Access in the European Union and in the United States.

    ERIC Educational Resources Information Center

    Bauer, Johannes M.; Berne, Michel; Maitland, Carleen F.

    2002-01-01

    Examines the effects of public policies towards traditional communications infrastructures on Internet access in Europe and the United States. Discusses competitive strategies and describes the influence of regulatory policies affecting market entry and the pricing of services on Internet access, based on empirical findings. (Author/LRW)

  20. 36 CFR 212.7 - Access procurement by the United States.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... AGRICULTURE TRAVEL MANAGEMENT Administration of the Forest Transportation System § 212.7 Access procurement by... 36 Parks, Forests, and Public Property 2 2010-07-01 2010-07-01 false Access procurement by the... system of a State, county, or other local public road authority. Forest roads that are or will be part...

  1. Access to care for Chagas disease in the United States: a health systems analysis.

    PubMed

    Manne-Goehler, Jennifer; Reich, Michael R; Wirtz, Veronika J

    2015-07-01

    There are 300,000 estimated cases of Chagas disease in the United States but limited data on access to care. This study analyzed trends in access to care for Chagas disease in the United States and assessed the national and state barriers to access. Data on cases in blood donors and drug releases were obtained from the AABB (formerly American Association of Blood Banks) and U.S. Centers for Disease Control and Prevention (CDC), respectively. Semi-structured in-depth interviews were conducted with 30 key informants at the national level and in five states where treatment had been released. Interview responses were analyzed according to the health systems dimensions of regulation, financing, payment, organization, and persuasion. Data indicate that 1,908 cases were identified in the blood donation system from 2007 to 2013 and that CDC released 422 courses of benznidazole or nifurtimox during this period. The barriers to access at the national level include limited diagnostic and institutionalized referral and care processes, lack of financing for patient-care activities, and limited awareness and training among providers. This study demonstrates that access to treatment of Chagas disease in the United States is limited. The lack of licensing is only one of several barriers to access, highlighting the need for a health systems perspective when scaling up access to these essential medicines.

  2. 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.

  3. 22 CFR 9b.1 - Press access to the Department of State.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... BUILDING PASSES § 9b.1 Press access to the Department of State. (a) Media correspondents without valid... enjoyed by members of the public. (b) Media correspondents holding valid Department of State press... the Department of State building. (c) Media correspondents, with or without a Department of...

  4. 22 CFR 9b.1 - Press access to the Department of State.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... BUILDING PASSES § 9b.1 Press access to the Department of State. (a) Media correspondents without valid... enjoyed by members of the public. (b) Media correspondents holding valid Department of State press... the Department of State building. (c) Media correspondents, with or without a Department of...

  5. 22 CFR 9b.1 - Press access to the Department of State.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... BUILDING PASSES § 9b.1 Press access to the Department of State. (a) Media correspondents without valid... enjoyed by members of the public. (b) Media correspondents holding valid Department of State press... the Department of State building. (c) Media correspondents, with or without a Department of...

  6. How to Develop State Guidelines for Access Assistants: Scribes, Readers, and Sign Language Interpreters

    ERIC Educational Resources Information Center

    Clapper, Ann T.; Morse, Amanda B.; Thurlow, Martha L.; Thompson, Sandra J.

    2006-01-01

    This manual offers states a tool to assist in the development or enhancement of guidelines for access assistants. Whether a state already has guidelines or is just in the process of establishing them, this manual will provide structure to the process and many examples of criteria already included by states. This manual was developed to accompany…

  7. Disparities in access to effective treatment for infertility in the United States: an Ethics Committee opinion.

    PubMed

    2015-11-01

    In the United States, economic, racial, ethnic, geographic, and other disparities exist in access to fertility treatment and in treatment outcomes. This opinion examines the factors that contribute to these disparities and proposes actions to address them.

  8. 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.

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

    DOE PAGES

    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 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

  10. 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.

  11. Effects of erbium doping of indium tin oxide electrode in resistive random access memory

    NASA Astrophysics Data System (ADS)

    Chen, Po-Hsun; Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Pan, Chih-Hung; Lin, Chih-Yang; Jin, Fu-Yuan; Chen, Min-Chen; Huang, Hui-Chun; Lo, Ikai; Zheng, Jin-Cheng; Sze, Simon M.

    2016-03-01

    Identical insulators and bottom electrodes were fabricated and capped by an indium tin oxide (ITO) film, either undoped or doped with erbium (Er), as a top electrode. This distinctive top electrode dramatically altered the resistive random access memory (RRAM) characteristics, for example, lowering the operation current and enlarging the memory window. In addition, the RESET voltage increased, whereas the SET voltage remained almost the same. A conduction model of Er-doped ITO is proposed through current-voltage (I-V) measurement and current fitting to explain the resistance switching mechanism of Er-doped ITO RRAM and is confirmed by material analysis and reliability tests.

  12. Oxidation state-dependent conformational changes in cytochrome c.

    PubMed

    Berghuis, A M; Brayer, G D

    1992-02-20

    High-resolution three-dimensional structural analyses of yeast iso-1-cytochrome c have now been completed in both oxidation states using isomorphous crystalline material and similar structure determination methodologies. This approach has allowed a comprehensive comparison to be made between these structures and the elucidation of the subtle conformational changes occurring between oxidation states. The structure solution of reduced yeast iso-1-cytochrome c has been published and the determination of the oxidized protein and a comparison of these structures are reported herein. Our data show that oxidation state-dependent changes are expressed for the most part in terms of adjustments to heme structure, movement of internally bound water molecules and segmental thermal parameter changes along the polypeptide chain, rather than as explicit polypeptide chain positional shifts, which are found to be minimal. This result is emphasized by the retention of all main-chain to main-chain hydrogen bond interactions in both oxidation states. Observed thermal factor changes primarily affect four segments of polypeptide chain. Residues 37-39 show less mobility in the oxidized state, with Arg38 and its side-chain being most affected. In contrast, residues 47-59, 65-72 and 81-85 have significantly higher thermal factors, with maximal increases being observed for Asn52, Tyr67 and Phe82. The side-chains of two of these residues are hydrogen bonded to the internally bound water molecule, Wat166, which shows a large 1.7 A displacement towards the positively charged heme iron atom in the oxidized protein. Further analyses suggest that Wat166 is a major factor in stabilizing both oxidation states of the heme through differential orientation of dipole moment, shift in distance to the heme iron atom and alterations in the surrounding hydrogen bonding network. It also seems likely that Wat166 movement leads to the disruption of the hydrogen bond from the side-chain of Tyr67 to the Met80

  13. 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.

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

    DOE PAGES

    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 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

  15. The influence of goal-state access cost on planning during problem solving.

    PubMed

    Waldron, Samuel M; Patrick, John; Duggan, Geoffrey B

    2011-03-01

    Two problem-solving experiments investigated the relationship between planning and the cost of accessing goal-state information using the theoretical framework of the soft constraints hypothesis (Gray & Fu, 2004; Gray, Simms, Fu, & Schoelles, 2006). In Experiment 1, 36 participants were allocated to low, medium, and high access cost conditions and completed a problem-solving version of the Blocks World Task. Both the nature of planning (memory based or display based) and its timing (before or during action) changed with high goal-state access cost (a mouse movement and a 2.5-s delay). In this condition more planning before action was observed, with less planning during action, evidenced by longer first-move latencies, more moves per goal-state inspection, and more short (≤ 0.8 s) and long (>8 s) "preplanned" intermove latencies. Experiment 2 used an eight-puzzle-like transformation task and replicated the effect of goal-state access cost when more complex planning was required, also confirmed by sampled protocol data. Planning before an episode of move making increased with higher goal-state access cost, and planning whilst making moves increased with lower access cost. These novel results are discussed in the context of the soft constraints hypothesis.

  16. Improved characteristics of amorphous indium-gallium-zinc-oxide-based resistive random access memory using hydrogen post-annealing

    NASA Astrophysics Data System (ADS)

    Kang, Dae Yun; Lee, Tae-Ho; Kim, Tae Geun

    2016-08-01

    The authors report an improvement in resistive switching (RS) characteristics of amorphous indium-gallium-zinc-oxide (a-IGZO)-based resistive random access memory devices using hydrogen post-annealing. Because this a-IGZO thin film has oxygen off-stoichiometry in the form of deficient and excessive oxygen sites, the film properties can be improved by introducing hydrogen atoms through the annealing process. After hydrogen post-annealing, the device exhibited a stable bipolar RS, low-voltage set and reset operation, long retention (>105 s), good endurance (>106 cycles), and a narrow distribution in each current state. The effect of hydrogen post-annealing is also investigated by analyzing the sample surface using X-ray photon spectroscopy and atomic force microscopy.

  17. Medicaid home and community-based services: how consumer access is restricted by state policies.

    PubMed

    Ng, Terence; Stone, Julie; Harrington, Charlene

    2015-01-01

    State Medicaid programs have expanded home and community-based services (HCBS). This article compares trends and variations in state policies for Medicaid HCBS programs in 2005 and 2010. State limitations on financial eligibility criteria and service benefits have remained stable. Although the use of consumer direction, independent providers, and family care providers has increased, some states do not have these options. The increased adoption of state cost control policies have led to large increases in persons on waiver wait lists. Access could be improved by standardizing and liberalizing state HCBS policies, but state fiscal concerns are barriers to rebalancing between HCBS and institutional services. PMID:25299976

  18. State preemption of local tobacco control policies restricting smoking, advertising, and youth access--United States, 2000-2010.

    PubMed

    2011-08-26

    Preemptive state tobacco control legislation prohibits localities from enacting tobacco control laws that are more stringent than state law. State preemption provisions can preclude any type of local tobacco control policy. The three broad types of state preemption tracked by CDC include preemption of local policies that restrict 1) smoking in workplaces and public places, 2) tobacco advertising, and 3) youth access to tobacco products. A Healthy People 2020 objective (TU-16) calls for eliminating state laws that preempt any type of local tobacco control law. A previous study reported that the number of states that preempt local smoking restrictions in one or more of three settings (government worksites, private-sector worksites, and restaurants) has decreased substantially in recent years. To measure progress toward achieving Healthy People 2020 objectives, this study expands on the previous analysis to track changes in state laws that preempt local advertising and youth access restrictions and to examine policy changes from December 31, 2000, to December 31, 2010. This new analysis found that, in contrast with the substantial progress achieved during the past decade in reducing the number of states that preempt local smoking restrictions, no progress has been made in reducing the number of states that preempt local advertising restrictions and youth access restrictions. Increased progress in removing state preemption provisions will be needed to achieve the relevant Healthy People 2020 objective.

  19. Existence and accessibility of igniting states in a tokamak inferred from its performance in tritiumless discharges

    SciTech Connect

    Carretta, U.R.; Minardi, E.

    1988-09-01

    The conditions for the existence and accessibility of ignited or subignited deuterium-tritium states are discussed in terms of the performance of the thermonuclear device in tritiumless discharges. The discussion includes the effects of the thermal instability of both the marginally igniting states and the nonstationary states in the start-up phase. These effects are an integral part of the problem of the accessibility to ignition under reliable conditions. Typical examples taken from the next generation of igniting tokamaks are discussed. The necessity of allowing sufficient excursion of the plasma column for a stable drive to ignition by feedback on the vertical field is underlined.

  20. A Stateful Multicast Access Control Mechanism for Future Metro-Area-Networks.

    ERIC Educational Resources Information Center

    Sun, Wei-qiang; Li, Jin-sheng; Hong, Pei-lin

    2003-01-01

    Multicasting is a necessity for a broadband metro-area-network; however security problems exist with current multicast protocols. A stateful multicast access control mechanism, based on MAPE, is proposed. The architecture of MAPE is discussed, as well as the states maintained and messages exchanged. The scheme is flexible and scalable. (Author/AEF)

  1. One State's Initiative to Increase Access to Higher Education for People with Intellectual Disabilities

    ERIC Educational Resources Information Center

    Mock, Martha; Love, Kristen

    2012-01-01

    This article focuses on a state-based initiative to engage youth with intellectual disabilities (ID), their families, universities, schools, agencies, and funders in improving access to inclusive postsecondary education (PSE). As opportunities in higher education for students with ID continue to increase across United States, there are differing…

  2. 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

  3. 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.

  4. 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.

  5. Molecular accessibility in oxidized and dried coals. Quarterly report, [January--March 1994

    SciTech Connect

    Kispert, L.D.

    1994-03-01

    The objective of this research project is to determine the molecular and structural changes that occur in swelled coal as a result of oxidation and moisture loss both in the presence and absence of light using our newly developed EPR spin probe method. Looking at the over-all picture of the because of the increased cross-linking and lack of decrease in retention would be observed because of the increased cross-linking and lack of structural accessibility of the spin probes. This decrease would be observed in coals swelled in both toluene and pyridine since neither solvent is known to disrupt covalent cross-linking in coal. As the concentration of free radicals in the coal is decreased, this process would become less significant, and the production of hydroperoxides would become more important. As the oxidation process continue, production of hydroxides would cause both polar spin probes to be more strongly retained. As the hydroxyls were oxidized further to ketones, the retention of spin probe VI would become stronger than spin probe VII. However, as the ketones and hydroxyls are further oxidized to carboxylic groups, this trend would be reversed and spin probe VII. would be retained more strongly than spin probe VI. Of course, since the reaction products can form cross-links with other sections of the coal, this process would much more convoluted. A more complete picture of this process and its application to each individual spin probe is currently being prepared. It is apparent that the EPR spin probe method is very sensitive to the oxidation process in coal.

  6. Structure and Oxidation State of Silica-Supported Manganese Oxide Catalysts and Reactivity for Acetone Oxidation with Ozone

    SciTech Connect

    Reed,C.; Lee, Y.; Oyama, S.

    2006-01-01

    Silica-supported manganese oxide catalysts with loadings of 3, 10, 15, and 20 wt % (as MnO{sub 2}) were characterized with use of X-ray absorption spectroscopy and X-ray diffraction (XRD). The edge positions in the X-ray absorption spectra indicated that the oxidation state for the manganese decreased with increasing metal oxide loading from a value close to that of Mn{sub 2}O{sub 3} (+3) to a value close to that of Mn{sub 3}O{sub 4} (+2 2/3). The XRD was consistent with these results as the diffractograms for the supported catalysts of higher manganese oxide loading matched those of a Mn{sub 3}O{sub 4} reference. The reactivity of the silica-supported manganese oxide catalysts in acetone oxidation with ozone as an oxidant was studied over the temperature range of 300 to 600 K. Both oxygen and ozone produced mainly CO{sub 2} as the product of oxidation, but in the case of ozone the reaction temperature and activation energy were significantly reduced. The effect of metal oxide loading was investigated, and the activity for acetone oxidation was greater for a 10 wt % MnO{sub x}/SiO{sub 2} catalyst sample compared to a 3 wt % MnO{sub x}/SiO{sub 2} sample.

  7. Disparities and access to healthy food in the United States: A review of food deserts literature.

    PubMed

    Walker, Renee E; Keane, Christopher R; Burke, Jessica G

    2010-09-01

    Increasingly, studies are focusing on the role the local food environment plays in residents' ability to purchase affordable, healthy and nutritious foods. In a food desert, an area devoid of a supermarket, access to healthy food is limited. We conducted a systematic review of studies that focused on food access and food desert research in the United States. The 31 studies identified utilized 9 measures to assess food access. Results from these studies can be summarized primarily into four major statements. Findings from other countries offer insight into ways, in which future research, policy development and program implementation in the U.S. may continue to be explored. PMID:20462784

  8. Disparities and access to healthy food in the United States: A review of food deserts literature.

    PubMed

    Walker, Renee E; Keane, Christopher R; Burke, Jessica G

    2010-09-01

    Increasingly, studies are focusing on the role the local food environment plays in residents' ability to purchase affordable, healthy and nutritious foods. In a food desert, an area devoid of a supermarket, access to healthy food is limited. We conducted a systematic review of studies that focused on food access and food desert research in the United States. The 31 studies identified utilized 9 measures to assess food access. Results from these studies can be summarized primarily into four major statements. Findings from other countries offer insight into ways, in which future research, policy development and program implementation in the U.S. may continue to be explored.

  9. 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.

  10. Influence of retardation caused by partially oxidized adsorbate upon the oxidation state of copper catalyst and its performance for selective propylene oxidation

    SciTech Connect

    Inui, T.; Ueda, T.; Suehiro, M.

    1980-09-01

    Propylene oxidation to acrolein on copper oxide catalyst was optimized at 300/sup 0/C, a 3.5:1 propylene-oxygen ratio, and a slightly reduced cuprous oxide catalyst of 2.17:1 copper-oxygen ratio. Increasing feed concentrations of both propylene and oxygen (in nitrogen) increased both conversion and selectivity for acrolein. The optimum oxidation state of the catalyst was obtained by starting with completely reduced copper; other initial oxidation states gave steady-state catalysts with higher oxidation states. High oxygen concentrations caused sintering and cupric oxide whisker growth.

  11. 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

  12. 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.

  13. 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

  14. State Public Policies and the Racial/Ethnic Stratification of College Access and Choice in the State of Maryland

    ERIC Educational Resources Information Center

    Perna, Laura W.; Steele, Patricia; Woda, Susan; Hibbert, Taifa

    2005-01-01

    This study uses descriptive analyses of data from multiple sources to examine changes during the 1990s in the racial/ethnic stratification of college access and choice in Maryland and to explore state public policies that may have influenced changes in the demand for and supply of higher education for students of different racial/ethnic groups…

  15. 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 ...

  16. 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

  17. 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

  18. 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.

  19. 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.

  20. Gate controllable resistive random access memory devices using reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Hazra, Preetam; Resmi, A. N.; Jinesh, K. B.

    2016-04-01

    The biggest challenge in the resistive random access memory (ReRAM) technology is that the basic operational parameters, such as the set and reset voltages, the current on-off ratios (hence the power), and their operational speeds, strongly depend on the active and electrode materials and their processing methods. Therefore, for its actual technological implementations, the unification of the operational parameters of the ReRAM devices appears to be a difficult task. In this letter, we show that by fabricating a resistive memory device in a thin film transistor configuration and thus applying an external gate bias, we can control the switching voltage very accurately. Taking partially reduced graphene oxide, the gate controllable switching is demonstrated, and the possible mechanisms are discussed.

  1. Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Pike, Sebastian D.; White, Edward R.; Shaffer, Milo S. P.; Williams, Charlotte K.

    2016-10-01

    The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.

  2. Microstructural transitions in resistive random access memory composed of molybdenum oxide with copper during switching cycles.

    PubMed

    Arita, Masashi; Ohno, Yuuki; Murakami, Yosuke; Takamizawa, Keisuke; Tsurumaki-Fukuchi, Atsushi; Takahashi, Yasuo

    2016-08-21

    The switching operation of a Cu/MoOx/TiN resistive random access memory (ReRAM) device was investigated using in situ transmission electron microscopy (TEM), where the TiN surface was slightly oxidized (ox-TiN). The relationship between the switching properties and the dynamics of the ReRAM microstructure was confirmed experimentally. The growth and/or shrinkage of the conductive filament (CF) can be classified into two set modes and two reset modes. These switching modes depend on the device's switching history, factors such as the amount of Cu inclusions in the MoOx layer and the CF geometry. High currents are needed to produce an observable change in the CF. However, sharp and stable switching behaviour can be achieved without requiring such a major change. The local region around the CF is thought to contribute to the ReRAM switching process. PMID:27456192

  3. Microstructural transitions in resistive random access memory composed of molybdenum oxide with copper during switching cycles

    NASA Astrophysics Data System (ADS)

    Arita, Masashi; Ohno, Yuuki; Murakami, Yosuke; Takamizawa, Keisuke; Tsurumaki-Fukuchi, Atsushi; Takahashi, Yasuo

    2016-08-01

    The switching operation of a Cu/MoOx/TiN resistive random access memory (ReRAM) device was investigated using in situ transmission electron microscopy (TEM), where the TiN surface was slightly oxidized (ox-TiN). The relationship between the switching properties and the dynamics of the ReRAM microstructure was confirmed experimentally. The growth and/or shrinkage of the conductive filament (CF) can be classified into two set modes and two reset modes. These switching modes depend on the device's switching history, factors such as the amount of Cu inclusions in the MoOx layer and the CF geometry. High currents are needed to produce an observable change in the CF. However, sharp and stable switching behaviour can be achieved without requiring such a major change. The local region around the CF is thought to contribute to the ReRAM switching process.The switching operation of a Cu/MoOx/TiN resistive random access memory (ReRAM) device was investigated using in situ transmission electron microscopy (TEM), where the TiN surface was slightly oxidized (ox-TiN). The relationship between the switching properties and the dynamics of the ReRAM microstructure was confirmed experimentally. The growth and/or shrinkage of the conductive filament (CF) can be classified into two set modes and two reset modes. These switching modes depend on the device's switching history, factors such as the amount of Cu inclusions in the MoOx layer and the CF geometry. High currents are needed to produce an observable change in the CF. However, sharp and stable switching behaviour can be achieved without requiring such a major change. The local region around the CF is thought to contribute to the ReRAM switching process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02602h

  4. Dual operation characteristics of resistance random access memory in indium-gallium-zinc-oxide thin film transistors

    NASA Astrophysics Data System (ADS)

    Yang, Jyun-Bao; Chang, Ting-Chang; Huang, Jheng-Jie; Chen, Yu-Chun; Chen, Yu-Ting; Tseng, Hsueh-Chih; Chu, Ann-Kuo; Sze, Simon M.

    2014-04-01

    In this study, indium-gallium-zinc-oxide thin film transistors can be operated either as transistors or resistance random access memory devices. Before the forming process, current-voltage curve transfer characteristics are observed, and resistance switching characteristics are measured after a forming process. These resistance switching characteristics exhibit two behaviors, and are dominated by different mechanisms. The mode 1 resistance switching behavior is due to oxygen vacancies, while mode 2 is dominated by the formation of an oxygen-rich layer. Furthermore, an easy approach is proposed to reduce power consumption when using these resistance random access memory devices with the amorphous indium-gallium-zinc-oxide thin film transistor.

  5. Dual operation characteristics of resistance random access memory in indium-gallium-zinc-oxide thin film transistors

    SciTech Connect

    Yang, Jyun-Bao; Chen, Yu-Ting; Chu, Ann-Kuo; Chang, Ting-Chang; Huang, Jheng-Jie; Chen, Yu-Chun; Tseng, Hsueh-Chih; Sze, Simon M.

    2014-04-14

    In this study, indium-gallium-zinc-oxide thin film transistors can be operated either as transistors or resistance random access memory devices. Before the forming process, current-voltage curve transfer characteristics are observed, and resistance switching characteristics are measured after a forming process. These resistance switching characteristics exhibit two behaviors, and are dominated by different mechanisms. The mode 1 resistance switching behavior is due to oxygen vacancies, while mode 2 is dominated by the formation of an oxygen-rich layer. Furthermore, an easy approach is proposed to reduce power consumption when using these resistance random access memory devices with the amorphous indium-gallium-zinc-oxide thin film transistor.

  6. Kidney transplant access in the Southeastern United States: the need for a top-down transformation.

    PubMed

    Srinivas, T R

    2014-07-01

    End-stage renal disease (ESRD) and poverty are highly prevalent conditions in the Southeastern United States. The American Southeast also has some of the lowest attainments of health status among its constituents. Transplantation rates are particularly low in the Southeast compared with other regions of the United States. These low kidney transplantation rates in the Southeast likely reflect poor access to medical care. This disproportionate lack of access to medical care among ESRD patients in the Southeast reflects the convergence and interaction of socioeconomic and biologic forces at the patient level interacting with the financial and organizational structure of the health-care system. Improving kidney transplant access in the Southeast will take disruptive political, financial and health system changes whose scope transcends transplant centers and dialysis units.

  7. Metal oxide resistive random access memory based synaptic devices for brain-inspired computing

    NASA Astrophysics Data System (ADS)

    Gao, Bin; Kang, Jinfeng; Zhou, Zheng; Chen, Zhe; Huang, Peng; Liu, Lifeng; Liu, Xiaoyan

    2016-04-01

    The traditional Boolean computing paradigm based on the von Neumann architecture is facing great challenges for future information technology applications such as big data, the Internet of Things (IoT), and wearable devices, due to the limited processing capability issues such as binary data storage and computing, non-parallel data processing, and the buses requirement between memory units and logic units. The brain-inspired neuromorphic computing paradigm is believed to be one of the promising solutions for realizing more complex functions with a lower cost. To perform such brain-inspired computing with a low cost and low power consumption, novel devices for use as electronic synapses are needed. Metal oxide resistive random access memory (ReRAM) devices have emerged as the leading candidate for electronic synapses. This paper comprehensively addresses the recent work on the design and optimization of metal oxide ReRAM-based synaptic devices. A performance enhancement methodology and optimized operation scheme to achieve analog resistive switching and low-energy training behavior are provided. A three-dimensional vertical synapse network architecture is proposed for high-density integration and low-cost fabrication. The impacts of the ReRAM synaptic device features on the performances of neuromorphic systems are also discussed on the basis of a constructed neuromorphic visual system with a pattern recognition function. Possible solutions to achieve the high recognition accuracy and efficiency of neuromorphic systems are presented.

  8. Financing Access and Participation in Primary Education: Is There a "Fast-Track" for Fragile States?

    ERIC Educational Resources Information Center

    Turrent, Victoria

    2011-01-01

    Despite moves to "fast-track" progress towards universal primary education, few fragile states have been able to access Fast Track Initiative (FTI) funding facilities. Weak systems and capacity have made these countries a high-risk proposition for donor investment. The absence of credible education sector plans has meant that the majority of…

  9. Hope, Opportunity, and Access: The In-State Tuition Debate in North Carolina

    ERIC Educational Resources Information Center

    Sanders, Marla S.

    2010-01-01

    This qualitative case study explores the political debate that surrounded North Carolina's House Bill 1183, also known as Access to Higher Education and A Better Economic Future. This bill would have made undocumented students eligible for in-state tuition at North Carolina's colleges and universities. This article discusses the political debate,…

  10. The Effects of a State Need-based Access Grant on Traditional and Nontraditional Student Persistence

    ERIC Educational Resources Information Center

    Davidson, J. Cody

    2015-01-01

    In 2011-2012, more than 236.7 billion dollars of student financial aid was disbursed to undergraduate and graduate students at postsecondary institutions in the United States. Today, many groups and organizations are advocating for financial aid to increase student access and success as well as to assist the neediest students. The purpose of this…

  11. Access to Care for Methadone Maintenance Patients in the United States

    ERIC Educational Resources Information Center

    Hettema, Jennifer E.; Sorensen, James L.

    2009-01-01

    This policy commentary addresses a significant access to care issue that faces methadone maintenance patients seeking residential treatment in the United States. Methadone maintenance therapy (MMT) has demonstrated strong efficacy in the outpatient treatment of opiate dependence. However, many opiate dependent patients are also in need of more…

  12. State Challenges to "Plyler v. Doe": Undocumented Immigrant Students and Public School Access

    ERIC Educational Resources Information Center

    Sutton, Lenford C.; Stewart, Tricia J.

    2013-01-01

    This article presents a review and analysis of selected state laws and initiatives that have attempted to restrict public school access for undocumented immigrant children in the wake of the landmark U.S. Supreme Court decision of "Plyler v. Doe." Sutton and Stewart begin with an overview of the Court's ruling in "Plyler,"…

  13. Resistance switching behavior of ZnO resistive random access memory with a reduced graphene oxide capping layer

    NASA Astrophysics Data System (ADS)

    Lin, Cheng-Li; Chang, Wei-Yi; Huang, Yen-Lun; Juan, Pi-Chun; Wang, Tse-Wen; Hung, Ke-Yu; Hsieh, Cheng-Yu; Kang, Tsung-Kuei; Shi, Jen-Bin

    2015-04-01

    In this work, we investigate the characteristics of ZnO resistive random access memory (RRAM) with a reduced graphene oxide (rGO) capping layer and the polarity effect of the SET/RESET bias on the RRAM. The rGO film insertion enhances the stability of the current-voltage (I-V) switching curve and the superior resistance ratio (˜105) of high-resistance state (HRS) to low-resistance state (LRS). Using the appropriate polarity of the SET/RESET bias applied to the rGO-capped ZnO RRAM enables the oxygen ions to move mainly at the interface of the rGO and ZnO films, resulting in the best performance. Presumably, the rGO film acts as an oxygen reservoir and enhances the easy in and out motion of the oxygen ions from the rGO film. The rGO film also prevents the interaction of oxygen ions and the Al electrode, resulting in excellent performance. In a pulse endurance test, the rGO-capped ZnO RRAM reveals superior endurance of up to 108 cycles over that of the ZnO RRAM without rGO insertion (106 cycles).

  14. 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.

  15. State Parity Laws and Access to Treatment for Substance Use Disorder in the United States: Implications for Federal Parity Legislation

    PubMed Central

    Wen, Hefei; Cummings, Janet R.; Hockenberry, Jason M.; Gaydos, Laura M.; Druss, Benjamin G.

    2014-01-01

    Context The passage of the 2008 Mental Health Parity and Addiction Equity Act (MHPAEA) and the 2010 Affordable Care Act (ACA) incorporated parity for substance use disorder (SUD) into federal legislation. Yet prior research provides us with scant evidence as to whether federal parity legislation will hold the potential for improving access to SUD treatment. Objective This study examined the effect of state-level SUD parity laws on state-aggregate SUD treatment rates from 2000 to 2008, to shed light on the impact of the recent federal-level SUD parity legislation. Design A quasi-experimental study design using a two-way (state and year) fixed-effect method Setting and Participants All known specialty SUD treatment facilities in the United States Interventions State-level SUD parity laws between 2000 and 2008 Main Outcome Measures State-aggregate SUD treatment rates in: (1) all specialty SUD treatment facilities, and (2) specialty SUD treatment facilities accepting private insurance Results The implementation of any SUD parity law increased the treatment rate by 9 percent (p<0.01) in all specialty SUD treatment facilities and by 15 percent (p<0.05) in facilities accepting private insurance. Full parity and parity-if-offered (i.e., parity only if SUD coverage is offered) increased SUD treatment rate by 13 percent (p<0.05) and 8 percent (p<0.05) in all facilities, and by 21 percent (p<0.05) and 10 percent (p<0.05) in those accepting private insurance. Conclusions We found a positive effect of the implementation of state SUD parity legislation on access to specialty SUD treatment. Furthermore, the positive association was more pronounced in states with more comprehensive parity laws. Our findings suggest that federal parity legislation holds the potential to improve access to SUD treatment. PMID:24154931

  16. KetoABNO/NOx Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation.

    PubMed

    Miles, Kelsey C; Abrams, M Leigh; Landis, Clark R; Stahl, Shannon S

    2016-08-01

    A method for aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids without racemization. The scope, utility, and limitations of the oxidation method are further evaluated with a series of achiral aldehydes bearing diverse functional groups.

  17. 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.

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

    DOE PAGES

    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 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

  19. 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.

  20. State abortion policy, geographic access to abortion providers and changing family formation.

    PubMed

    Lichter, D T; McLaughlin, D K; Ribar, D C

    1998-01-01

    This study examined whether new barriers to abortion access are likely to contribute to increased female headship in the US. State and country fixed effects models are estimated for the impact of geographic access to abortion providers, notification requirements, parental consent, and Medicaid funding restrictions. Data were obtained from county records from summary tape files of the 1980 and 1990 censuses; abortion provider information from the Alan Guttmacher Institute; and physicians active in OB-GYN patient care data from the Bureau of Health Professionals Area Resource File. Pooled data amounted to 6132 observations for 3066 counties. The data included nonmarital births without a marriage and marital births followed by separation or divorce. Sensitivity analysis accounted for local divorce rates. Fixed effects controls accounted for unobserved variables. Population-weighted descriptive statistics are provided for dependent and key independent variables. Abortion provider declines ranged from 13% to 19%. Findings indicate that declines in geographic access accounted for a small, but significant, decline in increased female headship. About 50% of the increase among Black female headship was accounted for by restrictions on Medicaid funding. A modest amount of the rise in White female headship was due to state parent notification requirements. The difference in the estimated impact of abortion providers in the state and county specific models supported findings of Kane and Staiger. Sensitivity models did not alter the effects of access to abortion providers and physicians. Findings suggest conflicting or competing public policy goals.

  1. 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.

  2. A Straightforward Electrochemical Approach to Imine‐ and Amine‐bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State

    PubMed Central

    Chapman, Michael R.; Henkelis, Susan E.; Kapur, Nikil

    2016-01-01

    Abstract Synthetic methods to prepare organometallic and coordination compounds such as Schiff‐base complexes are diverse, with the route chosen being dependent upon many factors such as metal–ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal–salen/salan complexes which comprise diverse metal–ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (MII/III/IV where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol‐switch is described which allows access to analytically pure FeII/III–salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers MnII/IV–salen complexes in high yield. PMID:27547645

  3. A Straightforward Electrochemical Approach to Imine- and Amine-bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State.

    PubMed

    Chapman, Michael R; Henkelis, Susan E; Kapur, Nikil; Nguyen, Bao N; Willans, Charlotte E

    2016-08-01

    Synthetic methods to prepare organometallic and coordination compounds such as Schiff-base complexes are diverse, with the route chosen being dependent upon many factors such as metal-ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal-salen/salan complexes which comprise diverse metal-ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (M(II/III/IV) where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol-switch is described which allows access to analytically pure Fe(II/III)-salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers Mn(II/IV)-salen complexes in high yield. PMID:27547645

  4. 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.

  5. 42 CFR 457.495 - State assurance of access to care and procedures to assure quality and appropriateness of care.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... appropriateness of care provided under the plan, including how the State will assure: (a) Access to well-baby care... 42 Public Health 4 2012-10-01 2012-10-01 false State assurance of access to care and procedures to assure quality and appropriateness of care. 457.495 Section 457.495 Public Health CENTERS FOR...

  6. 42 CFR 457.495 - State assurance of access to care and procedures to assure quality and appropriateness of care.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... appropriateness of care provided under the plan, including how the State will assure: (a) Access to well-baby care... 42 Public Health 4 2013-10-01 2013-10-01 false State assurance of access to care and procedures to assure quality and appropriateness of care. 457.495 Section 457.495 Public Health CENTERS FOR...

  7. 42 CFR 457.495 - State assurance of access to care and procedures to assure quality and appropriateness of care.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... appropriateness of care provided under the plan, including how the State will assure: (a) Access to well-baby care... 42 Public Health 4 2014-10-01 2014-10-01 false State assurance of access to care and procedures to assure quality and appropriateness of care. 457.495 Section 457.495 Public Health CENTERS FOR...

  8. 42 CFR 457.495 - State assurance of access to care and procedures to assure quality and appropriateness of care.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... appropriateness of care provided under the plan, including how the State will assure: (a) Access to well-baby care... 42 Public Health 4 2011-10-01 2011-10-01 false State assurance of access to care and procedures to assure quality and appropriateness of care. 457.495 Section 457.495 Public Health CENTERS FOR...

  9. 42 CFR 457.495 - State assurance of access to care and procedures to assure quality and appropriateness of care.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... appropriateness of care provided under the plan, including how the State will assure: (a) Access to well-baby care... 42 Public Health 4 2010-10-01 2010-10-01 false State assurance of access to care and procedures to assure quality and appropriateness of care. 457.495 Section 457.495 Public Health CENTERS FOR...

  10. 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.

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

    PubMed

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

    2016-06-29

    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. PMID:27168317

  12. Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles

    PubMed Central

    Pike, Sebastian D.; White, Edward R.; Shaffer, Milo S. P.; Williams, Charlotte K.

    2016-01-01

    The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11 cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2–4 nm) nanoparticles. PMID:27734828

  13. Hemodialysis access at initiation in the United States, 2005 to 2007: still "catheter first".

    PubMed

    Foley, Robert N; Chen, Shu-Cheng; Collins, Allan J

    2009-10-01

    Despite the broad consensus that native arteriovenous fistula is the access of choice for hemodialysis, national-level information about vascular access at dialysis initiation has been unavailable in the United States. For incident hemodialysis patients, June 2005 to October 2007 (n=220,157), vascular access type was determined from the new Centers for Medicare & Medicaid Services Medical Evidence Report (form CMS-2728). Proportions with each type at first dialysis, demographic and clinical associations of each type, and associations between initial access type and survival were assessed. The mean patient age was 63.6 years; 29.4% of patients were African American, and for 44.5%, end-stage renal disease was due to diabetes. Vascular access proportions were: fistula, 13.2% of patients; graft, 4.3%; catheter/maturing fistula, 16.0%; catheter/maturing graft, 3.3%; and catheter alone, 63.2%. Adjusted odds ratios (vs. fistula) of catheter use alone were > or = 1.50 for lack of insurance (1.62 [95% confidence interval 1.62-1.68]), nephrologist care for 0 to 12 months (2.75 [2.69-2.81]), other (2.19 [2.09-2.29]), or unknown (1.53 [1.44-1.63]) cause of renal disease, institutional residence (1.51 [1.45-1.57]), and 7 of 18 end-stage renal disease networks. Over a mean follow-up of 1 year, 26.0% of the study population died. Compared with fistula, adjusted mortality hazards ratios were 1.39 (1.32-1.47) for grafts, 1.49 (1.44-1.55) for catheters/maturing fistulas, 1.74 (1.65-1.84) for catheters/maturing grafts, and 2.18 (2.11-2.26) for catheters alone. While geographic variability is pronounced, vascular access at dialysis inception is typically suboptimal; suboptimal access exhibits a graded association with mortality. Lack of timely access to specialty care appears to limit optimal access.

  14. Effective access to justice against state and non-state actors in the Framework Convention on Global Health: A proposal.

    PubMed

    Hevia, Martin; Vacaflor, Carlos Herrera

    2013-06-14

    A Framework Convention on Global Health (FCGH) seeks to have a profound, effective, and broad impact: bringing access to health rights to the largest global community possible. One of the main issues the FCGH will address is how to make the right to health justiciable. An FCGH must articulate functional remedies for violations of the right to health by state or non-state actors. This paper analyzes one approach to ensuring the recognition of the rights defended in a future FCGH. Following the incremental development approach inspired by the architecture of other successful framework convention protocols, we propose the inclusion of access to health justice guidelines in an FCGH. This proposal is based on the amparo remedy, a figure already extant in the legislation of several Latin American countries; since its incorporation, these countries have witnessed a significant increase in litigation defending health rights. This is only one of many important advantages to broadly adopting guidelines based on the amparo remedy. The proposed guidelines would serve as a basic agreement on broad principles on access to health justice.

  15. 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.

  16. 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.

  17. Women's perceptions of access to prenatal care in the United States: a literature review.

    PubMed

    Phillippi, Julia C

    2009-01-01

    Women report many barriers to accessing prenatal care. This article reviews the literature from 1990 to the present on women's perceptions of access to prenatal care within the United States. Barriers can be classified into societal, maternal, and structural dimensions. Women may not be motivated to seek care, especially for unintended pregnancies. Societal and maternal reasons cited for poor motivation include a fear of medical procedures or disclosing the pregnancy to others, depression, and a belief that prenatal care is unnecessary. Structural barriers include long wait times, the location and hours of the clinic, language and attitude of the clinic staff and provider, the cost of services, and a lack of child-friendly facilities. Knowledge of women's views of access can help in development of policies to decrease barriers. Structural barriers could be reduced through changes in clinic policy and prenatal care format, and the creation of child-friendly waiting and examination rooms. Maternal and societal barriers can be addressed through community education. A focus in future research on facilitators of access can assist in creating open pathways to perinatal care for all women.

  18. Evaluating the Oxidation State of Fe in Oxide Minerals using Fe K-edge XANES

    NASA Astrophysics Data System (ADS)

    Marcus, M. A.

    2006-12-01

    Synchrotron based X-ray absorption spectroscopy has proven to be a useful tool for examining the chemical state of various elements in earth and space materials, ranging from soils to ferromanganese ocean nodules to meteorites. Iron is the most common redox-active element in the Earth's crust, and determining its oxidation state in-situ is vital in many applications. XANES (X-ray absorption near-edge spectroscopy) promises to provide the sought-for information, but it is surprisingly difficult to inspect a spectrum and read off the average oxidation state. In general, even for oxide minerals, the energy or shape of a single feature isn't enough to yield a reliable figure. Methods have been proposed in the past for the interpretation of Fe XANES spectra (1-3), but they tend to rely either on a detailed analysis of the weak pre-edge features, or on very accurate measurements of the energies of features. These requirements often make it impossible to use data of ordinary quality to determine the oxidation state of an unknown. Therefore, a new method is proposed which is usable with only ordinary levels of energy resolution, signal/noise, and energy calibration accuracy. The inflection point of the pre-edge feature is taken as the energy zero, thus rendering the method self-calibrating. Then, the energy positions of the "white-line" maximum and the halfway-up points are plotted. When this procedure is done with a variety of Fe2+, Fe3+ and mixed-valent standards, it becomes clear that contours of constant valence can be drawn. A polynomial fit of valence to these energy coordinates is done, which can then be applied to any unknown. This method is accurate to about 0.25 valence units for all available divalent, trivalent and mixed- valent oxide standards. We found that the Fe sulfides such as pyrite occupy a different area on the graph than do the oxides. Examples of the use of this method with unknowns will be presented. 1) M. Wilke, F. Farges, P.-E. Petit, G. E. Brown

  19. Intestinal oxidative state can alter nutrient and drug bioavailability

    PubMed Central

    Monteiro, Rosário; pestana, Diogo; de Freitas, Victor; Mateus, Nuno; azevedo, Isabel; Calhau, Conceição

    2009-01-01

    Organic cations (OCs) are substances of endogenous (e.g., dopamine, choline) or exogenous (e.g., drugs like cimetidine) origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs) can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants) was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide) uptake in an enterocyte cell line (Caco-2). Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells). In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability. PMID:20716920

  20. Aerobic oxidation of diverse primary alcohols to methyl esters with a readily accessible heterogeneous Pd/Bi/Te catalyst.

    PubMed

    Powell, Adam B; Stahl, Shannon S

    2013-10-01

    Efficient aerobic oxidative methyl esterification of primary alcohols has been achieved with a heterogeneous catalyst consisting of 1 mol % Pd/charcoal (5 wt %) in combination with bismuth(III) nitrate and tellurium metal. The Bi and Te additives significantly increase the reaction rate, selectivity, and overall product yields. This readily accessible catalyst system exhibits a broad substrate scope and is effective with both activated (benzylic) and unactivated (aliphatic) alcohols bearing diverse functional groups. PMID:24050194

  1. The Oxidation State of Europium in Halide Glasses

    PubMed Central

    Weber, J.K.R.; Vu, M.; Paßlick, C.; Schweizer, S.; Brown, D.E.; Johnson, C.E.; Johnson, J.A.

    2012-01-01

    The luminescent properties of divalent europium ions can be exploited to produce storage phosphors for x-ray imaging applications. The relatively high cost and limited availability of divalent europium halides makes it desirable to synthesize them from the readily available trivalent salts. In this work, samples of pure EuCl3 and fluoride glass melts doped with EuCl3 were processed at 700-800 °C in an inert atmosphere furnace. The Eu oxidation state in the resulting materials was determined using fluorescence and Mössbauer spectroscopy. Heat treatment of pure EuCl3 for 10 minutes at 710 °C resulted in a material comprising approximately equal amounts of Eu2+ and Eu3+. Glasses made using mixtures of EuCl2 and EuCl3 in the starting material contained both oxidation states. This paper describes the sample preparation and analysis and discusses the results in the context of chemical equilibria in the melts. PMID:22101252

  2. 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. PMID:27547546

  3. 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.

  4. Crystal structures of human peroxiredoxin 6 in different oxidation states.

    PubMed

    Kim, Kyung Hee; Lee, Weontae; Kim, Eunice EunKyeong

    2016-09-01

    Peroxiredoxins (Prxs) are a family of antioxidant enzymes found ubiquitously. Prxs function not only as H2O2 scavengers but also as highly sensitive H2O2 sensors and signal transducers. Since reactive oxygen species are involved in many cellular metabolic and signaling processes, Prxs play important roles in various diseases. Prxs can be hyperoxidized to the sulfinic acid (SO2H) or sulfonic acid (SO3H) forms in the presence of high concentrations of H2O2. It is known that oligomerization of Prx is changed accompanying oxidation states, and linked to the function. Among the six Prxs in mammals, Prx6 is the only 1-Cys Prx. It is found in all organs in humans, unlike some 2-Cys Prxs, and is present in all species from bacteria to humans. In addition, Prx6 has Ca(2+)-independent phospholipase A2 (PLA2) activity. Thus far only the crystal structure of Prx in the oxidized state has been reported. In this study, we present the crystal structures of human Prx6 in the reduced (SH) and the sulfinic acid (SO2H) forms. PMID:27353378

  5. 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).

  6. Minimum Ages of Legal Access for Tobacco in the United States From 1863 to 2015

    PubMed Central

    Apollonio, Dorie E.; Glantz, Stanton A.

    2016-01-01

    In the United States, state laws establish a minimum age of legal access (MLA) for most tobacco products at 18 years. We reviewed the history of these laws with internal tobacco industry documents and newspaper archives from 1860 to 2014. The laws appeared in the 1880s; by 1920, half of states had set MLAs of at least 21 years. After 1920, tobacco industry lobbying eroded them to between 16 and 18 years. By the 1980s, the tobacco industry viewed restoration of higher MLAs as a critical business threat. The industry’s political advocacy reflects its assessment that recruiting youth smokers is critical to its survival. The increasing evidence on tobacco addiction suggests that restoring MLAs to 21 years would reduce smoking initiation and prevalence, particularly among those younger than 18 years. PMID:27196658

  7. Minimum Ages of Legal Access for Tobacco in the United States From 1863 to 2015.

    PubMed

    Apollonio, Dorie E; Glantz, Stanton A

    2016-07-01

    In the United States, state laws establish a minimum age of legal access (MLA) for most tobacco products at 18 years. We reviewed the history of these laws with internal tobacco industry documents and newspaper archives from 1860 to 2014. The laws appeared in the 1880s; by 1920, half of states had set MLAs of at least 21 years. After 1920, tobacco industry lobbying eroded them to between 16 and 18 years. By the 1980s, the tobacco industry viewed restoration of higher MLAs as a critical business threat. The industry's political advocacy reflects its assessment that recruiting youth smokers is critical to its survival. The increasing evidence on tobacco addiction suggests that restoring MLAs to 21 years would reduce smoking initiation and prevalence, particularly among those younger than 18 years. PMID:27196658

  8. The digital divide in public e-health: barriers to accessibility and privacy in state health department websites.

    PubMed

    West, Darrell M; Miller, Edward Alan

    2006-08-01

    State health departments have placed a tremendous amount of information, data, and services online in recent years. With the significant increase in online resources at official health sites, though, have come questions concerning equity of access and the confidentiality of electronic medical materials. This paper reports on an examination of public health department websites maintained by the 50 state governments. Using a content analysis of health department sites undertaken each year from 2000 to 2005, we investigate several dimensions of accessibility and privacy: readability levels, disability access, non-English accessibility, and the presence of privacy and security statements. We argue that although progress has been made at improving the accessibility and confidentiality of health department electronic resources, there remains much work to be done to ensure quality access for all Americans in the area of public e-health.

  9. 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.

  10. Oxidative state and oxidative metabolism of the heart from rats with adjuvant-induced arthritis.

    PubMed

    Schubert, Amanda Caroline; Wendt, Mariana Marques Nogueira; de Sá-Nakanishi, Anacharis Babeto; Amado, Ciomar Aparecida Bersani; Peralta, Rosane Marina; Comar, Jurandir Fernando; Bracht, Adelar

    2016-06-01

    The aim of the present work was to investigate, in a more extensive way, the oxidative state and parameters related to energy metabolism of the heart tissue of rats using the model of adjuvant-induced arthritis. The latter is a model for the human arthritic disease. Measurements were done in the total tissue homogenate, isolated mitochondria and cytosolic fraction. The adjuvant-induced arthritis caused several modifications in the oxidative state of the heart which, in general, indicate an increased oxidative stress (+80% reactive oxygen species), protein damage (+53% protein carbonyls) and lipid damage (+63% peroxidation) in the whole tissue. The distribution of these changes over the various cell compartments was frequently unequal. For example, protein carbonyls were increased in the whole tissue and in the cytosol, but not in the mitochondria. No changes in GSH content of the whole tissue were found, but it was increased in the mitochondria (+33%) and decreased in the cytosol (-19%). The activity of succinate dehydrogenase was 77% stimulated by arthritis; the activities of glutamate dehydrogenase, isocitrate dehydrogenase and cytochrome c oxidase were diminished by 31, 25 and 35.3%, respectively. In spite of these alterations, no changes in the mitochondrial respiratory activity and in the efficiency of energy transduction were found. It can be concluded that the adjuvant-induced arthritis in rats causes oxidative damage to the heart with an unequal intracellular distribution. Compared to the liver and brain the modifications caused by arthritis in the heart are less pronounced on variables such as GSH levels and protein integrity. Possibly this occurs because the antioxidant system of the heart is less impaired by arthritis than that reported for the former tissues. Even so, the modifications caused by arthritis represent an imbalanced situation that probably contributes to the cardiac symptoms of the arthritis disease. PMID:27032477

  11. Core Formation and the Oxidation State of the Earth

    NASA Astrophysics Data System (ADS)

    Wood, B. J.; Wade, J.; Walter, M. J.

    2005-12-01

    We have investigated the effects of temperature, pressure and metal composition on the metal-silicate partitioning of V, Cr, Ni, Co, Mn, Nb, W, Ga, P and Si in order to refine the `deep magma ocean' model of core formation. Interactions in the liquid metal were accounted for by using metallurgical data while temperature effects were calculated using free energy data for liquid metals and liquid oxides. This approach enabled us to separate pressure effects from those of the other two variables. Mantle concentrations of the refractory elements can be well-matched by single-stage core segregation at 3750K and a pressure of 40 GPa. The calculated temperature is, however, 800 degrees above the peridotite liquidus at 40 GPa, and is therefore physically implausible. The base of the magma ocean, at which metal would pond during accretion must be saturated in crystals and should, therefore lie close to the liquidus. We find that dynamic accretion models, in which pressure increased as the earth grew, do not improve the match to the peridotite liquidus so long as the oxygen fugacity is fixed by the current Fe content of the mantle. If, however, we force temperature to lie on the peridotite liquidus as the earth grew, the mantle concentrations of refractory elements can be matched provided oxygen fugacity increased during accretion. To illustrate this we use accretionary models in which, as the earth grew, the base of the magma ocean was at half the mantle depth and applied gradual or step-changes in oxygen fugacity. If we apply a 2 log unit increase in oxygen fugacity, the siderophile element contents of the mantle are matched, the Si content of the core is about 5 weight per cent and the average core segregation temperature is 2800K, within the experimental range. Oxidation during accretion is an important component of heterogeneous accretion models, but the mechanisms proposed are generally untestable. Here we propose that an increase in oxidation state is a natural

  12. Cost-effective, transfer-free, flexible resistive random access memory using laser-scribed reduced graphene oxide patterning technology.

    PubMed

    Tian, He; Chen, Hong-Yu; Ren, Tian-Ling; Li, Cheng; Xue, Qing-Tang; Mohammad, Mohammad Ali; Wu, Can; Yang, Yi; Wong, H-S Philip

    2014-06-11

    Laser scribing is an attractive reduced graphene oxide (rGO) growth and patterning technology because the process is low-cost, time-efficient, transfer-free, and flexible. Various laser-scribed rGO (LSG) components such as capacitors, gas sensors, and strain sensors have been demonstrated. However, obstacles remain toward practical application of the technology where all the components of a system are fabricated using laser scribing. Memory components, if developed, will substantially broaden the application space of low-cost, flexible electronic systems. For the first time, a low-cost approach to fabricate resistive random access memory (ReRAM) using laser-scribed rGO as the bottom electrode is experimentally demonstrated. The one-step laser scribing technology allows transfer-free rGO synthesis directly on flexible substrates or non-flat substrates. Using this time-efficient laser-scribing technology, the patterning of a memory-array area up to 100 cm(2) can be completed in 25 min. Without requiring the photoresist coating for lithography, the surface of patterned rGO remains as clean as its pristine state. Ag/HfOx/LSG ReRAM using laser-scribing technology is fabricated in this work. Comprehensive electrical characteristics are presented including forming-free behavior, stable switching, reasonable reliability performance and potential for 2-bit storage per memory cell. The results suggest that laser-scribing technology can potentially produce more cost-effective and time-effective rGO-based circuits and systems for practical applications.

  13. Reframing Vulnerability: Mozambican Refugees’ Access to State-Funded Pensions in Rural South Africa

    PubMed Central

    2012-01-01

    Researchers at the South African Medical Research Council/University of the Witwatersrand Rural Public Health and Health Transitions Research Unit (Agincourt) fieldsite in rural South Africa consider Mozambican residents more vulnerable than others in the local population. These self-settled refugees, many of whom are still not South African citizens, primarily came to South Africa in the 1980s during the Mozambican Civil War. This perceived economic vulnerability is rooted in their difficulties in accessing social grants, until recently legally available only to those with South African citizenship documentation. This paper focuses on semi-structured interviews with 30 ‘older’ women of Mozambican-descent living in the Agincourt area. These interviews highlight three important aspects of vulnerability; the respondents: (1) perceive a risk of deportation despite their having lived in the country for 20 years, (2) are unable to easily access social grants, namely the state-funded old-age pension, and (3) struggle to make ends meet when faced with daily needs and crisis situations. All three of these vulnerabilities were mediated to some extent by these women’s resourcefulness. They generated ties to South Africa through obtaining identification-documents, used these documents to access pensions, and used the pensions to help them sustain their multigenerational households. PMID:19142721

  14. Reframing vulnerability: Mozambican refugees' access to state-funded pensions in rural South Africa.

    PubMed

    Schatz, Enid J

    2009-09-01

    Researchers at the South African Medical Research Council/University of the Witwatersrand Rural Public Health and Health Transitions Research Unit (Agincourt) fieldsite in rural South Africa consider Mozambican residents more vulnerable than others in the local population. These self-settled refugees, many of whom are still not South African citizens, primarily came to South Africa in the 1980s during the Mozambican Civil War. This perceived economic vulnerability is rooted in their difficulties in accessing social grants, until recently legally available only to those with South African citizenship documentation. This paper focuses on semi-structured interviews with 30 'older' women of Mozambican-descent living in the Agincourt area. These interviews highlight three important aspects of vulnerability; the respondents: (1) perceive a risk of deportation despite their having lived in the country for 20 years, (2) are unable to easily access social grants, namely the state-funded old-age pension, and (3) struggle to make ends meet when faced with daily needs and crisis situations. All three of these vulnerabilities were mediated to some extent by these women's resourcefulness. They generated ties to South Africa through obtaining identification-documents, used these documents to access pensions, and used the pensions to help them sustain their multigenerational households. PMID:19142721

  15. Prescription drug accessibility and affordability in the United States and abroad.

    PubMed

    Morgan, Steve; Kennedy, Jae

    2010-06-01

    This issue brief contrasts prescription drug access, affordability, and costs in the United States with six other high-income countries, drawing from Commonwealth Fund survey data of patient experiences as well as international spending and pricing data. The analysis reveals that Americans, particularly the relatively young and healthy, are more likely to use prescription drugs than are residents of Australia, Canada, Germany, the Netherlands, New Zealand, and the United Kingdom, but they also experience more financial barriers in accessing medications and spend more out-of-pocket for prescriptions. In the U.S., there are also larger income-related inequities in pharmaceutical use. Despite access barriers and disparities, spending per person in the U.S. is far higher, likely the result of paying higher prices for similar medications and using a more expensive mix of drugs. The authors say that value-based benefit designs, reference pricing, and group purchasing could reduce financial barriers and keep down pharmaceutical spending. PMID:20614652

  16. Racial and ethnic differences in pediatric access to preemptive kidney transplantation in the United States.

    PubMed

    Patzer, R E; Sayed, B A; Kutner, N; McClellan, W M; Amaral, S

    2013-07-01

    Preemptive kidney transplantation is the optimal treatment for pediatric end stage renal disease patients to avoid increased morbidity and mortality associated with dialysis. It is unknown how race/ethnicity and poverty influence preemptive transplant access in pediatric. We examined the incidence of living donor or deceased donor preemptive transplantation among all black, white, and Hispanic children (<18 years) in the United States Renal Data System from 2000 to 2009. Adjusted risk ratios for preemptive transplant were calculated using multivariable-adjusted models and examined across health insurance and neighborhood poverty levels. Among 8,053 patients, 1117 (13.9%) received a preemptive transplant (66.9% from LD, 33.1% from DD). In multivariable analyses, there were significant racial/ethnic disparities in access to LD preemptive transplant where blacks were 66% (RR = 0.34; 95% CI: 0.28-0.43) and Hispanics 52% (RR = 0.48; 95% CI: 0.35-0.67) less likely to receive a LD preemptive transplant versus whites. Blacks were 22% less likely to receive a DD preemptive transplant versus whites (RR = 0.78, 95% CI: 0.57-1.05), although results were not statistically significant. Future efforts to promote equity in preemptive transplant should address the critical issues of improving access to pre-ESRD nephrology care and overcoming barriers in living donation, including obstacles partially driven by poverty.

  17. Determination of the oxidation states of metals and metalloids: An analytical review

    NASA Astrophysics Data System (ADS)

    Vodyanitskii, Yu. N.

    2013-12-01

    The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

  18. Spin states and electronic conduction in Ni oxides

    NASA Astrophysics Data System (ADS)

    Dionne, Gerald F.

    1990-05-01

    Magnetic and electronic properties of the mixed-valence semiconductor LixNi2+1-2xNi3+xO are reinterpreted in terms of low-spin states for both Ni ions. Anomalous decreases in hopping electron activation energies are discussed on the basis of (i) breakdown in antiferromagnetic ordering through spin canting of the Ni sublattices through exchange isolation caused by diamagnetic Li1+ ions that group with the low-spin Ni3+ (S= (1)/(2) ) to form polarons, and (ii) enhanced disruption of magnetic superexchange that results from a combination of Li1+ dilutants and S=0 states of surrounding Ni2+ ions induced at low temperatures by static Jahn-Teller tetragonal distortions of the oxygen octahedra around the Ni3+ polarons. Reported magnetic ordering and conduction anomalies in La2-xSrxNiO4 are then compared to the behavior of Cu in LixCu1-xO, and in the high-Tc superconducting La2-xSrxCuO4 system. Spontaneous conduction through molecular-orbital states involving zero-spin Ni and Cu ions is discussed, together with the role of S=0 polarons in other oxide superconductors.

  19. Liquid state DNP for water accessibility measurements on spin-labeled membrane proteins at physiological temperatures.

    PubMed

    Doll, Andrin; Bordignon, Enrica; Joseph, Benesh; Tschaggelar, René; Jeschke, Gunnar

    2012-09-01

    We demonstrate the application of continuous wave dynamic nuclear polarization (DNP) at 0.35 T for site-specific water accessibility studies on spin-labeled membrane proteins at concentrations in the 10-100 μM range. The DNP effects at such low concentrations are weak and the experimentally achievable dynamic nuclear polarizations can be below the equilibrium polarization. This sensitivity problem is solved with an optimized home-built DNP probe head consisting of a dielectric microwave resonator and a saddle coil as close as possible to the sample. The performance of the probe head is demonstrated with both a modified pulsed EPR spectrometer and a dedicated CW EPR spectrometer equipped with a commercial NMR console. In comparison to a commercial pulsed ENDOR resonator, the home-built resonator has an FID detection sensitivity improvement of 2.15 and an electron spin excitation field improvement of 1.2. The reproducibility of the DNP results is tested on the water soluble maltose binding protein MalE of the ABC maltose importer, where we determine a net standard deviation of 9% in the primary DNP data in the concentration range between 10 and 100 μM. DNP parameters are measured in a spin-labeled membrane protein, namely the vitamin B(12) importer BtuCD in both detergent-solubilized and reconstituted states. The data obtained in different nucleotide states in the presence and absence of binding protein BtuF reveal the applicability of this technique to qualitatively extract water accessibility changes between different conformations by the ratio of primary DNP parameters ϵ. The ϵ-ratio unveils the physiologically relevant transmembrane communication in the transporter in terms of changes in water accessibility at the cytoplasmic gate of the protein induced by both BtuF binding at the periplasmic region of the transporter and ATP binding at the cytoplasmic nucleotide binding domains.

  20. Liquid state DNP for water accessibility measurements on spin-labeled membrane proteins at physiological temperatures

    NASA Astrophysics Data System (ADS)

    Doll, Andrin; Bordignon, Enrica; Joseph, Benesh; Tschaggelar, René; Jeschke, Gunnar

    2012-09-01

    We demonstrate the application of continuous wave dynamic nuclear polarization (DNP) at 0.35 T for site-specific water accessibility studies on spin-labeled membrane proteins at concentrations in the 10-100 μM range. The DNP effects at such low concentrations are weak and the experimentally achievable dynamic nuclear polarizations can be below the equilibrium polarization. This sensitivity problem is solved with an optimized home-built DNP probe head consisting of a dielectric microwave resonator and a saddle coil as close as possible to the sample. The performance of the probe head is demonstrated with both a modified pulsed EPR spectrometer and a dedicated CW EPR spectrometer equipped with a commercial NMR console. In comparison to a commercial pulsed ENDOR resonator, the home-built resonator has an FID detection sensitivity improvement of 2.15 and an electron spin excitation field improvement of 1.2. The reproducibility of the DNP results is tested on the water soluble maltose binding protein MalE of the ABC maltose importer, where we determine a net standard deviation of 9% in the primary DNP data in the concentration range between 10 and 100 μM. DNP parameters are measured in a spin-labeled membrane protein, namely the vitamin B12 importer BtuCD in both detergent-solubilized and reconstituted states. The data obtained in different nucleotide states in the presence and absence of binding protein BtuF reveal the applicability of this technique to qualitatively extract water accessibility changes between different conformations by the ratio of primary DNP parameters ɛ. The ɛ-ratio unveils the physiologically relevant transmembrane communication in the transporter in terms of changes in water accessibility at the cytoplasmic gate of the protein induced by both BtuF binding at the periplasmic region of the transporter and ATP binding at the cytoplasmic nucleotide binding domains.

  1. Food access and cost in American Indian communities in Washington State.

    PubMed

    O'Connell, Meghan; Buchwald, Dedra S; Duncan, Glen E

    2011-09-01

    Limited access to foods that make up a nutritious diet at minimal cost may influence eating behaviors and, ultimately, obesity. This study examined the number and type of food stores (convenience, grocery, supermarket) on federal reservations in Washington State, and the availability and cost of foods in the US Department of Agriculture Community Food Security Assessment Toolkit market basket, to describe the food environment of American Indians. Stores were identified by telephone survey of tribal headquarters, a commercial database, and on-site visitation. Foods were assessed using a standardized instrument containing 68 items in seven major food groups during April and May 2009. Store type and availability and cost of foods were recorded on a checklist. Fifty stores were identified on 22 American Indian reservations, including 25 convenience, 16 grocery, and 9 supermarkets. Across all stores, about 38% of checklist items were available, with supermarkets having the most and convenience stores the fewest. Foods from the dairy and sugars/sweets groups were the most prevalent, while fresh fruits/vegetables were the least. Cost of the most commonly available items was lowest in supermarkets. Seventeen reservations did not have a supermarket on their reservation, and the nearest off-reservation supermarket was about 10 miles from the tribe's headquarters, which was used as the standard for distance calculations. These results demonstrate that American Indians living on federal reservations in Washington State may have limited access to foods that make up a nutritious diet at minimal cost.

  2. Manganese oxidation state mediates toxicity in PC12 cells

    SciTech Connect

    Reaney, S.H. . E-mail: stevereaney@hotmail.com; Smith, D.R.

    2005-06-15

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 {mu}M Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 {mu}M produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 {mu}M), while Mn(III) exposures produced increases in LDH activity at lower exposures ({>=}50 {mu}M) than did Mn(II) (200 {mu}M only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 {mu}M Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity.

  3. 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

  4. 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.

  5. 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.

  6. "Inosaminoacids": novel inositol-amino acid hybrid structures accessed by microbial arene oxidation.

    PubMed

    Pilgrim, Sarah; Kociok-Köhn, Gabriele; Lloyd, Matthew D; Lewis, Simon E

    2011-04-28

    Microbial 1,2-dihydroxylation of sodium benzoate permits the rapid construction of novel inositol-amino acid hybrid structures. Both β- and γ-amino acids are accessible by means of an acylnitroso Diels-Alder cycloaddition.

  7. 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

  8. Web Accessibility in Europe and the United States: What We Are Doing to Increase Inclusion

    ERIC Educational Resources Information Center

    Wheaton, Joseph; Bertini, Patrizia

    2007-01-01

    Accessibility is hardly a new problem and certainly did not originate with the Web. Lack of access to buildings long preceded the call for accessible Web content. Although it is unlikely that rehabilitation educators look at Web page accessibility with indifference, many may also find it difficult to implement. The authors posit three reasons why…

  9. 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.

  10. 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.

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

    DOE PAGES

    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 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

  12. [Regionalization and access to healthcare in Brazilian states: historical and political-institutional conditioning factors].

    PubMed

    de Lima, Luciana Dias; Viana, Ana Luiza d'Ávila; Machado, Cristiani Vieira; de Albuquerque, Mariana Vercesi; de Oliveira, Roberta Gondim; Iozzi, Fabíola Lana; Scatena, João Henrique Gurtler; Mello, Guilherme Arantes; Pereira, Adelyne Maria Mendes; Coelho, Ana Paula Santana

    2012-11-01

    This article examines the healthcare regionalization process in the Brazilian states in the period from 2007 to 2010, seeking to identify the conditions that favor or impede this process. Referential analysis of public policies and especially of historical institutionalism was used. Three dimensions sum up the conditioning factors of regionalization: context (historical-structural, political-institutional and conjunctural), directionality (ideology, object, actors, strategies and instruments) and regionalization features (institutionality and governance). The empirical research relied mainly on the analysis of official documents and interviews with key actors in 24 states. Distinct patterns of influence in the states were observed, with regionalization being marked by important gains in institutionality and governance in the period. Nevertheless, inherent difficulties of the contexts prejudice greater advances. There is a pressing need to broaden the territorial focus in government planning and to integrate sectorial policies for medium and long-term regional development in order to empower regionalization and to overcome obstacles to the access to healthcare services in Brazil.

  13. Spin-patterned plasmonics: towards optical access to topological-insulator surface states.

    PubMed

    Spektor, Grisha; David, Asaf; Bartal, Guy; Orenstein, Meir; Hayat, Alex

    2015-12-14

    Topological insulators (TI) are new phases of matter with topologically protected surface states (SS) possessing novel physical properties such as spin-momentum locking. Coupling optical angular momentum to the SS is of interest for both fundamental understanding and applications in future spintronic devices. However, due to the nanoscale thickness of the surface states, the light matter interaction is dominated by the bulk. Here we propose and experimentally demonstrate a plasmonic cavity enabling both nanoscale light confinement and control of surface plasmon-polariton (SPP) spin angular momentum (AM)--towards coupling to topological-insulator SS. The resulting SPP field components within the cavity are arranged in a chess-board-like pattern. Each chess-board square exhibits approximately a uniform circular polarization (spin AM) of the local in-plane field interleaved by out-of-plane field vortices (orbital AM). As the first step, we demonstrate the predicted pattern experimentally by near-field measurements on a gold-air interface, with excellent agreement to our theory. Our results pave the way towards efficient optical access to topological-insulator surface states using plasmonics.

  14. Spin-patterned plasmonics: towards optical access to topological-insulator surface states.

    PubMed

    Spektor, Grisha; David, Asaf; Bartal, Guy; Orenstein, Meir; Hayat, Alex

    2015-12-14

    Topological insulators (TI) are new phases of matter with topologically protected surface states (SS) possessing novel physical properties such as spin-momentum locking. Coupling optical angular momentum to the SS is of interest for both fundamental understanding and applications in future spintronic devices. However, due to the nanoscale thickness of the surface states, the light matter interaction is dominated by the bulk. Here we propose and experimentally demonstrate a plasmonic cavity enabling both nanoscale light confinement and control of surface plasmon-polariton (SPP) spin angular momentum (AM)--towards coupling to topological-insulator SS. The resulting SPP field components within the cavity are arranged in a chess-board-like pattern. Each chess-board square exhibits approximately a uniform circular polarization (spin AM) of the local in-plane field interleaved by out-of-plane field vortices (orbital AM). As the first step, we demonstrate the predicted pattern experimentally by near-field measurements on a gold-air interface, with excellent agreement to our theory. Our results pave the way towards efficient optical access to topological-insulator surface states using plasmonics. PMID:26699065

  15. [The bioethics of protection and the state's role: moral problems in unequal access to drinking water].

    PubMed

    Pontes, Carlos Antonio Alves; Schramm, Fermin Roland

    2004-01-01

    The aim of this study is to examine unequal access to drinking water as a public health problem in terms of normative and analytical tools in the bioethics of protection. Therefore, we analyze both the moral implications of unequal treatment of primary needs, such as situations of vulnerability and threat to population groups, and the public sector's responsibility in supplying safe water. In addition, solutions are proposed for the protection of public health and the promotion of legitimate personal development projects. The bioethics of protection reaffirms the state's role in maintaining the drinking water supply and recommends avoiding a policy of privatization of this public good, meanwhile justifying public policies to correct situations of social injustice.

  16. Welcome to the wild west: protecting access to cross border fertility care in the United States.

    PubMed

    Mutcherson, Kimberley M

    2012-01-01

    As has been the case with other types of medical tourism, the phenomenon of cross border fertility care ("CBFC") has sparked concern about the lack of global or even national harmonization in the regulation of the fertility industry. The diversity of laws around the globe leads would-be parents to forum shop for a welcoming place to make babies. Focusing specifically on the phenomenon of travel to the United States, this Article takes up the question of whether there should be any legal barriers to those who come to the United States seeking CBFC. In part, CBFC suffers from the same general concerns raised about the use of fertility treatment in general, but it is possible to imagine a subset of arguments that would lead to forbidding or at least discouraging people from coming to the United States for CBFC, either as a matter of law or policy. This paper stands in opposition to any such effort and contemplates the moral and ethical concerns about CBFC and how, and if, those concerns warrant expression in law. Part I describes the conditions that lead some couples and individuals to leave their home countries to access fertility treatments abroad and details why the United States, with its comparatively liberal regulation of ART, has become a popular CBFC destination for travelers from around the world. Part II offers and refutes arguments supporting greater domestic control over those who seek to satisfy their desires for CBFC in the United States by reasserting the importance of the right of procreation while also noting appropriate concerns about justice and equality in the market for babies. Part III continues the exploration of justice by investigating the question of international cooperation in legislating against perceived wrongs. This Part concludes that consistent legislation across borders is appropriate where there is consensus about the wrong of an act, but it is unnecessary and inappropriate where there remain cultural conflicts about certain

  17. 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.

  18. Soluble and immobilized graphene oxide activates complement system differently dependent on surface oxidation state.

    PubMed

    Wibroe, Peter P; Petersen, Søren V; Bovet, Nicolas; Laursen, Bo W; Moghimi, S Moein

    2016-02-01

    Graphene oxide (GO) is believed to become applicable in biomedical products and medicine, thereby necessitating appropriate safety evaluation dependent on their applications and the route of administration. We have examined the effect of GO form (in solution versus immobilized) and oxidation state on two related elements of innate immunity: the complement system and interleukin-6 (IL-6) release in human blood. In solution, there was a decrease in GO-mediated complement activation with decreasing surface oxygen content (and altered oxygen functionality), whereas with immobilized GO complement response were reversed and increased with decreasing oxygen content. GO solutions, at concentrations below complement activating threshold, did not induce IL-6 release from human blood leukocytes, and further dampened lipopolysaccharide-induced IL-6 release in the whole blood. The latter effect became more profound with GO's having higher oxygen content. This protective role of GO solutions, however, disappeared at higher concentrations above complement-activating threshold. We discuss these results in relation to GO surface structure and properties, and implications for local administration and development of GO-based implantable devices.

  19. 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]).

  20. Access to and Use of Reproductive Health Information among In-School Adolescent Girls in Lagos State, Nigeria

    ERIC Educational Resources Information Center

    Nwalo, K. I. N.; Anasi, Stella N. I.

    2012-01-01

    Objective: This study investigated access to and use of reproductive health information among in-school adolescent girls in Lagos State, Nigeria. Design: Descriptive survey research design was adopted for the study. Setting: The study sample consisted of 1,800 girls randomly selected from 18 public senior secondary schools in Lagos State. Method:…

  1. In-State Tuition Policies under the Veterans Access, Choice and Accountability Act. ECS Education Policy Analysis

    ERIC Educational Resources Information Center

    Fulton, Mary; Sponsler, Brian A.

    2015-01-01

    Ensuring access and affordability to a postsecondary education for veterans and their dependents has long been a focus of federal and state education policy. Developing policy to support educational attainment among these individuals has required state policymakers to address residency requirements for veterans to determine eligibility for…

  2. 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.

  3. Valence-state reflectometry of complex oxide heterointerfaces

    DOE PAGES

    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.; et al

    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

  4. Switching operation and degradation of resistive random access memory composed of tungsten oxide and copper investigated using in-situ TEM

    PubMed Central

    Arita, Masashi; Takahashi, Akihito; Ohno, Yuuki; Nakane, Akitoshi; Tsurumaki-Fukuchi, Atsushi; Takahashi, Yasuo

    2015-01-01

    In-situ transmission electron microscopy (in-situ TEM) was performed to investigate the switching operation of a resistive random access memory (ReRAM) made of copper, tungsten oxide and titanium nitride (Cu/WOx/TiN). In the first Set (Forming) operation to initialize the device, precipitation appeared inside the WOx layer. It was presumed that a Cu conducting filament was formed, lowering the resistance (on-state). The Reset operation induced a higher resistance (the off-state). No change in the microstructure was identified in the TEM images. Only when an additional Reset current was applied after switching to the off-state could erasure of the filament be seen (over-Reset). Therefore, it was concluded that structural change relating to the resistance switch was localized in a very small area around the filament. With repeated switching operations and increasing operational current, the WOx/electrode interfaces became indistinct. At the same time, the resistance of the off-state gradually decreased. This is thought to be caused by Cu condensation at the interfaces because of leakage current through the area other than through the filament. This will lead to device degradation through mechanisms such as endurance failure. This is the first accelerated aging test of ReRAM achieved using in-situ TEM. PMID:26611856

  5. Probing access resistance of solid-state nanopores with a scanning-probe microscope tip.

    PubMed

    Hyun, Changbae; Rollings, Ryan; Li, Jiali

    2012-02-01

    An apparatus that integrates solid-state nanopore ionic current measurement with a scanning-probe microscope is developed. When a micrometer-scale scanning-probe tip is near a voltage-biased nanometer-scale pore (10–100 nm), the tip partially blocks the flow of ions to the pore and increases the pore access resistance. The apparatus records the current blockage caused by the probe tip and the location of the tip simultaneously. By measuring the current blockage map near a nanopore as a function of the tip position in 3D space in salt solution, the relative pore resistance increases due to the tip and ΔR/R0 is estimated as a function of the tip location, nanopore geometry, and salt concentration. The amplitude of ΔR/R0 also depends on the ratio of the pore length to its radius as Ohm's law predicts. When the tip is very close to the pore surface, ≈10 nm, experiments show that ΔR/R0 depends on salt concentration as predicted by the Poisson and Nernst–Planck equations. Furthermore, the measurements show that ΔR/R0 goes to zero when the tip is about five times the pore diameter away from the center of the pore entrance. The results in this work not only demonstrate a way to probe the access resistance of nanopores experimentally; they also provide a way to locate the nanopore in salt solution, and open the door to future nanopore experiments for detecting single biomolecules attached to a probe tip.

  6. Probing Access Resistance of Solid-state Nanopores with a Scanning Probe Microscope Tip.

    PubMed

    Hyun, Changbae; Rollings, Ryan; Li, Jiali

    2012-02-01

    An apparatus that integrates solid-state nanopore ionic current measurement with a Scanning Probe Microscope has been developed. When a micrometer-scale scanning probe tip is near a voltage biased nanometer-scale pore (10-100 nm), the tip partially blocks the flow of ions to the pore and increases the pore access resistance. The apparatus records the current blockage caused by the probe tip and the location of the tip simultaneously. By measuring the current blockage map near a nanopore as a function of the tip position in 3D space in salt solution, we estimate the relative pore resistance increase due to the tip, ΔR/R(0), as a function of the tip location, nanopore geometry, and salt concentration. The amplitude of ΔR/R(0) also depends on the ratio of the pore length to its radius as Ohm's law predicts. When the tip is very close to the pore surface, ~10 nm, our experiments show that ΔR/R(0) depends on salt concentration as predicted by the Poisson and Nernst-Planck equations. Furthermore, our measurements show that ΔR/R(0) goes to zero when the tip is about five times the pore diameter away from the center of the pore entrance. The results in this work not only demonstrate a way to probe the access resistance of nanopores experimentally, they also provide a way to locate the nanopore in salt solution, and open the door to future nanopore experiments for detecting single biomolecules attached to a probe tip.

  7. "One-pot" access to dihydrofurans via tandem oxidative difunctionalization and ring contraction of aminopyrans.

    PubMed

    Mandha, Santhosh Reddy; Alla, Manjula; Nanubolu, Jagadeesh Babu

    2014-07-01

    An operationally simple and efficient protocol for the construction of dihydrofuran derivatives has been accomplished via a sequential addition of N-chlorosuccinimide and a base to 2-amino-4H-pyran derivatives in alcohol medium. The one-pot protocol proceeding via tandem oxidative difunctionalization and ring contraction provides an entirely new strategy for the construction of the dihydrofuran skeleton. PMID:24846686

  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. Research access to privately owned wetland basins in the prairie pothole region of the United States

    USGS Publications Warehouse

    Fellows, David P.; Buhl, Thomas K.

    1995-01-01

    We describe efforts to obtain access for research to 81 wetland basins on 69 farms in four zones of the Prairie Pothole Region of North Dakota, South Dakota, and Minnesota. Access was obtained to 54% of the farms in areas where land was intensively cropped and 87% of farms in areas of low cropping intensity. On average, 1.35 operators had to be contacted and 1.70 interviews were required to obtain a decision on access to a farm. On 77% of the farms, cooperators placed at least one restriction on access, most commonly requiring walking access only or notification before nighttime work. Cost of obtaining access averaged $265/farm in wages and travel expenses. No cooperators were willing to sign written access agreements. Operators rescinded access to four farms and drained three wetland basins during the first year; six of the seven sites lost were in the intensively cropped portion of a low-wetland-density zone. The difficulty of obtaining and retaining research access to privately owned wetland basins in intensively cropped areas may be related to landowner attitudes towards wetlands. Researchers may have to rely on remote sensing or consider payment for access to secure representative research sites in such areas. Unwillingness of cooperators to sign access agreements may jeopardize research by the newly formed National Biological Service and other resource management agencies.

  10. 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.

  11. Solid-State NMR Characterization of Aluminum Oxide Nanofibers

    SciTech Connect

    Cross, Jennifer L; Tuttle, Ricky W; Ramsier, Rex D; Espe, Mathew

    2006-07-24

    Aluminum oxide nanofibers have been generated by an electrospinning process, creating fibers with diameters on the nanometer scale and aspect ratios greater than a thousand. These nanofibers have the potential of providing enhanced catalytic properties, due to their large surface area and controllable compositions. Solid-state NMR is being used to investigate both the bulk and surface properties of these materials. 27Al NMR has shown that no chemistry occurs during the electrospinning process, even though potentials in excess of 20 kV are applied to the sample. Thermal treatment of the fibers to convert them to alumina results in the formation of different phases, with the phases identified by the relative populations of 4-, 5-, and 6-coordinate alumina sites. Heating to 525°C or 1200°C produces a species similar to the catalytically active gamma-phase or conversion of the nanofibers into the thermodynamically stable alumina phase, respectively. 1H-27Al CP/MAS has shown that the alumina phase has a low population of surface hydroxyls, whereas the “gamma-alumina” form has a much higher fraction of 5-coordinate sites, compared to materials synthesized by traditional techniques. Organophosphates are being used as molecular probes in the characterization of the nanofiber surfaces. 31P CP/MAS data has revealed the presence of mono-, bi- and tri-denate bound phosphate groups on the surface, with the onset of surface alumina dissolution with sample heating. The application of 1H-31P HETCOR shows that the three different types of bound organophosphates are intermixed, rather than there being separate domains for each type. 31P-27Al CP is also being used to distinguish the types of surface alumina sites bound to the phosphate species.

  12. An EPR spin probe method for characterizing changes in the accessible regions of coal upon oxidation

    SciTech Connect

    Sady, W.; Kispert, L.D.; Spears, D.R.

    1992-01-01

    Eight Argonne Premium Coal Samples (APCS) were weathered in air and the structural and chemical changes that upon swelling with toluene and pyridine were, examined by an EPR spin probe method developed in this laboratory. Under mild oxidation conditions and swelling with toluene large structural changes were observed for lignite (Beulah-Zap) which suggested the collapse of the coal structure. This did not occur for higher rank coal. Upon oxidation and swelling with toluene and pyridine an increase occurred in the amino substituted spin probe concentration for coals with the carbon percent above 80%. A maximum was found for the creation of 5 {Angstrom} diameter pores upon swelling with pyridine at 85% C.

  13. An EPR spin probe method for characterizing changes in the accessible regions of coal upon oxidation

    SciTech Connect

    Sady, W.; Kispert, L.D.; Spears, D.R.

    1992-09-01

    Eight Argonne Premium Coal Samples (APCS) were weathered in air and the structural and chemical changes that upon swelling with toluene and pyridine were, examined by an EPR spin probe method developed in this laboratory. Under mild oxidation conditions and swelling with toluene large structural changes were observed for lignite (Beulah-Zap) which suggested the collapse of the coal structure. This did not occur for higher rank coal. Upon oxidation and swelling with toluene and pyridine an increase occurred in the amino substituted spin probe concentration for coals with the carbon percent above 80%. A maximum was found for the creation of 5 {Angstrom} diameter pores upon swelling with pyridine at 85% C.

  14. A Domino Oxidation/Arylation/Protodecarboxylation Reaction of Salicylaldehydes: Expanded Access to meta‐Arylphenols

    PubMed Central

    Luo, Junfei; Preciado, Sara; Araromi, Solomon Olatokunbo

    2015-01-01

    Abstract A method that allows salicylaldehydes to be efficiently transformed into meta‐arylated phenol derivatives through a cascade oxidation/arylation/protodecarboxylation sequence is presented. We demonstrate that the aldehyde functional group can be used as a convenient removable directing group to control site selectivity in C−H activation. Aldehydes are easily introduced into the starting materials and the group is readily cleaved after the C−H functionalization event. PMID:26097094

  15. Metal-free oxidative decarbonylative coupling of aromatic aldehydes with arenes: direct access to biaryls.

    PubMed

    Tang, Ren-Jin; He, Qing; Yang, Luo

    2015-04-01

    A metal-free oxidative decarbonylative coupling of aromatic aldehydes with electron-rich or electron-deficient arenes to produce biaryl compounds was developed. This novel coupling was proposed to proceed via a non-chain radical homolytic aromatic substitution (HAS) type mechanism, based on the substrate scope, ortho-regioselectivity, radical trapping experiments and DFT calculation studies. With the ready availability of aromatic aldehydes and arenes, metal-free conditions should make this coupling attractive for the biaryl synthesis.

  16. The oxidation state of nanophase Fe particles in lunar soil: Implications for space weathering

    NASA Astrophysics Data System (ADS)

    Thompson, Michelle S.; Zega, Thomas J.; Becerra, Patricio; Keane, James T.; Byrne, Shane

    2016-06-01

    We report measurements of the oxidation state of Fe nanoparticles within lunar soils that experienced varied degrees of space weathering. We measured >100 particles from immature, submature, and mature lunar samples using electron energy-loss spectroscopy (EELS) coupled to an aberration-corrected transmission electron microscope. The EELS measurements show that the nanoparticles are composed of a mixture of Fe0, Fe2+, and Fe3+ oxidation states, and exhibit a trend of increasing oxidation state with higher maturity. We hypothesize that the oxidation is driven by the diffusion of O atoms to the surface of the Fe nanoparticles from the oxygen-rich matrix that surrounds them. The oxidation state of Fe in the nanoparticles has an effect on modeled reflectance properties of lunar soil. These results are relevant to remote sensing data for the Moon and to the remote determination of relative soil maturities for various regions of the lunar surface.

  17. 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.

  18. [Activity of methane-oxidizing bacteria in the adsorbed state].

    PubMed

    Nesterov, A I; Nazarenko, A V

    1975-01-01

    Adsorption of pure cultures of methane oxidizing bacteria, Methylosinus trichosporium 20 and Methylococcus ucrainicus 21, on glass and coal was studied; the former strain was sorbed on both sorbents, the latter strain was sorbed on coal but not on glass. The rate of methane oxidation by the cells of adsorbed microorganisms was higher than in the case of free cells, and increased with a decrease in dimensions of the sorbent particles. PMID:1207502

  19. 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.

  20. Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: efficient access to α-alkyl vinylarenes.

    PubMed

    Zheng, Changwu; Stahl, Shannon S

    2015-08-18

    Branched-selective oxidative Heck coupling reactions have been developed between arylboronic acids and electronically unbiased terminal alkenes. The reactions exhibit high catalyst-controlled regioselectivity favoring the less common branched isomer. The reactions employ a catalyst composed of Pd(TFA)2/dmphen (TFA = trifluoroacetate, dmphen = 2,9-dimethyl-1,10-phenanthroline) and proceed efficiently at 45-60 °C under 1 atm of O2 without requiring other additives. A broad array of functional groups, including aryl halide, allyl silane and carboxylic acids are tolerated.

  1. Access Assistants for State Assessments: A Study of State Guidelines for Scribes, Readers, and Sign Language Interpreters. Synthesis Report 58

    ERIC Educational Resources Information Center

    Clapper, Ann T.; Morse, Amanda B.; Thompson, Sandra J.; Thurlow, Martha L.

    2005-01-01

    For several years, states have listed accommodations allowed on state assessments. States soon found that the definitions of these accommodations varied not only across states, but also within states and even in schools. Over the past few years, states have made greater attempts to define each accommodation and to decide whether the accommodation…

  2. 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

  3. Financial Aid, Access & Equity, and State Policy: An Interview with Richard Freeland, Commissioner of Higher Education for Massachusetts

    ERIC Educational Resources Information Center

    Jobs for the Future, 2012

    2012-01-01

    Many states are looking at effective ways to use financial incentives to encourage students to complete a postsecondary credential. JFF's new report, "Statewide Aid Policies to Improve College Access and Success", originally commissioned by the Massachusetts Department of Higher Education's Vision Project, has provided valuable background for that…

  4. 40 CFR 1400.9 - Access to off-site consequence analysis information by State and local government officials.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 34 2013-07-01 2013-07-01 false Access to off-site consequence analysis information by State and local government officials. 1400.9 Section 1400.9 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY AND DEPARTMENT OF JUSTICE ACCIDENTAL RELEASE...

  5. 40 CFR 1400.9 - Access to off-site consequence analysis information by State and local government officials.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 32 2010-07-01 2010-07-01 false Access to off-site consequence analysis information by State and local government officials. 1400.9 Section 1400.9 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY AND DEPARTMENT OF JUSTICE ACCIDENTAL RELEASE...

  6. 40 CFR 1400.9 - Access to off-site consequence analysis information by State and local government officials.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 34 2012-07-01 2012-07-01 false Access to off-site consequence analysis information by State and local government officials. 1400.9 Section 1400.9 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY AND DEPARTMENT OF JUSTICE ACCIDENTAL RELEASE...

  7. 40 CFR 1400.9 - Access to off-site consequence analysis information by State and local government officials.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 33 2011-07-01 2011-07-01 false Access to off-site consequence analysis information by State and local government officials. 1400.9 Section 1400.9 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY AND DEPARTMENT OF JUSTICE ACCIDENTAL RELEASE...

  8. 40 CFR 1400.9 - Access to off-site consequence analysis information by State and local government officials.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 33 2014-07-01 2014-07-01 false Access to off-site consequence analysis information by State and local government officials. 1400.9 Section 1400.9 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY AND DEPARTMENT OF JUSTICE ACCIDENTAL RELEASE...

  9. Public Perception of the Millennium Development Goals on Access to Safe Drinking Water in Cross River State, Nigeria

    ERIC Educational Resources Information Center

    Eni, David D.; Ojong, William M.

    2014-01-01

    This study evaluated the public perception of Millennium Development Goals (MDGs) of environmental sustainability with focus on the MDG target which has to do with reducing the proportion of people without access to safe drinking water in Cross River State, Nigeria. The stratified and systematic sampling techniques were adopted for the study,…

  10. Evaluation of soybean germplasm accessions for resistance to Phakopsora pachyrhizi populations in the southeastern United States, 2009-2012

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soybean [Glycine max (L.) Merr.] germplasm accessions from the USDA Soybean Germplasm Collection were screened for resistance to soybean rust (Phakopsora pachyrhizi) at up to five locations in the southeastern United States in 2009, 2011 and 2012. In 2009, plant introductions (PIs) from maturity gro...

  11. 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.

  12. United States Federal Health Care Websites: A Multimethod Evaluation of Website Accessibility for Individuals with Disabilities

    ERIC Educational Resources Information Center

    Brobst, John L.

    2012-01-01

    The problem addressed by this study is the observed low levels of compliance with federal policy on website accessibility. The study examines the two key federal policies that promote website accessibility, using a side-by-side policy analysis technique. The analysis examines the Americans with Disabilities Act of 1990 and Section 508 of the…

  13. The National Instructional Materials Accessibility Standard (NIMAS): State Implementation Update. inForum

    ERIC Educational Resources Information Center

    Etemad, Pontea; Burdette, Paula

    2009-01-01

    The National Instructional Materials Accessibility Standard (NIMAS) was added to the Individuals with Disabilities Act in 2004. The purpose of this standard is to provide guidance to schools to ensure that students with print disabilities have access to the general education curriculum through specially adapted print materials. In 2007, Project…

  14. What Does Role-Based Access Look Like? Examples from States

    ERIC Educational Resources Information Center

    Data Quality Campaign, 2008

    2008-01-01

    Data are only useful if people are able to access, understand and use them. Without access to the right information, stakeholders are forced to make decisions based on anecdote, experience or instinct. For information to be useful, it must be timely, readily available, and easy to understand. Different stakeholders need and are entitled to access…

  15. Beryllium chemistry the safe way: a theoretical evaluation of low oxidation state beryllium compounds.

    PubMed

    Couchman, Shannon A; Holzmann, Nicole; Frenking, Gernot; Wilson, David J D; Dutton, Jason L

    2013-08-28

    A theoretical study of compounds containing Be in the +1 or 0 oxidation state has been carried out. The molecules considered containing Be in the +1 oxidation state are analogues of the important Mg(I)-Mg(I) dimer supported by the β-diketiminate ligand. The molecules in the 0 oxidation state are NHC supported compounds analogous to "molecular allotropes" which has recently become a topic of importance in p-block chemistry. In this case, our results demonstrate that the Be(0) complexes are far more stable than the analogous Mg(0) complexes, highlighting the opportunities afforded in Be chemistry, despite the challenges presented by the toxicity of Be compounds.

  16. Identification of an iridium-containing compound with a formal oxidation state of IX.

    PubMed

    Wang, Guanjun; Zhou, Mingfei; Goettel, James T; Schrobilgen, Gary J; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian

    2014-10-23

    One of the most important classifications in chemistry and within the periodic table is the concept of formal oxidation states. The preparation and characterization of compounds containing elements with unusual oxidation states is of great interest to chemists. The highest experimentally known formal oxidation state of any chemical element is at present VIII, although higher oxidation states have been postulated. Compounds with oxidation state VIII include several xenon compounds (for example XeO4 and XeO3F2) and the well-characterized species RuO4 and OsO4 (refs 2-4). Iridium, which has nine valence electrons, is predicted to have the greatest chance of being oxidized beyond the VIII oxidation state. In recent matrix-isolation experiments, the IrO4 molecule was characterized as an isolated molecule in rare-gas matrices. The valence electron configuration of iridium in IrO4 is 5d(1), with a formal oxidation state of VIII. Removal of the remaining d electron from IrO4 would lead to the iridium tetroxide cation ([IrO4](+)), which was recently predicted to be stable and in which iridium is in a formal oxidation state of IX. There has been some speculation about the formation of [IrO4](+) species, but these experimental observations have not been structurally confirmed. Here we report the formation of [IrO4](+) and its identification by infrared photodissociation spectroscopy. Quantum-chemical calculations were carried out at the highest level of theory that is available today, and predict that the iridium tetroxide cation, with a Td-symmetrical structure and a d(0) electron configuration, is the most stable of all possible [IrO4](+) isomers. PMID:25341786

  17. Identification of an iridium-containing compound with a formal oxidation state of IX

    NASA Astrophysics Data System (ADS)

    Wang, Guanjun; Zhou, Mingfei; Goettel, James T.; Schrobilgen, Gary J.; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian

    2014-10-01

    One of the most important classifications in chemistry and within the periodic table is the concept of formal oxidation states. The preparation and characterization of compounds containing elements with unusual oxidation states is of great interest to chemists. The highest experimentally known formal oxidation state of any chemical element is at present VIII, although higher oxidation states have been postulated. Compounds with oxidation state VIII include several xenon compounds (for example XeO4 and XeO3F2) and the well-characterized species RuO4 and OsO4 (refs 2, 3, 4). Iridium, which has nine valence electrons, is predicted to have the greatest chance of being oxidized beyond the VIII oxidation state. In recent matrix-isolation experiments, the IrO4 molecule was characterized as an isolated molecule in rare-gas matrices. The valence electron configuration of iridium in IrO4 is 5d1, with a formal oxidation state of VIII. Removal of the remaining d electron from IrO4 would lead to the iridium tetroxide cation ([IrO4]+), which was recently predicted to be stable and in which iridium is in a formal oxidation state of IX. There has been some speculation about the formation of [IrO4]+ species, but these experimental observations have not been structurally confirmed. Here we report the formation of [IrO4]+ and its identification by infrared photodissociation spectroscopy. Quantum-chemical calculations were carried out at the highest level of theory that is available today, and predict that the iridium tetroxide cation, with a Td-symmetrical structure and a d0 electron configuration, is the most stable of all possible [IrO4]+ isomers.

  18. 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.

  19. Stationary and transient thermal states of barometric pumping in the access pit of an underground quarry.

    PubMed

    Perrier, Frédéric; Le Mouël, Jean-Louis

    2016-04-15

    The transition zone between free and underground atmospheres hosts spectacular phenomena, as demonstrated by temperature measurements performed in the 4.6m diameter and 20m deep vertical access pit of an abandoned underground quarry located in Vincennes, near Paris. In summer, a stable stratification of the atmosphere is maintained, with coherent temperature variations associated with atmospheric pressure changes, with a barometric tide S2 larger than 0.1°C peak to peak. When the winter regime of turbulent cold air avalanches is initiated, stratification with pressure induced signals can be restored transiently in the upper part of the pit, while the lower part remains fully mixed and insensitive to pressure variations. The amplitude of the pressure to temperature transfer function increases with frequency below 5×10(-4)Hz, with values at 3×10(-5)Hz varying from 0.1°C·hPa(-1) at the bottom up to 2°C·hPa(-1) towards the top of the pit. These temperature variations are accounted for by cave breathing, which is pressure induced motion of air amplified by the large volume of the quarry. This understanding is supported by a numerical model including advective heat transport, heat diffusion, and heat exchange with the pit walls. Mean lifetime in the pit is of the order of 9 to 13h, and barometric pumping results in an effective ventilation rate of the quarry of the order of 10(-7)s(-1). This study illustrates the important role of barometric pumping in heat and matter transport between atmosphere and lithosphere. The resulting stationary and transient states, revealed in this pit, are probably a general feature of functioning interface systems, and therefore are an important aspect to consider in problems of contaminant transport, or the preservation of precious heritage such as rare ecosystems or painted caves.

  20. Stationary and transient thermal states of barometric pumping in the access pit of an underground quarry.

    PubMed

    Perrier, Frédéric; Le Mouël, Jean-Louis

    2016-04-15

    The transition zone between free and underground atmospheres hosts spectacular phenomena, as demonstrated by temperature measurements performed in the 4.6m diameter and 20m deep vertical access pit of an abandoned underground quarry located in Vincennes, near Paris. In summer, a stable stratification of the atmosphere is maintained, with coherent temperature variations associated with atmospheric pressure changes, with a barometric tide S2 larger than 0.1°C peak to peak. When the winter regime of turbulent cold air avalanches is initiated, stratification with pressure induced signals can be restored transiently in the upper part of the pit, while the lower part remains fully mixed and insensitive to pressure variations. The amplitude of the pressure to temperature transfer function increases with frequency below 5×10(-4)Hz, with values at 3×10(-5)Hz varying from 0.1°C·hPa(-1) at the bottom up to 2°C·hPa(-1) towards the top of the pit. These temperature variations are accounted for by cave breathing, which is pressure induced motion of air amplified by the large volume of the quarry. This understanding is supported by a numerical model including advective heat transport, heat diffusion, and heat exchange with the pit walls. Mean lifetime in the pit is of the order of 9 to 13h, and barometric pumping results in an effective ventilation rate of the quarry of the order of 10(-7)s(-1). This study illustrates the important role of barometric pumping in heat and matter transport between atmosphere and lithosphere. The resulting stationary and transient states, revealed in this pit, are probably a general feature of functioning interface systems, and therefore are an important aspect to consider in problems of contaminant transport, or the preservation of precious heritage such as rare ecosystems or painted caves. PMID:26855357

  1. 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)

  2. 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.

  3. Prebiotic Potential of Reduced Oxidation State Phosphorus. The H-Phosphinate-Pyruvate System

    NASA Astrophysics Data System (ADS)

    Bryant, D. E.; Marriott, K. E. R.; MacGregor, S. A.; Fishwick, C. W. G.; Kilner, C.; Bullough, E. K.; Pasek, M. A.; Kee, T. P.

    2010-04-01

    Phosphorus (P) is central to life as we know it but problems with using geologically available orthophosphate en route to life remain. Here we discuss how reduced oxidation state P-chemistry may offer additional possibilities for prebiotic chemistry.

  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. A comparative genomic approach focused on Ciona intestinaJis, an invertebrate chordate, was u...

  5. 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,...

  6. 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...

  7. Biological role of nitric oxide: history, modern state, and perspectives for research.

    PubMed

    Vanin, A F

    1998-07-01

    This paper is an introduction to this issue of review papers on the biological role of nitric oxide. The history, modern state, and promising directions for research in this field are briefly considered. PMID:9721326

  8. 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

  9. Temperature induced complementary switching in titanium oxide resistive random access memory

    NASA Astrophysics Data System (ADS)

    Panda, D.; Simanjuntak, F. M.; Tseng, T.-Y.

    2016-07-01

    On the way towards high memory density and computer performance, a considerable development in energy efficiency represents the foremost aspiration in future information technology. Complementary resistive switch consists of two antiserial resistive switching memory (RRAM) elements and allows for the construction of large passive crossbar arrays by solving the sneak path problem in combination with a drastic reduction of the power consumption. Here we present a titanium oxide based complementary RRAM (CRRAM) device with Pt top and TiN bottom electrode. A subsequent post metal annealing at 400°C induces CRRAM. Forming voltage of 4.3 V is required for this device to initiate switching process. The same device also exhibiting bipolar switching at lower compliance current, Ic <50 μA. The CRRAM device have high reliabilities. Formation of intermediate titanium oxi-nitride layer is confirmed from the cross-sectional HRTEM analysis. The origin of complementary switching mechanism have been discussed with AES, HRTEM analysis and schematic diagram. This paper provides valuable data along with analysis on the origin of CRRAM for the application in nanoscale devices.

  10. A culture gap in the United States: Implications for policy on limiting access to firearms for suicidal persons.

    PubMed

    Marino, Elizabeth; Wolsko, Christopher; Keys, Susan G; Pennavaria, Laura

    2016-09-01

    Suicide is a critical public health problem worldwide. In the United States (US), firearm ownership is common, and firearms account for the majority of deaths by suicide. While suicide prevention strategies may include limiting access to firearms, the contentious nature of gun regulations in the US, particularly among members of rural communities, often gives rise to constitutional concerns and political polarization that could inhibit suicidal persons from seeking the help they need. We examine potential outcomes of public health strategies in the US that encourage limiting access to firearms for populations who both value firearm ownership and are vulnerable to suicide. Based on preliminary results from a firearm safety study, we argue that attempts to limit access to firearms among those at risk of suicide will only succeed when the most affected cultural groups are engaged in collaborative discussions. PMID:27638246

  11. A culture gap in the United States: Implications for policy on limiting access to firearms for suicidal persons.

    PubMed

    Marino, Elizabeth; Wolsko, Christopher; Keys, Susan G; Pennavaria, Laura

    2016-09-01

    Suicide is a critical public health problem worldwide. In the United States (US), firearm ownership is common, and firearms account for the majority of deaths by suicide. While suicide prevention strategies may include limiting access to firearms, the contentious nature of gun regulations in the US, particularly among members of rural communities, often gives rise to constitutional concerns and political polarization that could inhibit suicidal persons from seeking the help they need. We examine potential outcomes of public health strategies in the US that encourage limiting access to firearms for populations who both value firearm ownership and are vulnerable to suicide. Based on preliminary results from a firearm safety study, we argue that attempts to limit access to firearms among those at risk of suicide will only succeed when the most affected cultural groups are engaged in collaborative discussions.

  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. States in the Driver's Seat: Leveraging State Aid to Align Policies and Promote Access, Success, and Affordability

    ERIC Educational Resources Information Center

    Prescott, Brian T.; Longanecker, David A.

    2014-01-01

    With increasingly widespread calls to raise educational attainment levels without substantially growing public investment in higher education, policymakers and others have devoted growing attention to the role of financial aid programs in providing access to, promoting affordability for, and incentivizing success in college. Given relative levels…

  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. Access and closure of the left ventricular apex: state of play

    PubMed Central

    Ziegelmueller, Johannes Amadeus; Lange, Rüdiger

    2015-01-01

    Calcific aortic stenosis is the most frequent manifestation of valvular heart disease. The preferred treatment for patients of all age groups is surgical aortic valve replacement. Recently, transcatheter aortic valve implantation (TAVI) has become the standard of care for patients that are deemed to be at high risk for open heart surgery. The most common access route for TAVI is the retrograde transfemoral (TF) approach, followed by the antegrade transapical (TA) approach. Both access routes have distinct indications. While the TF route is least invasive and the access of choice at most centers, the apical route is used complementary in patients with poor femoral access. In addition, the TA approach holds various benefits such as a short distance from the operator to the annulus facilitating exact positioning of the valve and the possibility to accommodate larger sheaths. Furthermore, the TA approach not only provides direct access to the aortic valve but also the mitral valve allowing for a wide range of interventions. Various apical closure devices are currently being developed under the premise of increasing overall safety of the TA-TAVI approach by further standardizing the procedure, alleviating left ventricular access and minimizing the risk of complications, such as apical bleeding. The aim of this article is to give an overview of current devices for apical closure. The ideal apical closure device should be easy to put in place, leave a minimum of foreign material, provide complete hemostasis and have a minimal risk of displacement. So far the range of commercially available devices in Europe is very limited with only one CE-certified device on the market and one device that is expected to receive CE-certification soon. Off-the-shelf closure devices could help flatten the initial operator learning curve and facilitate a safe apical access, ultimately leading to an entirely percutaneous TA-TAVI approach. PMID:26543601

  17. Access and closure of the left ventricular apex: state of play.

    PubMed

    Ziegelmueller, Johannes Amadeus; Lange, Rüdiger; Bleiziffer, Sabine

    2015-09-01

    Calcific aortic stenosis is the most frequent manifestation of valvular heart disease. The preferred treatment for patients of all age groups is surgical aortic valve replacement. Recently, transcatheter aortic valve implantation (TAVI) has become the standard of care for patients that are deemed to be at high risk for open heart surgery. The most common access route for TAVI is the retrograde transfemoral (TF) approach, followed by the antegrade transapical (TA) approach. Both access routes have distinct indications. While the TF route is least invasive and the access of choice at most centers, the apical route is used complementary in patients with poor femoral access. In addition, the TA approach holds various benefits such as a short distance from the operator to the annulus facilitating exact positioning of the valve and the possibility to accommodate larger sheaths. Furthermore, the TA approach not only provides direct access to the aortic valve but also the mitral valve allowing for a wide range of interventions. Various apical closure devices are currently being developed under the premise of increasing overall safety of the TA-TAVI approach by further standardizing the procedure, alleviating left ventricular access and minimizing the risk of complications, such as apical bleeding. The aim of this article is to give an overview of current devices for apical closure. The ideal apical closure device should be easy to put in place, leave a minimum of foreign material, provide complete hemostasis and have a minimal risk of displacement. So far the range of commercially available devices in Europe is very limited with only one CE-certified device on the market and one device that is expected to receive CE-certification soon. Off-the-shelf closure devices could help flatten the initial operator learning curve and facilitate a safe apical access, ultimately leading to an entirely percutaneous TA-TAVI approach. PMID:26543601

  18. Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

    PubMed

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

    2013-01-15

    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 r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) 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 Fe(3)O(4) with the same particle size, but their r(1) 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.

  19. Access to enforcement and disciplinary data: information practices of state health professional regulatory boards of dentistry, medicine and nursing.

    PubMed

    Strong, Denise E

    2011-01-01

    This article describes a study of public access to enforcement and disciplinary information provided by the websites of health professional regulatory boards. The study explored the current state of transparency by specifically examining the availability of disciplinary data on the websites of state boards of medicine, nursing and dentistry. Web sites were reviewed regarding availability of enforcement and disciplinary data on the aforementioned state boards in each of the 50 states and the District of Columbia. The study found that there is more information about individual practitioners available from the boards than ever before. On the other hand, there has not been a comparable increase in information about the administrative practices and the work of the boards. Increased availability of this information would allow public administration and policy researchers to develop performance indicators of state boards and assist in improving policy decisions and allocation of resources.

  20. Impacts of Ion Irradiation on Hafnium oxide-based Resistive Random Access Memory Devices

    NASA Astrophysics Data System (ADS)

    He, Xiaoli

    The impacts of ion irradiation on so-called vacancy-change mechanism (VCM) and electrochemical-metallization mechanism (ECM) ReRAM devices based on HfO2 are investigated using various ion sources: H + (1 MeV), He+ (1 MeV), N+ (1 MeV), Ne+ (1.6 MeV) and Ar+ (2.75 MeV) over a range of total doses (105 -- 1011 rad(Si)) and fluences (1012 -- 1015 cm-2). VCM-ReRAM devices show robust resistive switching function after all irradiation experiments. VCM resistive switching parameters including set voltage (V set), reset voltage (Vreset), on-state resistance (R on) and off-state resistance (Roff) exhibited, in most cases, modest changes after irradiation. Decreases in forming voltage (Vf) and initial resistance (Rfresh) of fresh devices were observed after all irradiation experiments on VCM-ReRAM devices with the exception of Ar+ irradiation at the highest fluence (10 15 cm-2). In that case Rfresh increased by an order of magnitude. For VCM-ReRAM devices it was also observed that irradiation beyond a dose threshold of approximately 5 Grad(Si) could induce off-to-on state transition events. This behavior could lead to errors in a VCM-ReRAM memory system. ECM-ReRAM devices (based on HfO2) were also subjected to ion irradiation. Under proton irradiation ECM-ReRAM devices remained functional, but with relatively large positive variations (20-40%) in Vset, Vreset and Ron and large negative variations (˜ -60%) in Roff. In contrast to VCM HfO2-ReRAMs, ECM-based devices exhibited increased V f after irradiation, and no off-to-on transitions were observed. Interestingly, for ECM-ReRAM devices, high-fluence Ar irradiation resulted in a transition of the electrical conduction mechanism associated with the conductive filament forming process from a Poole-Frenkel conduction mechanism (pre-irradiation) to ionic conduction (post-Ar irradiation). ECM-ReRAM devices irradiated with lighter ions did not exhibit this effect. The different ion irradiation responses of the two types of HfO2-Re

  1. Dynamics of chromatin accessibility and epigenetic state in response to UV damage.

    PubMed

    Schick, Sandra; Fournier, David; Thakurela, Sudhir; Sahu, Sanjeeb Kumar; Garding, Angela; Tiwari, Vijay K

    2015-12-01

    Epigenetic mechanisms determine the access of regulatory factors to DNA during events such as transcription and the DNA damage response. However, the global response of histone modifications and chromatin accessibility to UV exposure remains poorly understood. Here, we report that UV exposure results in a genome-wide reduction in chromatin accessibility, while the distribution of the active regulatory mark H3K27ac undergoes massive reorganization. Genomic loci subjected to epigenetic reprogramming upon UV exposure represent target sites for sequence-specific transcription factors. Most of these are distal regulatory regions, highlighting their importance in the cellular response to UV exposure. Furthermore, UV exposure results in an extensive reorganization of super-enhancers, accompanied by expression changes of associated genes, which may in part contribute to the stress response. Taken together, our study provides the first comprehensive resource for genome-wide chromatin changes upon UV irradiation in relation to gene expression and elucidates new aspects of this relationship.

  2. 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.

  3. 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.

  4. 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...

  5. State Law, Policy, and Access to Information: The Case of Mandated Openness in Higher Education

    ERIC Educational Resources Information Center

    McLendon, Michael K.; Hearn, James C.

    2010-01-01

    Background/Context: Every state in the nation has legal requirements, state "sunshine laws," to ensure accountability and fairness in institutions receiving state funds and operating under state authority. These laws have come to significantly influence the ways in which the business of higher education is conducted. Purpose/Objective/Research…

  6. 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.

  7. 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.

  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. Evolution of conductive filament and its impact on reliability issues in oxide-electrolyte based resistive random access memory

    PubMed Central

    Lv, Hangbing; Xu, Xiaoxin; Liu, Hongtao; Liu, Ruoyu; Liu, Qi; Banerjee, Writam; Sun, Haitao; Long, Shibing; Li, Ling; Liu, Ming

    2015-01-01

    The electrochemical metallization cell, also referred to as conductive bridge random access memory, is considered to be a promising candidate or complementary component to the traditional charge based memory. As such, it is receiving additional focus to accelerate the commercialization process. To create a successful mass product, reliability issues must first be rigorously solved. In-depth understanding of the failure behavior of the ECM is essential for performance optimization. Here, we reveal the degradation of high resistance state behaves as the majority cases of the endurance failure of the HfO2 electrolyte based ECM cell. High resolution transmission electron microscopy was used to characterize the change in filament nature after repetitive switching cycles. The result showed that Cu accumulation inside the filament played a dominant role in switching failure, which was further supported by measuring the retention of cycle dependent high resistance state and low resistance state. The clarified physical picture of filament evolution provides a basic understanding of the mechanisms of endurance and retention failure, and the relationship between them. Based on these results, applicable approaches for performance optimization can be implicatively developed, ranging from material tailoring to structure engineering and algorithm design. PMID:25586207

  10. 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.

  11. Unparalleled Ease of Access to a Library of Biheteroaryl Fluorophores via Oxidative Cross-Coupling Reactions: Discovery of Photostable NIR Probe for Mitochondria.

    PubMed

    Cheng, Yangyang; Li, Gaocan; Liu, Yang; Shi, Yang; Gao, Ge; Wu, Di; Lan, Jingbo; You, Jingsong

    2016-04-13

    The development of straightforward accesses to organic functional materials through C-H activation is a revolutionary trend in organic synthesis. In this article, we propose a concise strategy to construct a large library of donor-acceptor-type biheteroaryl fluorophores via the palladium-catalyzed oxidative C-H/C-H cross-coupling of electron-deficient 2H-indazoles with electron-rich heteroarenes. The directly coupled biheteroaryl fluorophores, named Indazo-Fluors, exhibit continuously tunable full-color emissions with quantum yields up to 93% and large Stokes shifts up to 8705 cm(-1) in CH2Cl2. By further fine-tuning of the substituent on the core skeleton, Indazo-Fluor 3l (FW = 274; λem = 725 nm) is obtained as the lowest molecular weight near-infrared (NIR) fluorophore with emission wavelength over 720 nm in the solid state. The NIR dye 5h specifically lights up mitochondria in living cells with bright red luminescence. Typically, commercially available mitochondria trackers suffer from poor photostability. Indazo-Fluor 5h exhibits superior photostability and very low cytotoxicity, which would be a prominent reagent for in vivo mitochondria imaging. PMID:26854564

  12. Interfacial Electrode-Driven Enhancement of the Switching Parameters of a Copper Oxide-Based Resistive Random-Access Memory Device

    NASA Astrophysics Data System (ADS)

    Sangani, L. D. Varma; Kumar, Ch. Ravi; Krishna, M. Ghanashyam

    2016-01-01

    The characteristics of an Au/Cu x O/Au bipolar resistive random-access memory device are reported. It is demonstrated that switching parameters of this device structure can be enhanced by introducing an interfacial Al layer between the Au top electrode and the Cu x O-based dielectric layer. The set and reset voltages are, respectively, between -2.5 V to -6.0 V and +1.2 V to +3.0 V for the Al-based device. In contrast, the range of values are -0.5 V to -2.5 V and +0.5 V to +1.5 V for the set and reset voltages in the absence of Al. The Al-based device has a higher low resistance state value of 5-6 KΩ as compared to the 0.3-0.5 KΩ for the Au-based device, which leads to a 12 times lower power dissipation factor and lower reset current of 370 μA. Endurance studies carried out over 50 switching cycles show less than 2% variation in both the low resistance and high resistance values. The conduction is ohmic at low values of bias and non-ohmic at higher bias voltage which shows that the enhanced behaviour is a result of the formation of an insulating aluminum oxide layer at the Al-Cu x O interface.

  13. Poor People, Poor Places and Access to Health Care in the United States

    ERIC Educational Resources Information Center

    Kirby, James B.

    2008-01-01

    Research suggests that community-level poverty is associated with access to health care net of individual-level characteristics, but no research investigates whether this association differs by individual-level income. Using data from the Medical Expenditure Panel Surveys, the U.S. Census Bureau and the Health Resource and Services Administration,…

  14. Preserving Long-Term Access to United States Government Documents in Legacy Digital Formats

    ERIC Educational Resources Information Center

    Woods, Kam A.

    2010-01-01

    Over the past several decades, millions of digital objects of significant scientific, economic, cultural, and historic value have been published and distributed to libraries and archives on removable media. Providing long-term access to these documents, media files, and software executables is an increasingly complex task because of dependencies…

  15. The States and Public Higher Education Policy: Affordability, Access, and Accountability.

    ERIC Educational Resources Information Center

    Heller, Donald E., Ed.

    The selections in this volume explore the debates surrounding issues of affordability, access, and accountability in higher education. The contributors identify these issues as the three key policy issues facing public higher education in the opening years of the new century. Following an introduction, "The Changing Dynamics of Affordability,…

  16. 28 CFR 16.81 - Exemption of United States Attorneys Systems-limited access.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) Consumer Complaints (JUSTICE/USA-006). (4) Criminal Case Files (JUSTICE/USA-007). (5) Kline-District of..., Criminal Files (JUSTICE/USA-013). (9) Pre-trial Diversion Program Files (JUSTICE/USA-014). These exemptions... Systems-limited access. 16.81 Section 16.81 Judicial Administration DEPARTMENT OF JUSTICE PRODUCTION...

  17. 28 CFR 16.81 - Exemption of United States Attorneys Systems-limited access.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) Consumer Complaints (JUSTICE/USA-006). (4) Criminal Case Files (JUSTICE/USA-007). (5) Kline-District of..., Criminal Files (JUSTICE/USA-013). (9) Pre-trial Diversion Program Files (JUSTICE/USA-014). These exemptions... Systems-limited access. 16.81 Section 16.81 Judicial Administration DEPARTMENT OF JUSTICE PRODUCTION...

  18. 28 CFR 16.81 - Exemption of United States Attorneys Systems-limited access.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) Consumer Complaints (JUSTICE/USA-006). (4) Criminal Case Files (JUSTICE/USA-007). (5) Kline-District of..., Criminal Files (JUSTICE/USA-013). (9) Pre-trial Diversion Program Files (JUSTICE/USA-014). These exemptions... Systems-limited access. 16.81 Section 16.81 Judicial Administration DEPARTMENT OF JUSTICE PRODUCTION...

  19. Accessibility of Early Childhood Education and Care: A State of Affairs

    ERIC Educational Resources Information Center

    Vandenbroeck, Michel; Lazzari, Arianna

    2014-01-01

    We analyse both academic literature and practice reports to discover the main causes for unequal accessibility of high quality early childhood care and education (ECEC). In order to understand and to remedy this inequality we need to consider the interplay between elements of governance, of the management of services and elements on the level of…

  20. 75 FR 28331 - Meaningful Access to United States Currency for Blind and Visually Impaired Persons

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-05-20

    .... You may also e-mail electronic comments to meaningful.access@bep.gov . You may fax comments to 202-874... will be designated after BEP awards the CRPC contract. Except for the postage to mail application forms... the initial battery will be borne by the provider. Readers will be delivered by mail. There will be...

  1. Expanding Access to Early Head Start: State Initiatives for Infants & Toddlers at Risk

    ERIC Educational Resources Information Center

    Colvard, Jamie; Schmit, Stephanie

    2012-01-01

    The federal Early Head Start (EHS) program was created in 1994 to address the comprehensive needs of children under age 3 in low-income families and vulnerable low-income pregnant women. In addition to early learning opportunities, EHS's comprehensive early childhood development programs provide children and families with access to a range of…

  2. Assessment and Access: Hispanics in Higher Education. SUNY Series, United States Hispanic Studies.

    ERIC Educational Resources Information Center

    Keller, Gary D., Ed.; And Others

    This book contains 10 papers on solutions and barriers to improving the access of Hispanic American students to higher education. Following an introductory essay on: "Advances in Assessment and the Potential for Increasing the Number of Hispanics in Higher Education" (G. D. Keller), the papers are organized into four parts. Papers in part I…

  3. 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).

  4. The effect of the existing state of Y on high temperature oxidation properties of magnesium alloys

    NASA Astrophysics Data System (ADS)

    Yu, Xiaowen; Shen, Shijun; Jiang, Bin; Jiang, Zhongtao; Yang, Hong; Pan, Fusheng

    2016-05-01

    This paper studies the effect of the existing state of Y element on the high temperature oxidation resistance of magnesium alloys. Different levels of Al element were added into Mg-2.5Y alloy to obtain different existing state of Y. The oxidation rate of Mg-2.5Y-2.5Al alloy is the highest among Mg-2.5Y, Mg-2.5Y-2.5Al and Mg-2.5Y-4.2Al alloys at 500 °C. An effective and protective Y2O3/MgO composite oxide film was formed on the surface of Mg-2.5Y alloy after oxidized at 500 °C for 360 min. The results show that the dissolved Y element in the matrix was beneficial to improve the oxidation resistance of magnesium alloys. Once Y element transformed to the high temperature stable Al2Y compound, its ability in preventing oxidation would disappear. The formation of Al2Y compound severely deteriorated the oxidation resistance of Mg-2.5Y alloy. In addition, the dissolved Al can also cause the rise of oxidation resistance at a certain extent.

  5. Investigation of oxygen states and reactivities on a nanostructured cupric oxide surface

    NASA Astrophysics Data System (ADS)

    Svintsitskiy, D. A.; Stadnichenko, A. I.; Demidov, D. V.; Koscheev, S. V.; Boronin, A. I.

    2011-08-01

    Nanostructured copper (II) oxide was formed on clean copper foil at room temperature using activated oxygen produced by RF discharge. CuO particles of approximately 10-20 nm were observed on the surface by Scanning Tunneling Microscopy (STM). The copper states and oxygen species of the model cupric oxide were studied by means of X-ray Photoelectron Spectroscopy (XPS). These oxide particles demonstrated abnormally high reactivity with carbon monoxide (CO) at temperatures below 100 °C. The XPS data showed that the interaction of CO with the nanostructured cupric oxide resulted in reduction of the CuO particles to Cu 2O species. The reactivity of the nanostructured cupric oxide to CO was studied at 80 °C using XPS in step-by-step mode. The initial reactivity was estimated to be 5 × 10 -5 and was steadily reduced down to 5 × 10 -9 as the exposure was increased. O1s spectral analysis allowed us to propose that the high initial reactivity was caused by the presence of non-lattice oxygen states on the surface of the nanostructured CuO. We established that reoxidation of the partially reduced nanostructured cupric oxide by molecular oxygen O 2 restored the highly reactive oxygen form on the surface. These results allowed us to propose that the nanostructured cupric oxide could be used for low temperature catalytic CO oxidation. Some hypotheses concerning the nature of the non-lattice oxygen species with high reactivity are also discussed.

  6. 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. PMID:27052472

  7. 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.

  8. Oxidative state and oxidative metabolism in the brain of rats with adjuvant-induced arthritis.

    PubMed

    Wendt, Mariana Marques Nogueira; de Sá-Nakanishi, Anacharis Babeto; de Castro Ghizoni, Cristiane Vizioli; Bersani Amado, Ciomar Aparecida; Peralta, Rosane Marina; Bracht, Adelar; Comar, Jurandir Fernando

    2015-06-01

    The purpose of the present study was to evaluate the oxidative status of the brain of arthritic rats, based mainly on the observation that arthritis induces a pronounced oxidative stress in the liver of arthritis rats and that morphological alterations have been reported to occur in patients with rheumatoid arthritis. Rats with adjuvant-induced arthritis were used. These animals presented higher levels of reactive oxygen species (ROS) in the total brain homogenate (25% higher) and in the mitochondria (+55%) when compared to healthy rats. The nitrite plus nitrate contents, nitric oxide (NO) markers, were also increased in both mitochondria (+27%) and cytosol (+14%). Arthritic rats also presented higher levels of protein carbonyl groups in the total homogenate (+43%), mitochondria (+69%) and cytosol (+145%). Arthritis caused a diminution of oxygen consumption in isolated brain mitochondria only when ascorbate was the electron donor. The disease diminished the mitochondrial cytochrome c oxidase activity by 55%, but increased the transmembrane potential by 16%. The pro-oxidant enzyme xanthine oxidase was 150%, 110% and 283% higher, respectively, in the brain homogenate, mitochondria and cytosol of arthritic animals. The same occurred with the calcium-independent NO-synthase activity that was higher in the brain homogenate (90%) and cytosol (122%) of arthritic rats. The catalase activity, on the other hand, was diminished by arthritis in all cellular fractions (between 30 and 40%). It is apparent that the brain of rats with adjuvant-induced arthritis presents a pronounced oxidative stress and a significant injury to lipids and proteins, a situation that possibly contributes to the brain symptoms of the arthritis disease.

  9. Promoting healthy food consumption: a review of state-level policies to improve access to fruits and vegetables.

    PubMed

    Hood, Carlyn; Martinez-Donate, Ana; Meinen, Amy

    2012-12-01

    Research indicates poor nutrition is a leading determinant of the development of chronic disease, and increasing fruit and vegetable consumption is one method for decreasing obesity. Many policies have focused on increasing the demand for fruits and vegetables through price reductions and coupons. However, without ensuring a stable supply, increased demand can continue to raise prices, crowding out individuals who may otherwise have purchased fruits and vegetables and ultimately leading to continued disparities in access. This paper presents a review of selected state-level policy options recently proposed or implemented in states across the United States, and provides an evidence-based lens through which food access policy can be shaped in the Midwest. This review and potential framework uses Wisconsin to illustrate the feasibility of different state-level decisions and their potential impact on particular populations. Future supply-side policies to consider include expanding Electronic Benefit Transfer to the Special Supplemental Nutrition Program for Women, Infants and Children (WIC),program and farmers markets, incentivizing the purchase of locally grown produce, assisting local specialty farmers directly, and/or establishing a state-level food policy council. This review reveals that a food policy council would create a more sustainable policy analysis process to better ensure future policy adoption is truly comprehensive, encompassing the production, distribution and purchase of locally grown fruits and vegetables.

  10. Promoting healthy food consumption: a review of state-level policies to improve access to fruits and vegetables.

    PubMed

    Hood, Carlyn; Martinez-Donate, Ana; Meinen, Amy

    2012-12-01

    Research indicates poor nutrition is a leading determinant of the development of chronic disease, and increasing fruit and vegetable consumption is one method for decreasing obesity. Many policies have focused on increasing the demand for fruits and vegetables through price reductions and coupons. However, without ensuring a stable supply, increased demand can continue to raise prices, crowding out individuals who may otherwise have purchased fruits and vegetables and ultimately leading to continued disparities in access. This paper presents a review of selected state-level policy options recently proposed or implemented in states across the United States, and provides an evidence-based lens through which food access policy can be shaped in the Midwest. This review and potential framework uses Wisconsin to illustrate the feasibility of different state-level decisions and their potential impact on particular populations. Future supply-side policies to consider include expanding Electronic Benefit Transfer to the Special Supplemental Nutrition Program for Women, Infants and Children (WIC),program and farmers markets, incentivizing the purchase of locally grown produce, assisting local specialty farmers directly, and/or establishing a state-level food policy council. This review reveals that a food policy council would create a more sustainable policy analysis process to better ensure future policy adoption is truly comprehensive, encompassing the production, distribution and purchase of locally grown fruits and vegetables. PMID:23362705

  11. 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…

  12. 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.

  13. Solid oxide fuel cells in the United States

    NASA Astrophysics Data System (ADS)

    Hooie, Diane Traub

    This paper presents an overview of the solid-oxide fuel cell program being undertaken in the US. This program addresses both intermediate and high temperature fuel cells as well as a variety of configurations including planar/monolithic, and tubular. These projects also address a variety of issues such as material compatibility, life/degradation, fuel compatibility, and system scaleup and integration. The primary applications currently being developed is for power generation but a variety of other potential applications, such as transportation, are being considered. The funding for these projects is provided through a variety of sources including the US Government (primarily Departments of Energy, Transportation, and Defense), the Electric Power Research Institute (EPRI), the Gas Research Institute (GRI), and industry.

  14. 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...

  15. [Access to medicines for Alzheimer's disease provided by the Brazilian Unified National Health System in Minas Gerais State, Brazil].

    PubMed

    Almeida-Brasil, Celline Cardoso; Costa, Juliana de Oliveira; Aguiar, Viviane Celestino Ferreira Dos Santos; Moreira, Daniela Pena; Moraes, Edgar Nunes de; Acurcio, Francisco de Assis; Guerra, Augusto Afonso; Álvares, Juliana

    2016-08-01

    This study evaluated barriers to access to treatment for Alzheimer's disease based on administrative cases involving cholinesterase inhibitors (ChEIs) and submitted to the Minas Gerais State Health Secretariat in Brazil in 2012 and 2013. Drawing on data from 165 randomly selected cases, the study addressed the following dimensions of access: geographic accessibility, accommodation, acceptability, availability, and affordability. The administrative processing to supply ChEIs took an average of 39 days and was influenced by characteristics of the path taken by the user. The majority of the prescribers met less than 80% of the required criteria in the Clinical Protocol and Therapeutic Guidelines (CPTG) for Alzheimer's disease. As a result, 38% of requests for medication were denied. Private treatment with ChEIs cost the equivalent of 21 days of the monthly minimum wage. In conclusion, bureaucratic administrative procedures and prescribers' difficulty in following the CPTG hindered access to treatment of Alzheimer's disease and imposed a heavy burden on patients' pockets. PMID:27505179

  16. The Impact of State Appropriations and Grants on Access to Higher Education and Outmigration

    ERIC Educational Resources Information Center

    Toutkoushian, Robert K.; Hillman, Nicholas W.

    2012-01-01

    The question of how states can best use financial policy to achieve their goals is very important for many higher education stakeholders. In this study, the authors use panel data for all 50 states over a 20-year period to examine how state appropriations, need-based grants, and merit-based grants affect student enrollment in college and whether…

  17. Access or Barrier? Tuition and Fee Legislation for Undocumented Students across the States

    ERIC Educational Resources Information Center

    Nguyen, David H. K.; Serna, Gabriel R.

    2014-01-01

    States have responded in a variety of ways to undocumented immigration and its implications for higher education. Some states have allowed undocumented students to seek an affordable college education while others have created barriers. This article highlights the piecemeal legislation that the states have passed in order to respond to the needs…

  18. 77 FR 48199 - Privacy Act; System of Records: State-35, Information Access Programs Records

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-13

    ... writing to the Director; Office of Information Programs and Services, A/GIS/IPS; Department of State, SA-2... Information Programs and Services, A/GIS/IPS; Department of State, SA-2; 515 22nd Street NW.; Washington, DC... Information Programs and Services, A/GIS/IPS; SA-2, Department of State; 515 22nd Street NW.; Washington,...

  19. Characterizing Oxidation State using Bader Analysis, Maximally Localized Wannier Functions and Atomic Orbitals Projection

    NASA Astrophysics Data System (ADS)

    Reeves, Kyle; Kanai, Yosuke

    2013-03-01

    The concept of oxidation state of atoms in molecules and materials is widely used to predict and understand chemical and physical properties. This concept is perhaps driven more empirically than by any rigorous criteria differentiating one oxidation state from another. Within the oxidation state framework, an integer number of electrons is assigned to the nuclei within a system. In practice, a distribution of electron density makes it difficult to quantify such discrete assignments without some ambiguities. We explore three different charge analysis approaches in density functional theory calculations for addressing the oxidation state of important organometallic molecules [Ru(bpy)3]2+ and [Ru(bpy)3]3+, which are widely used for solar energy conversion applications. Bader charge analysis, Wannier function analysis, and atomic orbital projection are employed in this work. Given the highly-localized nature of the d-electrons of the ruthenium atom, the charge analysis methods are also compared with Hubbard-U correction. We also discuss how the solvation by water molecules influences the oxidation state characterization for these organometallic complexes.

  20. Charge Self-Regulation Upon Changing the Oxidation State of Transition Metals in Insulators

    SciTech Connect

    Raebiger, H.; Lany, S.; Zunger, A.

    2008-06-01

    Transition-metal atoms embedded in an ionic or semiconducting crystal can exist in various oxidation states that have distinct signatures in X-ray photoemission spectroscopy and 'ionic radii' which vary with the oxidation state of the atom. These oxidation states are often tacitly associated with a physical ionization of the transition-metal atoms--that is, a literal transfer of charge to or from the atoms. Physical models have been founded on this charge-transfer paradigm, but first-principles quantum mechanical calculations show only negligible changes in the local transition-metal charge as the oxidation state is altered. Here we explain this peculiar tendency of transition-metal atoms to maintain a constant local charge under external perturbations in terms of an inherent, homeostasis-like negative feedback. We show that signatures of oxidation states and multivalence--such as X-ray photoemission core-level shifts, ionic radii and variations in local magnetization--that have often been interpreted as literal charge transfer are instead a consequence of the negative-feedback charge regulation.

  1. Oxidation-resistive copper nanoparticles: photoreduction synthesis and their oxidation state measurements by XAFS and HRTEM

    NASA Astrophysics Data System (ADS)

    Tanaka, H.; Aoki, T.; Yonemura, M.; Miyagawa, M.; Okumura, K.

    2016-05-01

    We examined the synthesis of copper nanoparticles by photoreduction, and characterized them using optical spectroscopy, XAFS measurement, and electron microscopy. Ethanol solution of copper acetate with TiO2 nanoparticles was photoirradated. Optical absorption observation indicated that copper nanoparticles were formed in the solution. XAFS measurement indicated that the nanoparticles were metallic, not oxidized. Electron microscopy observation exhibited that the nanoparticles kept metallic even under exposure to air.

  2. Associations of supermarket accessibility with obesity and fruit and vegetable consumption in the conterminous United States

    PubMed Central

    2010-01-01

    Background Limited access to supermarkets may reduce consumption of healthy foods, resulting in poor nutrition and increased prevalence of obesity. Most studies have focused on accessibility of supermarkets in specific urban settings or localized rural communities. Less is known, however, about how supermarket accessibility is associated with obesity and healthy diet at the national level and how these associations differ in urban versus rural settings. We analyzed data on obesity and fruit and vegetable (F/V) consumption from the Behavioral Risk Factor Surveillance System for 2000-2006 at the county level. We used 2006 Census Zip Code Business Patterns data to compute population-weighted mean distance to supermarket at the county level for different sizes of supermarket. Multilevel logistic regression models were developed to test whether population-weighted mean distance to supermarket was associated with both obesity and F/V consumption and to determine whether these relationships varied for urban (metropolitan) versus rural (nonmetropolitan) areas. Results Distance to supermarket was greater in nonmetropolitan than in metropolitan areas. The odds of obesity increased and odds of consuming F/V five times or more per day decreased as distance to supermarket increased in metropolitan areas for most store size categories. In nonmetropolitan areas, however, distance to supermarket had no associations with obesity or F/V consumption for all supermarket size categories. Conclusions Obesity prevalence increased and F/V consumption decreased with increasing distance to supermarket in metropolitan areas, but not in nonmetropolitan areas. These results suggest that there may be a threshold distance in nonmetropolitan areas beyond which distance to supermarket no longer impacts obesity and F/V consumption. In addition, obesity and food environments in nonmetropolitan areas are likely driven by a more complex set of social, cultural, and physical factors than a single

  3. Data, Data Everywhere, but Access Remains a Big Issue for Researchers: A Review of Access Policies for Publicly-Funded Patient-Level Health Care Data in the United States

    PubMed Central

    Doshi, Jalpa A.; Hendrick, Franklin B.; Graff, Jennifer S.; Stuart, Bruce C.

    2016-01-01

    Introduction: High quality research regarding treatment effectiveness, quality, and value is critical for improving the U.S. health care system. Recognition of this has led federal and state officials to better leverage existing data sources such as medical claims and survey data, but access must be balanced with privacy concerns. Methods: We reviewed and catalogued data access policies for a selection of publicly-funded federal and state datasets to investigate how such policies may be promoting or limiting research activities. Results: We found significant variation in data access policies across federal agencies and across state agencies, including variation for multiple datasets available from the same agency. We also observed numerous indirect hurdles to use of data, including complex data use application procedures, high user fees, and prolonged wait times for data delivery. Conclusions: Policy makers and data owners should consider making changes to data access policies to maximize the utility and availability of these valuable resources. PMID:27141517

  4. Open access of publications by veterinary faculty in the United States and Canada.

    PubMed

    Nault, André J

    2011-01-01

    The free availability of full-text veterinary publications in MEDLINE-indexed journals by US and Canadian veterinary faculty from 2006-7 was determined. Additionally, publishing databases were searched to obtain general statistics on veterinary publishing. A survey of institutional initiatives to promote open-access journals and institutional repositories was also performed. Veterinary faculty published a total of 4,872 articles indexed by MEDLINE in 679 different journals. Of these articles, 1,334 (27%) were available as free full text and were published in 245 different journals. Although 51 veterinary-specific journals offering immediate and free full-text access were identified, few articles in this study appeared in these titles. Rather, most free scholarly articles by veterinary faculty appeared in journals with an embargo period. Academic veterinary institutions may want to recommend acceptance of alternate forms of information dissemination (such as open-access journals and journals published only digitally) to encourage greater global dissemination of their research findings. The promotion and use of digital institutional repositories is also an area for future investment and warrants additional research. PMID:21805933

  5. Open access of publications by veterinary faculty in the United States and Canada.

    PubMed

    Nault, André J

    2011-01-01

    The free availability of full-text veterinary publications in MEDLINE-indexed journals by US and Canadian veterinary faculty from 2006-7 was determined. Additionally, publishing databases were searched to obtain general statistics on veterinary publishing. A survey of institutional initiatives to promote open-access journals and institutional repositories was also performed. Veterinary faculty published a total of 4,872 articles indexed by MEDLINE in 679 different journals. Of these articles, 1,334 (27%) were available as free full text and were published in 245 different journals. Although 51 veterinary-specific journals offering immediate and free full-text access were identified, few articles in this study appeared in these titles. Rather, most free scholarly articles by veterinary faculty appeared in journals with an embargo period. Academic veterinary institutions may want to recommend acceptance of alternate forms of information dissemination (such as open-access journals and journals published only digitally) to encourage greater global dissemination of their research findings. The promotion and use of digital institutional repositories is also an area for future investment and warrants additional research.

  6. 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

    2015-09-01

    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 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.

  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. Private sector participation in delivering tertiary health care: a dichotomy of access and affordability across two Indian states

    PubMed Central

    Katyal, Anuradha; Singh, Prabal Vikram; Bergkvist, Sofi; Samarth, Amit; Rao, Mala

    2015-01-01

    Poor quality care in public sector hospitals coupled with the costs of care in the private sector have trapped India's poor in a vicious cycle of poverty, ill health and debt for many decades. To address this, the governments of Andhra Pradesh (AP) and Maharashtra (MH), India, have attempted to improve people’s access to hospital care by partnering with the private sector. A number of government-sponsored schemes with differing specifications have been launched to facilitate this strategy. Aims This article aims to compare changes in access to, and affordability and efficiency of private and public hospital inpatient (IP) treatments between MH and AP from 2004 to 2012 and to assess whether the health financing innovations in one state resulted in larger or smaller benefits compared with the other. Methods We used data from household surveys conducted in 2004 and 2012 in the two states and undertook a difference-in-difference (DID) analysis. The results focus on hospitalization, out-of-pocket expenditure and length of stay. Results The average IP expenditure for private hospital care has increased in both states, but more so in MH. There was also an observable increase in both utilization of and expenditure on nephrology treatment in private hospitals in AP. The duration of stay recorded in days for private hospitals has increased slightly in MH and declined in AP with a significant DID. The utilization of public hospitals has reduced in AP and increased in MH. Conclusion The state of AP appears to have benefited more than MH in terms of improved access to care by involving the private sector. The Aarogyasri scheme is likely to have contributed to these impacts in AP at least in part. Our study needs to be followed up with repeated evaluations to ascertain the long-term impacts of involving the private sector in providing hospital care. PMID:25759452

  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. Arginine de novo and nitric oxide production in disease states.

    PubMed

    Luiking, Yvette C; Ten Have, Gabriella A M; Wolfe, Robert R; Deutz, Nicolaas E P

    2012-11-15

    Arginine is derived from dietary protein intake, body protein breakdown, or endogenous de novo arginine production. The latter may be linked to the availability of citrulline, which is the immediate precursor of arginine and limiting factor for de novo arginine production. Arginine metabolism is highly compartmentalized due to the expression of the enzymes involved in arginine metabolism in various organs. A small fraction of arginine enters the NO synthase (NOS) pathway. Tetrahydrobiopterin (BH4) is an essential and rate-limiting cofactor for the production of NO. Depletion of BH4 in oxidative-stressed endothelial cells can result in so-called NOS3 "uncoupling," resulting in production of superoxide instead of NO. Moreover, distribution of arginine between intracellular transporters and arginine-converting enzymes, as well as between the arginine-converting and arginine-synthesizing enzymes, determines the metabolic fate of arginine. Alternatively, NO can be derived from conversion of nitrite. Reduced arginine availability stemming from reduced de novo production and elevated arginase activity have been reported in various conditions of acute and chronic stress, which are often characterized by increased NOS2 and reduced NOS3 activity. Cardiovascular and pulmonary disorders such as atherosclerosis, diabetes, hypercholesterolemia, ischemic heart disease, and hypertension are characterized by NOS3 uncoupling. Therapeutic applications to influence (de novo) arginine and NO metabolism aim at increasing substrate availability or at influencing the metabolic fate of specific pathways related to NO bioavailability and prevention of NOS3 uncoupling. These include supplementation of arginine or citrulline, provision of NO donors including inhaled NO and nitrite (sources), NOS3 modulating agents, or the targeting of endogenous NOS inhibitors like asymmetric dimethylarginine.

  11. US state variation in autism insurance mandates: balancing access and fairness.

    PubMed

    Johnson, Rebecca A; Danis, Marion; Hafner-Eaton, Chris

    2014-10-01

    This article examines how nations split decision-making about health services between federal and sub-federal levels, creating variation between states or provinces. When is this variation ethically acceptable? We identify three sources of ethical acceptability-procedural fairness, value pluralism, and substantive fairness-and examine these sources with respect to a case study: the fact that only 30 out of 51 US states or territories passed mandates requiring private insurers to offer extensive coverage of autism behavioral therapies, creating variation for privately insured children living in different US states. Is this variation ethically acceptable? To address this question, we need to analyze whether mandates go to more or less needy states and whether the mandates reflect value pluralism between states regarding government's role in health care. Using time-series logistic regressions and data from National Survey of Children with Special Health Care Needs, Individual with Disabilities Education Act, legislature political composition, and American Board of Pediatrics workforce data, we find that the states in which mandates are passed are less needy than states in which mandates have not been passed, what we call a cumulative advantage outcome that increases between-state disparities rather than a compensatory outcome that decreases between-state disparities. Concluding, we discuss the implications of our analysis for broader discussions of variation in health services provision.

  12. US state variation in autism insurance mandates: balancing access and fairness.

    PubMed

    Johnson, Rebecca A; Danis, Marion; Hafner-Eaton, Chris

    2014-10-01

    This article examines how nations split decision-making about health services between federal and sub-federal levels, creating variation between states or provinces. When is this variation ethically acceptable? We identify three sources of ethical acceptability-procedural fairness, value pluralism, and substantive fairness-and examine these sources with respect to a case study: the fact that only 30 out of 51 US states or territories passed mandates requiring private insurers to offer extensive coverage of autism behavioral therapies, creating variation for privately insured children living in different US states. Is this variation ethically acceptable? To address this question, we need to analyze whether mandates go to more or less needy states and whether the mandates reflect value pluralism between states regarding government's role in health care. Using time-series logistic regressions and data from National Survey of Children with Special Health Care Needs, Individual with Disabilities Education Act, legislature political composition, and American Board of Pediatrics workforce data, we find that the states in which mandates are passed are less needy than states in which mandates have not been passed, what we call a cumulative advantage outcome that increases between-state disparities rather than a compensatory outcome that decreases between-state disparities. Concluding, we discuss the implications of our analysis for broader discussions of variation in health services provision. PMID:24789870

  13. Race/Ethnicity and Geographic Access to Medicaid Substance Use Disorder Treatment Facilities in the United States

    PubMed Central

    Cummings, Janet R.; Wen, Hefei; Ko, Michelle; Druss, Benjamin G.

    2014-01-01

    Background Although substance use disorders (SUD) are prevalent and associated with adverse consequences, treatment rates remain extremely low. Unlike physical and mental health problems, treatment for SUD is predominantly provided in a separate specialty sector and more heavily financed by public sources. The Medicaid expansion under the Affordable Care Act (ACA) has the potential to increase access to treatment for SUD, but only if an infrastructure exists to serve new enrollees. Objective This study examines the availability of outpatient SUD treatment facilities that accept Medicaid across U.S. counties, and whether counties with a higher percentage of racial/ethnic minorities are more likely to have gaps in this infrastructure. Design We used data from the 2009 National Survey of Substance Abuse Treatment Services and the 2011-2012 Area Resource file to examine sociodemographic factors associated with county-level access to SUD treatment facilities that serve Medicaid enrollees. We estimated a probit model with state indicators to adjust for state-level heterogeneity in demographics, politics, and policies. Independent variables assessed county racial/ethnic composition (i.e., percentage Black and percentage Hispanic), percentage living in poverty, percentage living in a rural area, percentage insured with Medicaid, percentage uninsured, and total population. Participants U.S. Counties in all 50 states. Main Outcome Measure Dichotomous indicator for counties with at least one outpatient SUD treatment facility that accepts Medicaid. Results About sixty percent of U.S. counties have at least one outpatient SUD facility that accepts Medicaid, although this rate is lower in many Southern and Midwestern states. Counties with a higher percentage of Black (Marginal Effect [M.E.]=−3.1; 95% CI= −5.2,−0.9%), rural (M.E.=−9.2%; 95% CI=−11.1%,−7.4%), and/or uninsured (M.E.= −9.5%, 95% CI=−13.0%,−5.9%) residents are less likely to have one of these

  14. Current state of open access to journal publications from the University of Zagreb School of Medicine

    PubMed Central

    Škorić, Lea; Vrkić, Dina; Petrak, Jelka

    2016-01-01

    Aims To identify the share of open access (OA) papers in the total number of journal publications authored by the members of the University of Zagreb School of Medicine (UZSM) in 2014. Methods Bibliographic data on 543 UZSM papers published in 2014 were collected using PubMed advanced search strategies and manual data collection methods. The items that had “free full text” icons were considered as gold OA papers. Their OA availability was checked using the provided link to full-text. The rest of the UZSM papers were analyzed for potential green OA through self-archiving in institutional repository. Papers published by Croatian journals were particularly analyzed. Results Full texts of approximately 65% of all UZSM papers were freely available. Most of them were published in gold OA journals (55% of all UZSM papers or 85% of all UZSM OA papers). In the UZSM repository, there were additional 52 freely available authors’ manuscripts from subscription-based journals (10% of all UZSM papers or 15% of all UZSM OA papers). Conclusion The overall proportion of OA in our study is higher than in similar studies, but only half of gold OA papers are accessible via PubMed directly. The results of our study indicate that increased quality of metadata and linking of the bibliographic records to full texts could assure better visibility. Moreover, only a quarter of papers from subscription-based journals that allow self-archiving are deposited in the UZSM repository. We believe that UZSM should consider mandating all faculty members to deposit their publications in UZSM OA repository to increase visibility and improve access to its scientific output. PMID:26935617

  15. Evaluating two experimental approaches for measuring ecosystem carbon oxidation state and oxidative ratio

    NASA Astrophysics Data System (ADS)

    Masiello, C. A.; Gallagher, M. E.; Randerson, J. T.; Deco, R. M.; Chadwick, O. A.

    2008-09-01

    Degree of oxidation of organic carbon (Cox) is a fundamental property of the carbon cycle, reflecting the synthesis and decomposition of natural organic matter. Cox is also related to ecosystem oxidative ratio (OR), the molar ratio of O2 to CO2 fluxes associated with net ecosystem exchange (NEE). Here we compare two methods for measuring Cox and OR: (1) %C, %H, %N, and %O elemental analysis, and (2) heat of combustion (ΔHc) measured by means of bomb calorimetry coupled with %C elemental analysis (hereafter referred to as calorimetry). Compared with %C, %N, %H, and %O elemental analysis, calorimetry generates Cox and OR data more rapidly and cheaply. However, calorimetric measurements yield less accurate Cox and OR data. We additionally report Cox and OR data for a pair of biomass standards and a suite of biomass samples. The OR values we measured in these samples were less variable than OR data reported in the literature (generated by simultaneous measurement of ecosystem O2 and CO2 gas mixing ratios). Our biomass OR values had a mean of 1.03 and range of 0.99-1.06. These estimates are lower than the OR value of 1.10 that is often used to partition uptake of fossil fuel CO2 between the ocean and the terrestrial biosphere.

  16. Ensuring Equitable Access to Strong Teachers: Important Elements of an Effective State Action Plan

    ERIC Educational Resources Information Center

    Metz, Rachel

    2015-01-01

    Every community has strong teachers who help their students learn to high levels. But far too often low-income students and students of color are short-changed when it comes to teacher quality. Federal law requires states to end these disparities. But states, recognizing that most hiring, compensation, and promotional decisions, not to mention…

  17. Design Guidelines: Study of Handicapped Accessibility in South Carolina State Parks.

    ERIC Educational Resources Information Center

    South Carolina State Dept. of Parks, Recreation, and Tourism, Columbia. Div. of Engineering and Planning.

    The publication provides guidelines for the design of new facilities or rehabilitation of existing facilities to accommodate physically handicapped persons in the South Carolina State Parks system. The guidelines are also recommended for use in regional, special district, county, and municipal parks within the state. The guidelines were developed…

  18. Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides

    SciTech Connect

    Wen, Xiaodong; Martin, Richard L.; Henderson, Thomas M.; Scuseria, Gustavo E.

    2013-02-13

    The actinide oxides have been extensively studied in the context of the nuclear fuel cycle. They are also of fundamental interest as members of a class of strongly correlated materials, the Mott insulators. Their complex physical and chemical properties make them challenging systems to characterize, both experimentally and theoretically. Chiefly, this is because actinide oxides can exhibit both electronic localization and electronic delocalization and have partially occupied f orbitals, which can lead to multiple possibilities for ground states. Of particular concern for theoretical work is that the large number of competing states display strong correlations which are dffcult to capture with computationally tractable methods.

  19. 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.

  20. Low oxidation state aluminum-containing cluster anions: Cp∗AlnH-, n = 1-3

    NASA Astrophysics Data System (ADS)

    Zhang, Xinxing; Ganteför, Gerd; Eichhorn, Bryan; Mayo, Dennis; Sawyer, William H.; Gill, Ann F.; Kandalam, Anil K.; Schnöckel, Hansgeorg; Bowen, Kit

    2016-08-01

    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.

  1. 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.

  2. 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. PMID:20127784

  3. Corannulene reduction. Spectroscopic detection of all anionic oxidation states

    SciTech Connect

    Baumgarten, M.; Gherghel, L.; Wagner, M.; Weitz, A.; Rabinovitz, M. |; Cheng, P.C.; Scott, L.T.

    1995-06-14

    The reduction of corannulene (1) has been followed by parallel detection of optical absorption, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) spectroscopies. The major findings are the existence of a diamagnetic dianion that can be observed in NMR and negligible counterion influences in the mono- and dianion. The diamagnetic state of the dianion is also supported by vanishing EPR intensity and semiempirical calculations and exhibits one indistinguishable proton NMR resonance at -5.6 ppm for potassium and lithium as counterions, respectively. The NMR signal is strongly temperature dependent and can only be obtained at low temperature (T < 230 K) where the line width decreases with temperature. Further reduction to the trianion and tetraanion succeeds with Li as the reducing metal, but not with K even at ambient temperatures. The EPR spectra of the trianion show a pronounced temperature dependence with at least two Li cations being strongly coupled. 18 refs., 3 figs., 3 tabs.

  4. 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.

  5. Improving Access to Malaria Rapid Diagnostic Test in Niger State, Nigeria: An Assessment of Implementation up to 2013.

    PubMed

    Awoleye, Olatunji Joshua; Thron, Chris

    2016-01-01

    Nigeria's 2009-2013 malaria strategic plan adopted WHO diagnosis and treatment guidelines, which include the use of rapid diagnostic tests (RDTs) prior to prescribing treatment with artemisinin combination therapies (ACTs). The current study explores accessibility barriers to the use of RDTs in Niger State and makes recommendations for improving the uptake of RDTs. The study employs literature review, review of data from the Niger State Health Management Information System for January-October 2013, and application of Peters' conceptual framework for assessing access to health services. Data showed that 27 percent of public health facilities (HFs) implemented RDTs, with the aid of donor funds. In these facilities, 77 percent of fever cases presented during the study period were tested with RDTs; 53 percent of fever cases were confirmed cases of malaria, while 60 percent of fever cases were treated. Stockouts of RDTs were a major constraint, and severe fever tended to trigger presumptive treatment. We conclude that although implementation of RDTs led to a reduction in the use of ACTs at HFs, more substantial reduction could be achieved if the state government directed more resources towards the acquisition of RDTs as well as raising the level of awareness of potential users. PMID:27042376

  6. Improving Access to Malaria Rapid Diagnostic Test in Niger State, Nigeria: An Assessment of Implementation up to 2013

    PubMed Central

    Awoleye, Olatunji Joshua; Thron, Chris

    2016-01-01

    Nigeria's 2009–2013 malaria strategic plan adopted WHO diagnosis and treatment guidelines, which include the use of rapid diagnostic tests (RDTs) prior to prescribing treatment with artemisinin combination therapies (ACTs). The current study explores accessibility barriers to the use of RDTs in Niger State and makes recommendations for improving the uptake of RDTs. The study employs literature review, review of data from the Niger State Health Management Information System for January–October 2013, and application of Peters' conceptual framework for assessing access to health services. Data showed that 27 percent of public health facilities (HFs) implemented RDTs, with the aid of donor funds. In these facilities, 77 percent of fever cases presented during the study period were tested with RDTs; 53 percent of fever cases were confirmed cases of malaria, while 60 percent of fever cases were treated. Stockouts of RDTs were a major constraint, and severe fever tended to trigger presumptive treatment. We conclude that although implementation of RDTs led to a reduction in the use of ACTs at HFs, more substantial reduction could be achieved if the state government directed more resources towards the acquisition of RDTs as well as raising the level of awareness of potential users. PMID:27042376

  7. Understanding Digital Technology Access and Use Among New York State Residents to Enhance Dissemination of Health Information

    PubMed Central

    Gerstner, Gena; Pergolino, Kristen; Graham, Yvonne; Strogatz, David

    2016-01-01

    Background Many state and local health departments, as well as community organizations, have been using new technologies to disseminate health information to targeted populations. Yet little data exist that show access and use patterns, as well as preferences for receiving health information, at the state level. Objective This study was designed to obtain information about media and technology use, and health information seeking patterns, from a sample of New York State (NYS) residents. Methods A cross-sectional telephone survey (with mobile phones and landlines) was developed to assess media and technology access, use patterns, and preferences for receiving health information among a sample of 1350 residents in NYS. The survey used random digit dialing methodology. A weighted analysis was conducted utilizing Stata/SE software. Results Data suggest that NYS residents have a high level of computer and Internet use; 82% have at least one working computer at home, and 85% use the Internet at least sometimes. Mobile phone use is also high; 90% indicated having a mobile phone, and of those 63% have a smartphone. When asked about preferences for receiving health information from an organization, many people preferred websites (49%); preferences for other sources varied by demographic characteristics. Conclusions Findings suggest that the Internet and other technologies are viable ways to reach NYS residents, but agencies and organizations should still consider using traditional methods of communication in some cases, and determine appropriate channels based on the population of interest. PMID:27227163

  8. Avenues and barriers to access of services for immigrant elders: state and local policies for OAA units on aging.

    PubMed

    Okafor, Maria C

    2009-07-01

    The diversification and aging of the US population has been at the root of many political and policy debates in recent years. Of particular interest has been the place of immigrants in an aging society, and what rights these immigrants are entitled to. The objective of this article is to describe the current avenues and barriers to access of services for immigrant elders and examine potential solutions for reform. The article begins with a historical overview of the policy issue, followed by the current status of the issue in the United States and suggestions for reform.

  9. 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

    2015-10-01

    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.

  10. Access road from State Route 240 to the 200 West Area, Hanford Site, Richland, Washington: Environmental assessment

    SciTech Connect

    Not Available

    1994-02-01

    The US Department of Energy (DOE) proposes to construct an access road on the Hanford Site, from State Route (SR) 240 to Beloit Avenue in the 200 West Area. Traffic volume during shift changes creates an extremely serious congestion and safety problem on Route 4S from the Wye barricade to the 200 Areas. A Risk Evaluation (Trost 1992) indicated that there is a probability of 1.53 fatal accidents on Route 4S within 2 years. To help alleviate this danger, a new 3.5-kilometer (2.2-mile)-long access road would be constructed from Beloit Avenue in the 200 West Area to SR 240. In addition, administrative controls such as redirecting traffic onto alternate routes would be used to further reduce traffic volume. The proposed access road would provide an alternative travel-to-work route for many outer area personnel, particularly those with destinations in the 200 West Area. This proposal is the most reasonable alternative to reduce the problem. While traffic safety would be greatly improved, a small portion of the shrub-steppe habitat would be disturbed. The DOE would offset any habitat damage by re-vegetation or other appropriate habitat enhancement activities elsewhere on the Hanford Site. This Environmental Assessment (EA) provides information about the environmental impacts of the proposed action, so a decision can be made to either prepare an Environmental Impact Statement or issue a Finding of No Significant Impact.

  11. [Factors associated with waiting time and access to kidney transplants in Belo Horizonte, Minas Gerais State, Brazil'].

    PubMed

    Machado, Elaine Leandro; Gomes, Isabel Cristina; Acurcio, Francisco de Assis; César, Cibele Comini; Almeida, Maria Cristina de Mattos; Cherchiglia, Mariangela Leal

    2012-12-01

    The objective of this study was to analyze factors associated with access to kidney transplants from living and cadaver donors in Belo Horizonte, Minas Gerais State, Brazil. The authors conducted a non-concurrent cohort study of patients on the waiting list for kidney transplants from 2000 to 2004 and followed until transplantation, death, exclusion, or continued presence on the line at the end of the study on December 31, 2005. The Cox model was used for competing risks. Of the 835 patients, 22.7% were transplanted. Lower risk of transplantation from living donors and cadavers was observed in patients with more time on dialysis and blood type O. Lower risk of transplantation from living donors was observed in residents in a high health risk area and in recipients with diabetes. The greatest disparity in access was observed in transplants from living donors, since there were no significant socio-demographic differences in transplants from cadaver donors. One can infer that the organ allocation system contributed to mitigating socio-demographic inequalities, and that clinical issues were more relevant in access to transplants from cadaver donors.

  12. 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.

  13. A geospatial approach to evaluation of accessibility to secondary educational institution in Ogun State, Nigeria

    NASA Astrophysics Data System (ADS)

    Ogunyemi, S. A.; Muibi, K. H.; Eguaroje, O. E.; Fabiyi, O. O.; Halilu, A. S.

    2014-06-01

    The study therefore examined the spatial distribution of secondary school and the accessibility levels to students in Yewa South local Government area of Nigeria and the factors that give rise to them with a view to providing a framework for effective placement of students. Primary and secondary data were used for the study. Primary data was collected using questionnaire and a hand-held GPS receiver used to capture the coordinate points of schools and other relevant data. Secondary data include administrative map, population figures of both students and Teachers, Names and addresses of the secondary schools in the study area, the school placement sheet and list of schools. The data analysis was carried out using network analysis. School location, number of secondary schools in each ward and the total area were used to determine the pattern of distribution of secondary schools in the study area. Settlements, roads, schools location, number of secondary schools, ward and school enrolments were used to generate both school accessibility and effective placement measure using network analysis. Network analyses were also performed to evaluate nearest school to student and a set of origin-destination (OD) matrix. However, the whole of 25 secondary schools in Yewa south were considered for network analysis ward by ward, and the results of the distance students travel from their settlements to their various schools were shown for all the secondary schools in each ward. Out of 415 Students, 210 students travel below 2 km to their schools which constitute 50.60% total number of students in the local government area while 205 students travel above 2 km to their schools which constitute 49.40%.

  14. 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

  15. Accessing long-lived nuclear singlet states between chemically equivalent spins without breaking symmetry

    PubMed Central

    Feng, Yesu; Davis, Ryan M.; Warren, Warren S.

    2013-01-01

    Long-lived nuclear spin states could greatly enhance the applicability of hyperpolarized nuclear magnetic resonance. Using singlet states between inequivalent spin pairs has been shown to extend the signal lifetime by more than an order of magnitude compared to the spin lattice relaxation time (T1), but they have to be prevented from evolving into other states. In the most interesting case the singlet is between chemically equivalent spins, as it can then be inherently an eigenstate. However this presents major challenges in the conversion from bulk magnetization to singlet. In the only case demonstrated so far, a reversible chemical reaction to break symmetry was required. Here we present a pulse sequence technique that interconverts between singlet spin order and bulk magnetization without breaking the symmetry of the spin system. This technique is independent of field strength and is applicable to a broad range of molecules. PMID:23505397

  16. 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.

  17. 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)

  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. 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…

  1. 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…

  2. 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

  3. 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.

  4. 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.

  5. Comparing racial and immigrant health status and health care access in later life in Canada and the United States.

    PubMed

    Prus, Steven G; Tfaily, Rania; Lin, Zhiqiu

    2010-09-01

    Little comparative research exists on health experiences and conditions of minority groups in Canada and the United States, despite both countries having a racially diverse population with a significant proportion of immigrants. This article explores race and immigrant disparities in health and health care access across the two countries. The study focus was on middle and old age given the change and increasing diversity in health and health care policy, such as Medicare. Logistic regression analysis of data from the 2002-2003 Joint Canada/United States Survey of Health shows that the joint effect of race and nativity on health outcomes - health differences between native and foreign-born Whites and non-Whites - is largely insignificant in Canada but considerable in the U.S. Non-White native and foreign-born Americans within both 45-to-64 and 65-and-over age groups experience significant disadvantage in health status and access to care, irrespective of health insurance coverage, demographic, socio-economic, and lifestyle factors.

  6. Racial/ethnic disparities in chronic diseases of youths and access to health care in the United States.

    PubMed

    Price, James H; Khubchandani, Jagdish; McKinney, Molly; Braun, Robert

    2013-01-01

    Racial/ethnic minorities are 1.5 to 2.0 times more likely than whites to have most of the major chronic diseases. Chronic diseases are also more common in the poor than the nonpoor and this association is frequently mediated by race/ethnicity. Specifically, children are disproportionately affected by racial/ethnic health disparities. Between 1960 and 2005 the percentage of children with a chronic disease in the United States almost quadrupled with racial/ethnic minority youth having higher likelihood for these diseases. The most common major chronic diseases of youth in the United States are asthma, diabetes mellitus, obesity, hypertension, dental disease, attention-deficit/hyperactivity disorder, mental illness, cancers, sickle-cell anemia, cystic fibrosis, and a variety of genetic and other birth defects. This review will focus on the psychosocial rather than biological factors that play important roles in the etiology and subsequent solutions to these health disparities because they should be avoidable and they are inherently unjust. Finally, this review examines access to health services by focusing on health insurance and dental insurance coverage and access to school health services. PMID:24175301

  7. Paying the price works: increasing goal-state access cost improves problem solving and mitigates the effect of interruption.

    PubMed

    Morgan, Phillip L; Patrick, John

    2013-01-01

    The aim of this paper was to investigate whether it was possible to induce more internal planning in the four-disk Tower of Hanoi (ToH) in order not only to produce more efficient problem solving but also to make it more resistant to the negative effect of interruption. The theoretical frameworks of soft constraints and the memory for goals model underpinned Experiments 1 and 2. In both experiments, three goal-state access cost conditions were used: high (mouse movements and 2.5-s delay), medium (mouse movements) and low (goal state always available). In Experiment 1, more memory-based planning was induced by the high cost condition, which resulted in fewer moves to solution and the gradual development of an efficient subgoaling strategy, resulting in more perfect solutions. In Experiment 2, the same condition protected performance against a 10-s interruption irrespective of the interrupting task (blank screen, mental arithmetic, or three-disk ToH). The more memory-based planning strategy, induced by high access cost, presumably strengthened participants' goals during planning and problem solving, making them less susceptible to decay and interference from interruption. These novel results are discussed in the context of other recent studies. PMID:22928975

  8. Increasing Student Access and Success in Dual Enrollment Programs: 13 Model State-Level Policy Components

    ERIC Educational Resources Information Center

    Zinth, Jennifer Dounay

    2014-01-01

    Dual enrollment or concurrent enrollment programs allow eligible high school students to take postsecondary courses for college and, usually, high school credit. Programs are nearly ubiquitous--in 2014, courses for dual or concurrent enrollment credit are offered in every state and the District of Columbia. Statewide policies govern these programs…

  9. The 2% Transition: Supporting Access to State Assessments for Students with Disabilities

    ERIC Educational Resources Information Center

    Jamgochian, Elisa M.; Ketterlin-Geller, Leanne R.

    2015-01-01

    Most students with disabilities participate in state assessments with or without accommodations [based on each student's Individualized Education Program (IEP)]. A small number of students with the most severe or profound intellectual disabilities participate in an alternate assessment based on alternate achievement standards (AA-AAS). Until…

  10. Access to Supplemental Educational Services in the Central Region States. Issues & Answers. REL 2007-No. 007

    ERIC Educational Resources Information Center

    Barley, Zoe; Wegner, Sandra K.

    2007-01-01

    The Central Region states (Colorado, Kansas, Missouri, Nebraska, North Dakota, South Dakota, and Wyoming) lag behind the nation in the rate of participation in supplemental educational services that schools failing to make adequate progress for three consecutive years must offer to eligible students under the No Child Left Behind Act. This study…

  11. Does Access to High Quality Early Education Vary by State Policy Context?

    ERIC Educational Resources Information Center

    Connors, Maia C.; Morris, Pamela A.; Friedman-Krauss, Allison H.

    2015-01-01

    Research suggests that attending high quality, formal early childhood education (ECE) is associated with stronger cognitive and social-emotional skills, especially for low-income children. Yet at current funding levels, federally-funded programs like Head Start cannot serve all eligible children. Thus, state-level policies governing the…

  12. Comparative susceptibility of kudzu accessions from Southeastern United States to infection by Phakopsora pachyrhizi

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soybean rust, caused by Phakopsora pachyrhizi, was first discovered in the United States (U.S.), in the fall of 2004. The potential for economic loss in the U.S. hinges largely on whether or not the pathogen can readily survive winters in the absence of soybean. Kudzu (Pueraria montana var. lobata...

  13. Serrano II: Equal Access to School Resources and Fiscal Neutrality--A View from Washington State.

    ERIC Educational Resources Information Center

    Andrews, Michael E.

    This paper discusses an approach to solving the school financing problem that treats separately the twin concerns of taxational and educational equity. Part 1 reviews the decision of the California supreme court in Serrano 1 as it relates to these concerns and the manner in which the state district court on remand attempted to utilize the concept…

  14. State Policy Recommendations for Providing Educators Access to College- and Career-Ready Open Educational Resources

    ERIC Educational Resources Information Center

    Voss, Hans

    2015-01-01

    As states and districts transition to college- and career-ready standards and aligned assessments, the need for high-quality instructional materials is clear. Open Educational Resources (OER) offer a low-cost solution with high potential to assist teachers nationwide in helping students meet the demands of higher standards. More and more…

  15. Increasing Access to Higher Education among Low-Income Students: The Washington State Achievers Program

    ERIC Educational Resources Information Center

    Myers, Carrie B.; Brown, Doreen E.; Pavel, D. Michael

    2010-01-01

    The purpose of this study was to assess how a comprehensive precollege intervention and developmental program among low-income high school students contributed to college enrollment outcomes measured in 2006. Our focus was on the Fifth Cohort of the Washington State Achievers (WSA) Program, which provides financial, academic, and college…

  16. US State Variation in Autism Insurance Mandates: Balancing Access and Fairness

    ERIC Educational Resources Information Center

    Johnson, Rebecca A.; Danis, Marion; Hafner-Eaton, Chris

    2014-01-01

    This article examines how nations split decision-making about health services between federal and sub-federal levels, creating variation between states or provinces. When is this variation ethically acceptable? We identify three sources of ethical acceptability--procedural fairness, value pluralism, and substantive fairness--and examine these…

  17. Access or Inclusion? Conceptualisation and Operationalisation of Gender Equality in Zimbabwean State Universities

    ERIC Educational Resources Information Center

    Chauraya, Efiritha

    2014-01-01

    This article explores concerns about gender inequality in Zimbabwean state universities. The researcher's interest arose from the realisation of persistent gender inequalities despite initiatives to close gender gaps. Of particular concern is the conceptualization and operationalisation of gender equality in institutions. Focusing only on the…

  18. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  19. 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.

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

    SciTech Connect

    Liang, W.

    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 S{sub 2} 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 S{sub 2} state with the g{approx}4 electron paramagnetic resonance (EPR) signal (S{sub 2}-g4 state) was compared with that in the S{sub 2} state with multiline signal (S{sub 2}-MLS state) and the S{sub 1} state. The S{sub 2}-g4 state has a higher XAS inflection point energy than that of the S{sub 1} state, indicating the oxidation of Mn in the advance from the S{sub 1} to the S{sub 2}-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 S{sub 2}-g4 state is different from that in the S{sub 2}-MLS or the S{sub 1} state. In the S{sub 2}-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 {angstrom} and 2.85 {angstrom}. Very little distance disorder exists in the second shell of the S{sub 1} or S{sub 2}-MLS states. The third shell of the S{sub 2}-g4 state at about 3.3 {angstrom} also contains increased heterogeneity relative to that of the S{sub 2}-MLS or the S{sub 1} 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 {open_quotes}pure{close_quotes} S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S{sub 1} {yields} S{sub 2} transition.

  1. Washington state initiative trims Medicaid budget, ED utilization without denying access.

    PubMed

    2014-06-01

    In its first year of operation, Washington state's "ER is for Emergencies" initiative has helped to save the state's Medicaid budget $33.6 million. The initiative, which is based on the implementation of seven best practices, has succeeded in part by improving care coordination and by linking EDs across the state so information can be shared electronically. Leaders of the effort concede that while state pressure was essential in pushing providers to address excess use of the ED for nonemergency needs, they stress that the approach worked because all sides were willing to sit down and hammer out a solution. Further, they note that the infrastructure is now in place to address other problems in a similar fashion. An analysis of claims data shows that in the first year of the initiative, ED visits by Medicaid recipients declined by 9.9%, and the rate of visits by frequent ED utilizers declined by 10.7%. The analysis also shows that ED visits resulting in a scheduled drug prescription fell by 24%, and the rate of visits for a low-acuity diagnosis declined by 14.2%. While many EDs had to adjust their staffing and other resources to accommodate reduced volumes, others experienced few changes or even saw an uptick in volume, possibly from implementation of the Affordable Care Act. Leaders of the effort say the biggest challenge involved with implementing the initiative was securing administrative buy-in for investments that would likely result in improved efficiency and care, but also reduced revenue--at least initially.

  2. Accessing High Pressure States Relevant to Core Conditions in the Giant Planets

    SciTech Connect

    Remington, B A; Cavallo, R M; Edwards, M J; Ho, D D; Lorenz, K T; Lorenzana, H E; Lasinski, B F; McNaney, J M; Pollaine, S M; Smith, R F

    2004-04-15

    We have designed an experimental technique to use on the National Ignition Facility (NIF) laser to achieve very high pressure (P{sub max} > 10 Mbar = 1000 GPa), dense states of matter at moderate temperatures (kT < 0.5 eV = 6000 K), relevant to the core conditions of the giant planets. A discussion of the conditions in the interiors of the giant planets is given, and an experimental design that can approach those conditions is described.

  3. 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

    2015-11-01

    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

  4. 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.

  5. 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}.

  6. Accessibility to Oral Antiviral Therapy for Patients with Chronic Hepatitis C in the United States

    PubMed Central

    Saab, Sammy; Jimenez, Melissa; Fong, Tiffany; Wu, Crystal; Bau, Sherona; Jamal, Zoha; Grotts, Jonathan; Elashoff, David

    2016-01-01

    Abstract Background: Hepatitis C (HCV) direct acting antiviral agents (DAAs) are safe, effective, and tolerable. Most contraindications to interferon-based treatment are no long applicable. The aims of this study were to understand the predictors of approval to drug accessibility. Methods: We studied all consecutive patients with HCV prescribed DAAs between October 2014 and July 2015. Data on demographic, socio-economic status, comorbidities, baseline laboratory values, and assessment of liver disease severity, insurance, and specialty pharmacy type were collected. Multivariate analyses were performed to identify predictors of prescription approval. Results: In total, 410 patients were prescribed DAAs between October 2014 and July 2015. Of those, 332 (81%) patients were insurance approved for therapy. Of the 332 patients accepted, 251 were accepted after the first prescription attempt, and 38 were accepted after the second and third attempts. The number of attempts for the other 43 approved patients was unknown. Older age (p = 0.001), employment (p = 0.001), lack of comorbidities (p = 0.02), liver transplantation (p = 0.018), and advanced liver disease (p = 0.001) were more likely associated with obtaining approval. Household income was not associated with insurance approval. In the multivariate analysis, Medicare insurance (odds ratio [OR]) 2.67, 95% confidence interval [CI] 0.96–7.20), lack of nonliver comorbidities (OR 2.72, 95% CI 1.35–5.43), and the presence of advanced liver disease (OR 1.82, 95% CI 1.04–3.24) independently predicted drug approval. Conclusion: Despite the availability of DAAs for HCV, barriers from insurance carriers continue to impair widespread use. Patients with advanced liver disease, Medicare, and without comorbidities are most likely to be insurance approved for DAAs. PMID:27350937

  7. 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

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

    SciTech Connect

    Lucier, G.M.

    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 PtF{sub 6}{sup {minus}}, RuF{sub 6}{sup {minus}}, or RhF{sub 6}{sup {minus}}, 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 IrF{sub 6}{sup {minus}} to IrF{sub 6} at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag{sup 2+} (MF{sub 6}{sup {minus}}){sub 2} salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag{sup 2+}. The anion must also be a poor F{sup {minus}} donor; otherwise, either AgF{sup +} salts or AgF{sub 2} are generated.

  9. Dialysis vascular access management by interventional nephrology programs at University Medical Centers in the United States.

    PubMed

    Vachharajani, Tushar J; Moossavi, Shahriar; Salman, Loay; Wu, Steven; Dwyer, Amy C; Ross, Jamie; Dukkipati, Ramanath; Maya, Ivan D; Yevzlin, Alexander S; Agarwal, Anil; Abreo, Kenneth D; Work, Jack; Asif, Arif

    2011-01-01

    The development of interventional nephrology has undoubtedly led to an improvement in patient care at many facilities across the United States. However, these services have traditionally been offered by interventional nephrologists in the private practice arena. While interventional nephrology was born in the private practice setting, several academic medical centers across the United States have now developed interventional nephrology programs. University Medical Centers (UMCs) that offer interventional nephrology face challenges, such as smaller dialysis populations, limited financial resources, and real or perceived political "turf" issues." Despite these hurdles, several UMCs have successfully established interventional nephrology as an intricate part of a larger nephrology program. This has largely been accomplished by consolidating available resources and collaborating with other specialties irrespective of the size of the dialysis population. The collaboration with other specialties also offers an opportunity to perform advanced procedures, such as application of excimer laser and endovascular ultrasound. As more UMCs establish interventional nephrology programs, opportunities for developing standardized training centers will improve, resulting in better quality and availability of nephrology-related procedures, and providing an impetus for research activities. PMID:21999740

  10. United States Human Access to Space, Exploration of the Moon and Preparation for Mars Exploration

    NASA Technical Reports Server (NTRS)

    Rhatigan, Jennifer L.

    2009-01-01

    In the past, men like Leonardo da Vinci and Jules Verne imagined the future and envisioned fantastic inventions such as winged flying machines, submarines, and parachutes, and posited human adventures like transoceanic flight and journeys to the Moon. Today, many of their ideas are reality and form the basis for our modern world. While individual visionaries like da Vinci and Verne are remembered for the accuracy of their predictions, today entire nations are involved in the process of envisioning and defining the future development of mankind, both on and beyond the Earth itself. Recently, Russian, European, and Chinese teams have all announced plans for developing their own next generation human space vehicles. The Chinese have announced their intention to conduct human lunar exploration, and have flown three crewed space missions since 2003, including a flight with three crew members to test their extravehicular (spacewalking) capabilities in September 2008. Very soon, the prestige, economic development, scientific discovery, and strategic security advantage historically associated with leadership in space exploration and exploitation may no longer be the undisputed province of the United States. Much like the sponsors of the seafaring explorers of da Vinci's age, we are motivated by the opportunity to obtain new knowledge and new resources for the growth and development of our own civilization. NASA's new Constellation Program, established in 2005, is tasked with maintaining the United States leadership in space, exploring the Moon, creating a sustained human lunar presence, and eventually extending human operations to Mars and beyond. Through 2008, the Constellation Program developed a full set of detailed program requirements and is now completing the preliminary design phase for the new Orion Crew Exploration Vehicle (CEV), the Ares I Crew Launch Vehicle, and the associated infrastructure necessary for humans to explore the Moon. Component testing is well

  11. 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.

  12. 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.

  13. Access, affordability, and insurance complexity are often worse in the United States compared to ten other countries.

    PubMed

    Schoen, Cathy; Osborn, Robin; Squires, David; Doty, Michelle M

    2013-12-01

    The United States is in the midst of the most sweeping health insurance expansions and market reforms since the enactment of Medicare and Medicaid in 1965. Our 2013 survey of the general population in eleven countries-Australia, Canada, France, Germany, the Netherlands, New Zealand, Norway, Sweden, Switzerland, the United Kingdom, and the United States-found that US adults were significantly more likely than their counterparts in other countries to forgo care because of cost, to have difficulty paying for care even when insured, and to encounter time-consuming insurance complexity. Signaling the lack of timely access to primary care, adults in the United States and Canada reported long waits to be seen in primary care and high use of hospital emergency departments, compared to other countries. Perhaps not surprisingly, US adults were the most likely to endorse major reforms: Three out of four called for fundamental change or rebuilding. As US health insurance expansions unfold, the survey offers benchmarks to assess US progress from an international perspective, plus insights from other countries' coverage-related policies. PMID:24226092

  14. Access, affordability, and insurance complexity are often worse in the United States compared to ten other countries.

    PubMed

    Schoen, Cathy; Osborn, Robin; Squires, David; Doty, Michelle M

    2013-12-01

    The United States is in the midst of the most sweeping health insurance expansions and market reforms since the enactment of Medicare and Medicaid in 1965. Our 2013 survey of the general population in eleven countries-Australia, Canada, France, Germany, the Netherlands, New Zealand, Norway, Sweden, Switzerland, the United Kingdom, and the United States-found that US adults were significantly more likely than their counterparts in other countries to forgo care because of cost, to have difficulty paying for care even when insured, and to encounter time-consuming insurance complexity. Signaling the lack of timely access to primary care, adults in the United States and Canada reported long waits to be seen in primary care and high use of hospital emergency departments, compared to other countries. Perhaps not surprisingly, US adults were the most likely to endorse major reforms: Three out of four called for fundamental change or rebuilding. As US health insurance expansions unfold, the survey offers benchmarks to assess US progress from an international perspective, plus insights from other countries' coverage-related policies.

  15. Observation of a thermally accessible triplet state resulting from rotation around a main-group π bond.

    PubMed

    Kostenko, Arseni; Tumanskii, Boris; Karni, Miriam; Inoue, Shigeyoshi; Ichinohe, Masaaki; Sekiguchi, Akira; Apeloig, Yitzhak

    2015-10-01

    We report the first direct spectroscopic observation by electron paramagnetic resonance (EPR) spectroscopy of a triplet diradical that is formed in a thermally induced rotation around a main-group π bond, that is, the SiSi double bond of tetrakis(di-tert-butylmethylsilyl)disilene (1). The highly twisted ground-state geometry of singlet 1 allows access to the perpendicular triplet diradical 2 at moderate temperatures of 350-410 K. DFT-calculated zero-field splitting (ZFS) parameters of 2 accurately reproduce the experimentally observed half-field transition. Experiment and theory suggest a thermal equilibrium between 1 and 2 with a very low singlet-triplet energy gap of only 7.3 kcal mol(-1) . PMID:26297814

  16. Probing the Folded State of Fibronectin Type III Domains in Stretched Fibrils by Measuring Buried Cysteine Accessibility*

    PubMed Central

    Lemmon, Christopher A.; Ohashi, Tomoo; Erickson, Harold P.

    2011-01-01

    Fibronectin (FN) is an extracellular matrix protein that is assembled into fibrils by cells during tissue morphogenesis and wound healing. FN matrix fibrils are highly elastic, but the mechanism of elasticity has been debated: it may be achieved by mechanical unfolding of FN-III domains or by a conformational change of the molecule without domain unfolding. Here, we investigate the folded state of FN-III domains in FN fibrils by measuring the accessibility of buried cysteines. Four of the 15 FN-III domains (III-2, -3, -9, and -11) appear to unfold in both stretched fibrils and in solution, suggesting that these domains spontaneously open and close even in the absence of tension. Two FN-III domains (III-6 and -12) appear to unfold only in fibrils and not in solution. These results suggest that domain unfolding can at best contribute partially to the 4-fold extensibility of fibronectin fibrils. PMID:21652701

  17. Observation of a thermally accessible triplet state resulting from rotation around a main-group π bond.

    PubMed

    Kostenko, Arseni; Tumanskii, Boris; Karni, Miriam; Inoue, Shigeyoshi; Ichinohe, Masaaki; Sekiguchi, Akira; Apeloig, Yitzhak

    2015-10-01

    We report the first direct spectroscopic observation by electron paramagnetic resonance (EPR) spectroscopy of a triplet diradical that is formed in a thermally induced rotation around a main-group π bond, that is, the SiSi double bond of tetrakis(di-tert-butylmethylsilyl)disilene (1). The highly twisted ground-state geometry of singlet 1 allows access to the perpendicular triplet diradical 2 at moderate temperatures of 350-410 K. DFT-calculated zero-field splitting (ZFS) parameters of 2 accurately reproduce the experimentally observed half-field transition. Experiment and theory suggest a thermal equilibrium between 1 and 2 with a very low singlet-triplet energy gap of only 7.3 kcal mol(-1) .

  18. 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.

  19. 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

  20. 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.

  1. Oxidation of Plasma Cysteine/Cystine Redox State in Endotoxin-Induced Lung Injury

    PubMed Central

    Iyer, Smita S.; Jones, Dean P.; Brigham, Kenneth L.; Rojas, Mauricio

    2009-01-01

    Several lines of evidence indicate that perturbations in the extracellular thiol/disulfide redox environment correlate with the progression and severity of acute lung injury (ALI). Cysteine (Cys) and its disulfide Cystine (CySS) constitute the most abundant, low-molecular-weight thiol/disulfide redox couple in the plasma, and Cys homeostasis is adversely affected during the inflammatory response to infection and injury. While much emphasis has been placed on glutathione (GSH) and glutathione disulfide (GSSG), little is known about the regulation of the Cys/CySS couple in ALI. The purpose of the present study was to determine whether endotoxin administration causes a decrease in Cys and/or an oxidation of the plasma Cys/CySS redox state (Eh Cys/CySS), and to determine whether these changes were associated with changes in plasma Eh GSH/GSSG. Mice received endotoxin intraperitoneally, and GSH and Cys redox states were measured at time points known to correlate with the progression of endotoxin-induced lung injury. Eh in mV was calculated using Cys, CySS, GSH, and GSSG values by high-performance liquid chromatography and the Nernst equation. We observed distinct effects of endotoxin on the GSH and Cys redox systems during the acute phase; plasma Eh Cys/CySS was selectively oxidized early in response to endotoxin, while Eh GSH/GSSG remained unchanged. Unexpectedly, subsequent oxidation of Eh GSH/GSSG and Eh Cys/CySS occurred as a consequence of endotoxin-induced anorexia. Taken together, the results indicate that enhanced oxidation of Cys, altered transport of Cys and CySS, and decreased food intake each contribute to the oxidation of plasma Cys/CySS redox state in endotoxemia. PMID:18664641

  2. 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.

  3. Prion gene (PRNP) haplotype variation in United States goat breeds (Open Access publication)

    PubMed Central

    White, Stephen; Herrmann-Hoesing, Lynn; O'rourke, Katherine; Waldron, Daniel; Rowe, Joan; Alverson, Janet

    2008-01-01

    Scrapie eradication efforts cost 18 million dollars annually in the United States and rely heavily upon PRNP genotyping of sheep. Genetic resistance might reduce goat scrapie and limit the risk of goats serving as a scrapie reservoir, so PRNP coding sequences were examined from 446 goats of 10 breeds, 8 of which had not been previously examined at PRNP. The 10 observed alleles were all related to one of two central haplotypes by a single amino acid substitution. At least five of these alleles (M142, R143, S146, H154, and K222) have been associated with increased incubation time or decreased odds of scrapie. To the best of our knowledge, neither S146 nor K222 has been found in any goats with scrapie, though further evaluation will be required to demonstrate true resistance. S146 was more common, present in several breeds at widely varying frequencies, while K222 was observed only in two dairy breeds at low frequency. Overall, this study provides frequency data on PRNP alleles in US goats, shows the pattern of relationships between haplotypes, and demonstrates segregation of multiple scrapieassociated alleles in several breeds not examined before at PRNP. PMID:18694550

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Filling in the GAPS: evaluating completeness and coverage of open-access biodiversity databases in the United States

    DOE PAGES

    Troia, Matthew J.; McManamay, Ryan A.

    2016-06-12

    Primary biodiversity data constitute observations of particular species at given points in time and space. Open-access electronic databases provide unprecedented access to these data, but their usefulness in characterizing species distributions and patterns in biodiversity depend on how complete species inventories are at a given survey location and how uniformly distributed survey locations are along dimensions of time, space, and environment. Our aim was to compare completeness and coverage among three open-access databases representing ten taxonomic groups (amphibians, birds, freshwater bivalves, crayfish, freshwater fish, fungi, insects, mammals, plants, and reptiles) in the contiguous United States. We compiled occurrence records frommore » the Global Biodiversity Information Facility (GBIF), the North American Breeding Bird Survey (BBS), and federally administered fish surveys (FFS). In this study, we aggregated occurrence records by 0.1° × 0.1° grid cells and computed three completeness metrics to classify each grid cell as well-surveyed or not. Next, we compared frequency distributions of surveyed grid cells to background environmental conditions in a GIS and performed Kolmogorov–Smirnov tests to quantify coverage through time, along two spatial gradients, and along eight environmental gradients. The three databases contributed >13.6 million reliable occurrence records distributed among >190,000 grid cells. The percent of well-surveyed grid cells was substantially lower for GBIF (5.2%) than for systematic surveys (BBS and FFS; 82.5%). Still, the large number of GBIF occurrence records produced at least 250 well-surveyed grid cells for six of nine taxonomic groups. Coverages of systematic surveys were less biased across spatial and environmental dimensions but were more biased in temporal coverage compared to GBIF data. GBIF coverages also varied among taxonomic groups, consistent with commonly recognized geographic, environmental, and institutional

  12. Filling in the GAPS: evaluating completeness and coverage of open-access biodiversity databases in the United States.

    PubMed

    Troia, Matthew J; McManamay, Ryan A

    2016-07-01

    Primary biodiversity data constitute observations of particular species at given points in time and space. Open-access electronic databases provide unprecedented access to these data, but their usefulness in characterizing species distributions and patterns in biodiversity depend on how complete species inventories are at a given survey location and how uniformly distributed survey locations are along dimensions of time, space, and environment. Our aim was to compare completeness and coverage among three open-access databases representing ten taxonomic groups (amphibians, birds, freshwater bivalves, crayfish, freshwater fish, fungi, insects, mammals, plants, and reptiles) in the contiguous United States. We compiled occurrence records from the Global Biodiversity Information Facility (GBIF), the North American Breeding Bird Survey (BBS), and federally administered fish surveys (FFS). We aggregated occurrence records by 0.1° × 0.1° grid cells and computed three completeness metrics to classify each grid cell as well-surveyed or not. Next, we compared frequency distributions of surveyed grid cells to background environmental conditions in a GIS and performed Kolmogorov-Smirnov tests to quantify coverage through time, along two spatial gradients, and along eight environmental gradients. The three databases contributed >13.6 million reliable occurrence records distributed among >190,000 grid cells. The percent of well-surveyed grid cells was substantially lower for GBIF (5.2%) than for systematic surveys (BBS and FFS; 82.5%). Still, the large number of GBIF occurrence records produced at least 250 well-surveyed grid cells for six of nine taxonomic groups. Coverages of systematic surveys were less biased across spatial and environmental dimensions but were more biased in temporal coverage compared to GBIF data. GBIF coverages also varied among taxonomic groups, consistent with commonly recognized geographic, environmental, and institutional sampling biases. This

  13. Filling in the GAPS: evaluating completeness and coverage of open-access biodiversity databases in the United States.

    PubMed

    Troia, Matthew J; McManamay, Ryan A

    2016-07-01

    Primary biodiversity data constitute observations of particular species at given points in time and space. Open-access electronic databases provide unprecedented access to these data, but their usefulness in characterizing species distributions and patterns in biodiversity depend on how complete species inventories are at a given survey location and how uniformly distributed survey locations are along dimensions of time, space, and environment. Our aim was to compare completeness and coverage among three open-access databases representing ten taxonomic groups (amphibians, birds, freshwater bivalves, crayfish, freshwater fish, fungi, insects, mammals, plants, and reptiles) in the contiguous United States. We compiled occurrence records from the Global Biodiversity Information Facility (GBIF), the North American Breeding Bird Survey (BBS), and federally administered fish surveys (FFS). We aggregated occurrence records by 0.1° × 0.1° grid cells and computed three completeness metrics to classify each grid cell as well-surveyed or not. Next, we compared frequency distributions of surveyed grid cells to background environmental conditions in a GIS and performed Kolmogorov-Smirnov tests to quantify coverage through time, along two spatial gradients, and along eight environmental gradients. The three databases contributed >13.6 million reliable occurrence records distributed among >190,000 grid cells. The percent of well-surveyed grid cells was substantially lower for GBIF (5.2%) than for systematic surveys (BBS and FFS; 82.5%). Still, the large number of GBIF occurrence records produced at least 250 well-surveyed grid cells for six of nine taxonomic groups. Coverages of systematic surveys were less biased across spatial and environmental dimensions but were more biased in temporal coverage compared to GBIF data. GBIF coverages also varied among taxonomic groups, consistent with commonly recognized geographic, environmental, and institutional sampling biases. This

  14. 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.

  15. 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.

  16. 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.

  17. Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

    PubMed

    Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

    2015-03-01

    Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

  18. Reducing operation voltages by introducing a low-k switching layer in indium–tin-oxide-based resistance random access memory

    NASA Astrophysics Data System (ADS)

    Jin, Fu-Yuan; Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Pan, Chih-Hung; Lin, Chih-Yang; Chen, Po-Hsun; Chen, Min-Chen; Huang, Hui-Chun; Lo, Ikai; Zheng, Jin-Cheng; Sze, Simon M.

    2016-06-01

    In this letter, we inserted a low dielectric constant (low-k) or high dielectric constant (high-k) material as a switching layer in indium–tin-oxide-based resistive random-access memory. After measuring the two samples, we found that the low-k material device has very low operating voltages (‑80 and 110 mV for SET and RESET operations, respectively). Current fitting results were then used with the COMSOL software package to simulate electric field distribution in the layers. After combining the electrical measurement results with simulations, a conduction model was proposed to explain resistance switching behaviors in the two structures.

  19. Reducing operation voltages by introducing a low-k switching layer in indium-tin-oxide-based resistance random access memory

    NASA Astrophysics Data System (ADS)

    Jin, Fu-Yuan; Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Pan, Chih-Hung; Lin, Chih-Yang; Chen, Po-Hsun; Chen, Min-Chen; Huang, Hui-Chun; Lo, Ikai; Zheng, Jin-Cheng; Sze, Simon M.

    2016-06-01

    In this letter, we inserted a low dielectric constant (low-k) or high dielectric constant (high-k) material as a switching layer in indium-tin-oxide-based resistive random-access memory. After measuring the two samples, we found that the low-k material device has very low operating voltages (-80 and 110 mV for SET and RESET operations, respectively). Current fitting results were then used with the COMSOL software package to simulate electric field distribution in the layers. After combining the electrical measurement results with simulations, a conduction model was proposed to explain resistance switching behaviors in the two structures.

  20. 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

  1. Iodine-mediated solvent-controlled selective electrophilic cyclization and oxidative esterification of o-alkynyl aldehydes: an easy access to pyranoquinolines, pyranoquinolinones, and isocumarins.

    PubMed

    Verma, Akhilesh K; Rustagi, Vineeta; Aggarwal, Trapti; Singh, Amit P

    2010-11-19

    Chemoselective behavior of iodine in different solvents in the electrophilic iodocyclization of o-alkynyl aldehydes is described. o-Alkynyl aldehydes 3a-t on reaction with I2 in CH2Cl2 with appropriate nucleophiles provides pyrano[4,3-b]quinolines 4a-f, via formation of cyclic iodonium intermediate Q; however, using alcohols as a solvent as well as nucleophile, o-alkynyl esters 5a-y were obtained selectively in good to excellent yields via formation of hypoiodide intermediate R. Subsequently, o-alkynyl esters were converted in to pyranoquinolinones 6a-i and isocoumarin 6j by electrophilic iodocyclization. This developed oxidative esterification provides a novel access for the chemoselective synthesis of esters 5q-u from aldehydes 3n-p without oxidizing primary alcohol present in the substrate.

  2. Homicide and geographic access to gun dealers in the United States

    PubMed Central

    Wiebe, Douglas J; Krafty, Robert T; Koper, Christopher S; Nance, Michael L; Elliott, Michael R; Branas, Charles C

    2009-01-01

    Modification of FFLs through federal, state, and local regulation may be a feasible intervention to reduce gun homicide in major cities. PMID:19549293

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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.

  5. Multiplet splitting for the XPS of heavy elements: Dependence on oxidation state

    NASA Astrophysics Data System (ADS)

    Bagus, Paul S.; Nelin, Connie J.; Al-Salik, Yahya; Ilton, Eugene S.; Idriss, Hicham

    2016-01-01

    Multiplet splittings in X-ray Photo-electron Spectroscopy, XPS, are a means of distinguishing different open shell occupations, or different oxidation states, in a material being studied. Indeed, especially for 3d transition metal complexes, they have provided fingerprints of the metal oxidation state. The present work provides theoretical and experimental evidence that it may also be possible to use multiplets to characterize the oxidation state of heavy metal, lanthanide and actinide, cations in complexes. However, it is important to make a proper choice of the XPS region to study in order to obtain large multiplet splittings. We identify a low binding energy, BE, peak that had been observed for Ce(III) in CeOx as a high spin coupled multiplet. Furthermore, we show that a low BE feature with reasonable intensity is characteristic of other XPS regions and of other metals. This feature arises from a high spin multiplet and serves as a fingerprint to distinguish closed shell from open shell cations. Evidence is presented that it may also be possible to distinguish different open shell occupations.

  6. 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.

  7. 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.

  8. Do the higher oxidation states of the photosynthetic O2-evolving system contain bound H2O?

    PubMed

    Radmer, R; Ollinger, O

    1986-01-01

    A modified mass spectrometer was used to determine whether the higher oxidation states of the photosynthetic O2-evolving system contain substrate water that is not freely exchangeable with the external medium. Our data indicated that the higher oxidation states contain no appreciable bound, non-exchangeable H2O. This suggests that H2O oxidation takes place via a rapid, concerted, all-or-none mechanism rather than by a mechanism involving stable, partially oxidized, H2O-derived intermediates. These findings set definite constraints on possible mechanisms of O2 evolution.

  9. 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

  10. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    SciTech Connect

    Nelson, George J.; Harris, William M.; Izzo, John R. Jr.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu Yijin; Pianetta, Piero

    2011-04-25

    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.

  11. Three-dimensional mapping of nickel oxidation states using full field x-ray absorption near edge structure nanotomography

    NASA Astrophysics Data System (ADS)

    Nelson, George J.; Harris, William M.; Izzo, John R.; Grew, Kyle N.; Chiu, Wilson K. S.; Chu, Yong S.; Yi, Jaemock; Andrews, Joy C.; Liu, Yijin; Pianetta, Piero

    2011-04-01

    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.

  12. Structural differences between the ready and unready oxidized states of [NiFe] hydrogenases.

    PubMed

    Volbeda, Anne; Martin, Lydie; Cavazza, Christine; Matho, Michaël; Faber, Bart W; Roseboom, Winfried; Albracht, Simon P J; Garcin, Elsa; Rousset, Marc; Fontecilla-Camps, Juan C

    2005-05-01

    [NiFe] hydrogenases catalyze the reversible heterolytic cleavage of molecular hydrogen. Several oxidized, inactive states of these enzymes are known that are distinguishable by their very different activation properties. So far, the structural basis for this difference has not been understood because of lack of relevant crystallographic data. Here, we present the crystal structure of the ready Ni-B state of Desulfovibrio fructosovorans [NiFe] hydrogenase and show it to have a putative mu-hydroxo Ni-Fe bridging ligand at the active site. On the other hand, a new, improved refinement procedure of the X-ray diffraction data obtained for putative unready Ni-A/Ni-SU states resulted in a more elongated electron density for the bridging ligand, suggesting that it is a diatomic species. The slow activation of the Ni-A state, compared with the rapid activation of the Ni-B state, is therefore proposed to result from the different chemical nature of the ligands in the two oxidized species. Our results along with very recent electrochemical studies suggest that the diatomic ligand could be hydro-peroxide. PMID:15803334

  13. Expanding Access

    ERIC Educational Resources Information Center

    Roach, Ronald

    2007-01-01

    There is no question that the United States lags behind most industrialized nations in consumer access to broadband Internet service. For many policy makers and activists, this shortfall marks the latest phase in the struggle to overcome the digital divide. To remedy this lack of broadband affordability and availability, one start-up firm--with…

  14. Increasing Access for Economically Disadvantaged Students: The NSF/CSEM & S-STEM Programs at Louisiana State University

    NASA Astrophysics Data System (ADS)

    Wilson, Zakiya S.; Iyengar, Sitharama S.; Pang, Su-Seng; Warner, Isiah M.; Luces, Candace A.

    2012-10-01

    Increasing college degree attainment for students from disadvantaged backgrounds is a prominent component of numerous state and federal legislation focused on higher education. In 1999, the National Science Foundation (NSF) instituted the "Computer Science, Engineering, and Mathematics Scholarships" (CSEMS) program; this initiative was designed to provide greater access and support to academically talented students from economically disadvantaged backgrounds. Originally intended to provide financial support to lower income students, this NSF program also advocated that additional professional development and advising would be strategies to increase undergraduate persistence to graduation. This innovative program for economically disadvantaged students was extended in 2004 to include students from other disciplines including the physical and life sciences as well as the technology fields, and the new name of the program was Scholarships for Science, Technology, Engineering and Mathematics (S-STEM). The implementation of these two programs in Louisiana State University (LSU) has shown significant and measurable success since 2000, making LSU a Model University in providing support to economically disadvantaged students within the STEM disciplines. The achievement of these programs is evidenced by the graduation rates of its participants. This report provides details on the educational model employed through the CSEMS/S-STEM projects at LSU and provides a path to success for increasing student retention rates in STEM disciplines. While the LSU's experience is presented as a case study, the potential relevance of this innovative mentoring program in conjunction with the financial support system is discussed in detail.

  15. 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.

  16. 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.

  17. 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

  18. Peptide translocation through the plasma membrane of human cells: Can oxidative stress be exploited to gain better intracellular access?

    PubMed Central

    Wang, Ting-Yi; Pellois, Jean-Philippe

    2016-01-01

    ABSTRACT Cell-penetrating peptides (CPPs) enter cells primarily by escaping from endosomal compartments or by directly translocating across the plasma membrane. Due to their capability of permeating into the cytosolic space of the cell, CPPs are utilized for the delivery of cell-impermeable molecules. However, the fundamental mechanisms and parameters associated with the penetration of CPPs and their cargos through the lipid bilayer have not been fully determined. This in turn has hampered their usage in biotechnological or therapeutic applications. We have recently reported that the cell penetration activity of poly-arginine CPPs (PACPPs) is dependent on the oxidation status of the plasma membrane of cells. Our data support a model where the positively-charged PACPP binds negatively-charged lipids exposed on the cell surface as a result of oxidative damage. The PACPP then crosses the membrane via formation of inverted micelles with these anionic lipids. This model provides a plausible explanation for the high variability in the cell delivery efficiency of a PACPP often observed in different settings. Notably, taking into account the current literature describing the effects of lipid oxidation, our data point to a highly complex and underappreciated interplay between PACPPs and oxidized membrane species. Overall, a better understanding of oxidation-dependent cell penetration might provide a fundamental basis for development of optimal cell permeable peptides (including cyclic peptides, stapled peptides, peptoids, etc…) and of robust delivery protocols. PMID:27574543

  19. Peptide translocation through the plasma membrane of human cells: Can oxidative stress be exploited to gain better intracellular access?

    PubMed

    Wang, Ting-Yi; Pellois, Jean-Philippe

    2016-01-01

    Cell-penetrating peptides (CPPs) enter cells primarily by escaping from endosomal compartments or by directly translocating across the plasma membrane. Due to their capability of permeating into the cytosolic space of the cell, CPPs are utilized for the delivery of cell-impermeable molecules. However, the fundamental mechanisms and parameters associated with the penetration of CPPs and their cargos through the lipid bilayer have not been fully determined. This in turn has hampered their usage in biotechnological or therapeutic applications. We have recently reported that the cell penetration activity of poly-arginine CPPs (PACPPs) is dependent on the oxidation status of the plasma membrane of cells. Our data support a model where the positively-charged PACPP binds negatively-charged lipids exposed on the cell surface as a result of oxidative damage. The PACPP then crosses the membrane via formation of inverted micelles with these anionic lipids. This model provides a plausible explanation for the high variability in the cell delivery efficiency of a PACPP often observed in different settings. Notably, taking into account the current literature describing the effects of lipid oxidation, our data point to a highly complex and underappreciated interplay between PACPPs and oxidized membrane species. Overall, a better understanding of oxidation-dependent cell penetration might provide a fundamental basis for development of optimal cell permeable peptides (including cyclic peptides, stapled peptides, peptoids, etc…) and of robust delivery protocols. PMID:27574543

  20. Peptide translocation through the plasma membrane of human cells: Can oxidative stress be exploited to gain better intracellular access?

    PubMed

    Wang, Ting-Yi; Pellois, Jean-Philippe

    2016-01-01

    Cell-penetrating peptides (CPPs) enter cells primarily by escaping from endosomal compartments or by directly translocating across the plasma membrane. Due to their capability of permeating into the cytosolic space of the cell, CPPs are utilized for the delivery of cell-impermeable molecules. However, the fundamental mechanisms and parameters associated with the penetration of CPPs and their cargos through the lipid bilayer have not been fully determined. This in turn has hampered their usage in biotechnological or therapeutic applications. We have recently reported that the cell penetration activity of poly-arginine CPPs (PACPPs) is dependent on the oxidation status of the plasma membrane of cells. Our data support a model where the positively-charged PACPP binds negatively-charged lipids exposed on the cell surface as a result of oxidative damage. The PACPP then crosses the membrane via formation of inverted micelles with these anionic lipids. This model provides a plausible explanation for the high variability in the cell delivery efficiency of a PACPP often observed in different settings. Notably, taking into account the current literature describing the effects of lipid oxidation, our data point to a highly complex and underappreciated interplay between PACPPs and oxidized membrane species. Overall, a better understanding of oxidation-dependent cell penetration might provide a fundamental basis for development of optimal cell permeable peptides (including cyclic peptides, stapled peptides, peptoids, etc…) and of robust delivery protocols.

  1. 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.

  2. Secondary Measures of Access to Abortion Services in the United States, 2011 and 2012: Gestational Age Limits, Cost, and Harassment

    PubMed Central

    Jerman, Jenna; Jones, Rachel K.

    2016-01-01

    Background Aspects of U.S. clinical abortion service provision such as gestational age limits, charges for abortion services, and anti-abortion harassment can impact the accessibility of abortion; this study documents changes in these measures between 2008 and 2012. Methods In 2012 and 2013, we surveyed all known abortion-providing facilities in the United States (n = 1,720). This study summarizes information obtained about gestational age limits, charges, and exposure to anti-abortion harassment among clinics; response rates for relevant items ranged from 54% (gestational limits) to 80% (exposure to harassment). Weights were constructed to compensate for nonresponding facilities. We also examine the distribution of abortions and abortion facilities by region. Findings Almost all abortion facilities (95%) offered abortions at 8 weeks’ gestation; 72% did so at 12 weeks, 34% at 20 weeks, and 16% at 24 weeks in 2012. In 2011 and 2012, the median charge for a surgical abortion at 10 weeks gestation was $495, and $500 for an early medication abortion, compared with $503 and $524 (adjusted for inflation) in 2009. In 2011, 84% of clinics experienced at least one form of harassment, only slightly higher than found in 2009. Hospitals and physicians’ offices accounted for a substantially smaller proportion of facilities in the Midwest and South. Clinics in the Midwest and South were exposed to more harassment than their counterparts in the Northeast and West. Conclusions Although there was a substantial decline in abortion incidence between 2008 and 2011, the secondary measures of abortion access examined in this study changed little during this time period. PMID:24981401

  3. 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.

  4. A State Survey's Experience with the National Geothermal Database System: Lessons Learned to Improve Data Discovery, Access, and Stewardship

    NASA Astrophysics Data System (ADS)

    Hills, D. J.; Richard, S. M.

    2013-12-01

    State Geological Surveys in the U.S., in conjunction with the U.S. Geological Survey, have thousands of databases, directories, and 85,000+ geologic maps that collectively constitute a national geoscience data 'backbone' for research and practical applications. Much of this data has been at-risk in its current format or difficult to access. Organized by the Association of American State Geologists (AASG) with funding from the U.S. Department of Energy, the National Geothermal Data System (NGDS) has been able to make large quantities of geothermal-relevant geoscience data available to the public by creating a national, sustainable, distributed, and interoperable network of data providers. State Surveys or their equivalent have been instrumental to the success of the NGDS, but many have not had previous experience developing the necessary resources for credibility, sustainability, and interoperability beyond their area. The Geological Survey of Alabama (GSA) was no exception; here we expand upon some of the lessons the GSA has learned throughout this process, including a vision of a path forward. A major challenge that had to be overcome was the disconnect between interoperability requirements for the content models and the research interests of scientists providing the data. This was overcome by open and direct dialogue between the content developers and content providers. Although the iterative process could be frustrating at times, the result is a robust and thoroughly tested content model for geothermal data. This content model will provide an excellent starting point for other geoscience data content models. The greatest challenges the GSA encountered during the NGDS project were lack of standardization of our own data resources; lack of documentation; unknown quality of data; and lack of provenance of data. Moving forward, the GSA now has a model for stewardship of data, including what information and metadata should be collected to ensure future

  5. 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.

  6. 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.

  7. Synthesis of carbon-encapsulated iron nanoparticles via solid state reduction of iron oxide nanoparticles

    SciTech Connect

    Bystrzejewski, M.

    2011-06-15

    The encapsulation of iron nanoparticles in protective carbon cages leads to unique hybrid core-shell nanomaterials. Recent literature reports suggest that such nanocomposites can be obtained in a relatively simple process involving the solid state carbothermal reduction of iron oxide nanoparticles. This approach is very attractive because it does not require advanced equipment and consumes less energy in comparison to widely used plasma methods. The presented more-in-depth study shows that the carbothermal approach is sensitive to temperature and the process yield strongly depends on the morphology and crystallinity of the carbon material used as a reductant. - Graphical abstract: Reduction of iron oxide nanoparticles by carbon black at 1200 deg. C yields well crystallized carbon-encapsulated iron nanoparticles. Highlights: > Carbon-encapsulated iron nanoparticles were synthesized by carbothermal reduction of iron oxide nanoparticles. > The process has the highest selectivity at 1200 C. > Lower temperatures result in iron oxide nanoparticles wrapped in carbon matrix. > The encapsulation rate of Fe at 1200 deg. C was found to be 15%.

  8. Spectroscopic characterization of zinc oxide nanorods synthesized by solid-state reaction

    NASA Astrophysics Data System (ADS)

    Prasad, Virendra; D'Souza, Charlene; Yadav, Deepti; Shaikh, A. J.; Vigneshwaran, Nadanathangam

    2006-09-01

    Well-crystallized zinc oxide nanorods have been fabricated by single step solid-state reaction using zinc acetate and sodium hydroxide, at room temperature. The sodium lauryl sulfate (SLS) stabilized zinc oxide nanorods were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and photoluminescence spectroscopy. The X-ray diffraction revealed the wurtzite structure of zinc oxide. The size estimation by XRD and TEM confirmed that the ZnO nanorods are made of single crystals. The growth of zinc oxide crystals into rod shape was found to be closely related to its hexagonal nature. The mass ratio of SLS:ZnO in the nanorods was found to be 1:10 based on the thermogravimetric analysis. Blue shift of photoluminescence emission was noticed in the ZnO nanorods when compared to that of ZnO bulk. FT-IR analysis confirmed the binding of SLS with ZnO nanorods. Apart from ease of preparation, this method has the advantage of eco-friendliness since the solvent and other harmful chemicals were eliminated in the synthesis protocol.

  9. Solid state chemistry of nitrogen oxides--part I: surface consumption of NO.

    PubMed

    Minissale, M; Fedoseev, G; Congiu, E; Ioppolo, S; Dulieu, F; Linnartz, H

    2014-05-14

    The role of nitrogen and oxygen chemistry in the interstellar medium is still rather poorly understood. Nitric oxide, NO, has been proposed as an important precursor in the formation of larger N- and O-bearing species, such as hydroxylamine, NH2OH, and nitrogen oxides, NO2 and N2O. The topic of this study is the solid state consumption of NO via oxygenation and the formation of NO2 and other nitrogen oxides (ONNO2 and N2O4) under conditions close to those encountered on icy grains in quiescent interstellar clouds. In our experiments nitric oxide and oxygen allotropes (O, O2, and O3) or N atoms are co-deposited under ultra-high vacuum conditions on different substrates (silicate, graphite, compact ASW ice, and gold) at temperatures ranging between 10 and 35 K. Reaction products are monitored via Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS) and Temperature Programmed Desorption (TPD) using mass spectrometry. We find that NO2 is efficiently formed in NO + O/O2/O3/N solid surface reactions. These are essentially barrier free and offer a pathway for the formation of NO2 in space. Nitrogen dioxide, however, has not been astronomically detected, contradicting the efficient reaction channel found here. This is likely due to other pathways, including regular hydrogenation reactions, as discussed separately in part II of this study.

  10. The impact of the initial state on the kinetics of oxidation ion- modified fuel cladding alloy E110

    NASA Astrophysics Data System (ADS)

    Kalin, B. A.; Volkov, N. V.; Valikov, R. A.; Yashin, A. S.; Yakutkina, T. V.

    2016-04-01

    The paper examines the impact of the initial state (the presence of impurities, surface preparation), and surface alloying on the kinetics of the oxidation of fuel cladding alloy E110. The studies concluded that the use of ionic polishing instead of traditional chemical polishing helps to reduce the rate of oxidation of zirconium alloys. Also studied the effect of alloying elements introduced in the surface layers of claddings by ion mixing on the kinetics of the oxidation of the alloy E110.

  11. Control of lipid oxidation during exercise: role of energy state and mitochondrial factors.

    PubMed

    Sahlin, K; Harris, R C

    2008-12-01

    Despite considerable progress during recent years our understanding of how lipid oxidation (LOx) is controlled during exercise remains incomplete. This review focuses on the role of mitochondria and energy state in the control of LOx. LOx increases in parallel with increased energy demand up to an exercise intensity of about 50-60% of VO(2max) after which the contribution of lipid decreases. The switch from lipid to carbohydrate (CHO) is of energetic advantage due to the increased ATP/O(2) yield. In the low-intensity domain (<50%VO(2max)) a moderate reduction in energy state will stimulate both LOx and CHO oxidation and relative fuel utilization is mainly controlled by substrate availability and the capacity of the metabolic pathways. In the high-intensity domain (>60%VO(2max)) there is a pronounced decrease in energy state, which will stimulate glycolysis in excess of the substrate requirements of the oxidative processes. This will lead to acidosis, reduced levels of free Coenzyme A (CoASH) and reduced levels of free carnitine. Acidosis and reduced carnitine may limit the carnitine-mediated transfer of long-chain fatty acids (LCFA) into mitochondria and may thus explain the observed reduction in LOx during high-intensity exercise. Another potential mechanism, suggested in this review, is that Acyl-CoA synthetase (ACS), an initial step in LCFA catabolism, functions as a regulator of LOx. ACS activity is suggested to be under control of CoASH and energy state. Furthermore, evidence exists that additional control points exist beyond mitochondrial FA influx. The nature and site of this control remain to be investigated. PMID:18557841

  12. 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.

  13. Pd-Catalyzed C-H activation/oxidative cyclization of acetanilide with norbornene: concise access to functionalized indolines.

    PubMed

    Gao, Yang; Huang, Yubing; Wu, Wanqing; Huang, Kefan; Jiang, Huanfeng

    2014-08-01

    An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C-H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C-H activation of acetanilides is supposed to be a key intermediate in this transformation. PMID:24942255

  14. Structures of the superoxide reductase from Pyrococcus furiosus in the oxidized and reduced states.

    PubMed

    Yeh, A P; Hu, Y; Jenney, F E; Adams, M W; Rees, D C

    2000-03-14

    Superoxide reductase (SOR) is a blue non-heme iron protein that functions in anaerobic microbes as a defense mechanism against reactive oxygen species by catalyzing the reduction of superoxide to hydrogen peroxide [Jenney, F. E., Jr., Verhagen, M. F. J. M., Cui, X. , and Adams, M. W. W. (1999) Science 286, 306-309]. Crystal structures of SOR from the hyperthermophilic archaeon Pyrococcus furiosus have been determined in the oxidized and reduced forms to resolutions of 1.7 and 2.0 A, respectively. SOR forms a homotetramer, with each subunit adopting an immunoglobulin-like beta-barrel fold that coordinates a mononuclear, non-heme iron center. The protein fold and metal center are similar to those observed previously for the homologous protein desulfoferrodoxin from Desulfovibrio desulfuricans [Coelho, A. V., Matias, P., Fülöp, V., Thompson, A., Gonzalez, A., and Carrondo, M. A. (1997) J. Bioinorg. Chem. 2, 680-689]. Each iron is coordinated to imidazole nitrogens of four histidines in a planar arrangement, with a cysteine ligand occupying an axial position normal to this plane. In two of the subunits of the oxidized structure, a glutamate carboxylate serves as the sixth ligand to form an overall six-coordinate, octahedral coordinate environment. In the remaining two subunits, the sixth coordination site is either vacant or occupied by solvent molecules. The iron centers in all four subunits of the reduced structure exhibit pentacoordination. The structures of the oxidized and reduced forms of SOR suggest a mechanism by which superoxide accessibility may be controlled and define a possible binding site for rubredoxin, the likely physiological electron donor to SOR. PMID:10704199

  15. 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.

  16. Improving dielectric performance in anodic aluminum oxide via detection and passivation of defect states

    SciTech Connect

    Mibus, M.; Zangari, G.; Jensen, C.; Hu, X.; Reed, M. L.; Knospe, C.

    2014-06-16

    The electronic and ionic transports in 32–56 nm thick anodic aluminum oxide films are investigated before and after a 1-h anneal at 200–400 °C in argon. Results are correlated to their defect density as measured by the Mott-Schottky technique. Solid state measurements show that electronic conduction upon annealing is hindered by an increase in the Schottky emission barrier, induced by a reduction in dopant density. Using an electrochemical contact, the films fail rapidly under cathodic polarization, unless defect density is decreased down to 10{sup 17} cm{sup −3}, resulting in a three order of magnitude reduction in current and no visible gas evolution. Under anodic polarization, the decrease in defect density delays the onset of ionic conduction as well as further oxide growth and failure.

  17. The role of iron redox state in the genotoxicity of ultrafine superparamagnetic iron oxide nanoparticles.

    PubMed

    Singh, Neenu; Jenkins, Gareth J S; Nelson, Bryant C; Marquis, Bryce J; Maffeis, Thierry G G; Brown, Andy P; Williams, Paul M; Wright, Chris J; Doak, Shareen H

    2012-01-01

    Ultrafine superparamagnetic iron oxide nanoparticles (USPION) hold great potential for revolutionising biomedical applications such as MRI, localised hyperthermia, and targeted drug delivery. Though evidence is increasing regarding the influence of nanoparticle physico-chemical features on toxicity, data however, is lacking that assesses a range of such characteristics in parallel. We show that iron redox state, a subtle though important physico-chemical feature of USPION, dramatically modifies the cellular uptake of these nanoparticles and influences their induction of DNA damage. Surface chemistry was also found to have an impact and evidence to support a potential mechanism of oxidative DNA damage behind the observed responses has been demonstrated. As human exposure to ferrofluids is predicted to increase through nanomedicine based therapeutics, these findings are important in guiding the fabrication of USPION to ensure they have characteristics that support biocompatibility. PMID:22027595

  18. 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.

  19. Anomalous capacitive behaviors of graphene oxide based solid-state supercapacitors.

    PubMed

    Zhang, Qing; Scrafford, Kathryn; Li, Mingtao; Cao, Zeyuan; Xia, Zhenhai; Ajayan, Pulickel M; Wei, Bingqing

    2014-01-01

    Substantial differences in charge storage mechanisms exist between dielectric capacitors (DCs) and electrochemical capacitors (ECs), resulting in orders of magnitude difference of stored charge density in them. However, if ionic diffusion, the major charge transport mechanism in ECs, is confined within nanoscale dimensions, the Helmholtz layers and diffusion layers will overlap, resulting in dismissible ionic diffusion. An interesting contradiction between appreciable energy density and unrecognizable ionic diffusion is observed in solid-state capacitors made from reduced graphene oxide films that challenge the fundamental charge storage mechanisms proposed in such devices. A new capacitive model is proposed, which combines the two distinct charge storage mechanisms of DCs and ECs, to explain the contradiction, of high storage capacity yet undetectable ionic diffusion, seen in graphene oxide based supercapacitors.

  20. 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...

  1. 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

  2. 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.

  3. Biological Alteration of Basaltic Glass With Altered Composition and Oxidation States

    NASA Astrophysics Data System (ADS)

    Bailey, B. E.; Staudigel, H.; Templeton, A.; Tebo, B. M.; Ryerson, F.; Plank, T.; Schroder, C.; Klingelhoefer, G.

    2004-12-01

    The ocean crust is an extreme and oligotrophic environment and yet recent studies have shown that reactions between oceanic crust and seawater are capable of supporting microbial life. We are specifically targeting volcanic glass as a source of energy and nutrients necessary to support endolithic microbial communities. A significant amount of chemical energy is available from the process of iron oxidation and our goal is to determine the ability of microorganisms to use Fe(II) as an energy source as well as liberate other essential nutrients from the host rock. In addition, microbes may oxidize Mn or use phosphate from glass. To explore the dependency of microbial life on these nutrients and energy sources, we produce basaltic glasses with varying Fe oxidation states and relative abundance of iron, manganese and phosphate and introduce them to microbial isolates and consortia both in the laboratory and in deep-ocean environments. The natural exposure experiments occur in a variety of settings including hydrothermal vents and cold deep seawater (Loihi Seamount), brines (Mediterranean), and basaltic flows at spreading ridges (EPR), when possible on submarine lava flows of recent and known age. Upon collection of the exposure experiments, we compare basalt colonizing microbial communities on our synthetic glasses with the in situ glass communities through a large culturing effort and molecular (t-RFLP) studies. So far we have produced a number of enrichment cultures and isolated several iron-oxidizing and manganese-oxidizing bacteria that were used to inoculate glasses in the laboratory. Laboratory experiments concentrate on biofilm formation and dissolution of the colonized glasses. Continued collection of exposure experiments on a yearly time-scale provides valuable information regarding spatial and temporal variations in microbial community diversity and structure. We have also analyzed the authigenic reaction products of seafloor, microbially mediated alteration

  4. Deregulation, Distrust, and Democracy: State and Local Action to Ensure Equitable Access to Healthy, Sustainably Produced Food.

    PubMed

    Wiley, Lindsay F

    2015-01-01

    Environmental, public health, alternative food, and food justice advocates are working together to achieve incremental agricultural subsidy and nutrition assistance reforms that increase access to fresh fruits and vegetables. When it comes to targeting food and beverage products for increased regulation and decreased consumption, however, the priorities of various food reform movements diverge. This article argues that foundational legal issues, including preemption of state and local authority to protect the public's health and welfare, increasing First Amendment protection for commercial speech, and eroding judicial deference to legislative policy judgments, present a more promising avenue for collaboration across movements than discrete food reform priorities around issues like sugary drinks, genetic modification, or organics. Using the Vermont Genetically Modified Organism (GMO) Labeling Act litigation, the Kauai GMO Cultivation Ordinance litigation, the New York City Sugary Drinks Portion Rule litigation, and the Cleveland Trans Fat Ban litigation as case studies, I discuss the foundational legal challenges faced by diverse food reformers, even when their discrete reform priorities diverge. I also 'explore the broader implications of cooperation among groups that respond differently to the "irrationalities" (from the public health perspective) or "values" (from the environmental and alternative food perspective) that permeate public risk perception for democratic governance in the face of scientific uncertainty. PMID:26591820

  5. Deregulation, Distrust, and Democracy: State and Local Action to Ensure Equitable Access to Healthy, Sustainably Produced Food.

    PubMed

    Wiley, Lindsay F

    2015-01-01

    Environmental, public health, alternative food, and food justice advocates are working together to achieve incremental agricultural subsidy and nutrition assistance reforms that increase access to fresh fruits and vegetables. When it comes to targeting food and beverage products for increased regulation and decreased consumption, however, the priorities of various food reform movements diverge. This article argues that foundational legal issues, including preemption of state and local authority to protect the public's health and welfare, increasing First Amendment protection for commercial speech, and eroding judicial deference to legislative policy judgments, present a more promising avenue for collaboration across movements than discrete food reform priorities around issues like sugary drinks, genetic modification, or organics. Using the Vermont Genetically Modified Organism (GMO) Labeling Act litigation, the Kauai GMO Cultivation Ordinance litigation, the New York City Sugary Drinks Portion Rule litigation, and the Cleveland Trans Fat Ban litigation as case studies, I discuss the foundational legal challenges faced by diverse food reformers, even when their discrete reform priorities diverge. I also 'explore the broader implications of cooperation among groups that respond differently to the "irrationalities" (from the public health perspective) or "values" (from the environmental and alternative food perspective) that permeate public risk perception for democratic governance in the face of scientific uncertainty.

  6. Difficulties in access and estimates of public beds in intensive care units in the state of Rio de Janeiro

    PubMed Central

    Goldwasser, Rosane Sonia; Lobo, Maria Stella de Castro; de Arruda, Edilson Fernandes; Angelo, Simone Aldrey; Silva, José Roberto Lapa e; de Salles, André Assis; David, Cid Marcos

    2016-01-01

    ABSTRACT OBJECTIVE To estimate the required number of public beds for adults in intensive care units in the state of Rio de Janeiro to meet the existing demand and compare results with recommendations by the Brazilian Ministry of Health. METHODS The study uses a hybrid model combining time series and queuing theory to predict the demand and estimate the number of required beds. Four patient flow scenarios were considered according to bed requests, percentage of abandonments and average length of stay in intensive care unit beds. The results were plotted against Ministry of Health parameters. Data were obtained from the State Regulation Center from 2010 to 2011. RESULTS There were 33,101 medical requests for 268 regulated intensive care unit beds in Rio de Janeiro. With an average length of stay in regulated ICUs of 11.3 days, there would be a need for 595 active beds to ensure system stability and 628 beds to ensure a maximum waiting time of six hours. Deducting current abandonment rates due to clinical improvement (25.8%), these figures fall to 441 and 417. With an average length of stay of 6.5 days, the number of required beds would be 342 and 366, respectively; deducting abandonment rates, 254 and 275. The Brazilian Ministry of Health establishes a parameter of 118 to 353 beds. Although the number of regulated beds is within the recommended range, an increase in beds of 122.0% is required to guarantee system stability and of 134.0% for a maximum waiting time of six hours. CONCLUSIONS Adequate bed estimation must consider reasons for limited timely access and patient flow management in a scenario that associates prioritization of requests with the lowest average length of stay. PMID:27191155

  7. 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.

  8. 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.

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

    PubMed

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

    2011-12-01

    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. PMID:22129728

  10. 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

  11. The current acceptance, accessibility and recognition of Chinese and Ayurvedic medicine in the United States in the public, governmental, and industrial sectors.

    PubMed

    Park, Jongbae J; Beckman-Harned, Selena; Cho, Gayoung; Kim, Duckhee; Kim, Hangon

    2012-06-01

    To assess the current level of acceptance in the United States of complementary and alternative medicine, recent research into the prevalence, acceptance, accessibility, and recognition of complementary and alternative therapies were reviewed. Several signs point to an increasing acceptance of complementary and alternative medicine in the United States; the use of complementary and alternative medicine is significantly increasing, many aspects of Chinese medicine and Ayurveda are becoming mainstream, practitioners in the United States are beginning to be licensed, and insurance companies are beginning to cover some complementary and alternative therapies. Remaining challenges to true acceptance include the restrictive Western mindset, the absence of published studies, a lack of consistent manufacturing processes and quality standards, and a fear of adulteration. Although the field still faces many challenges, alternative and complementary medicine, including Chinese medicine and Ayurvedic medicine, is becoming more accepted and accessible in the United States.

  12. Measurement of the oxidation state of mitochondrial cytochrome c from the neocortex of the mammalian brain

    PubMed Central

    Sakata, Y.; Abajian, M.; Ripple, M. O.; Springett, R.

    2012-01-01

    Diffuse optical remission spectra from the mammalian neocortex at visible wavelengths contain spectral features originating from the mitochondria. A new algorithm is presented, based on analytically relating the first differential of the attenuation spectrum to the first differential of the chromophore spectra, that can separate and calculate the oxidation state of cytochrome c as well as the absolute concentration and saturation of hemoglobin. The algorithm is validated in phantoms and then tested on the neocortex of the rat during an anoxic challenge. Implementation of the algorithm will provide detailed information of mitochondrial oxygenation and mitochondrial function in physiological studies of the mammalian brain. PMID:22876356

  13. SOLID-STATE SYNTHESIS AND SOME PROPERTIES OF MAGNESIUM-DOPED COPPER ALUMINUM OXIDES

    SciTech Connect

    Liu, Chang; Ren, Fei; Wang, Hsin; Case, Eldon D; Morelli, Donald

    2010-01-01

    Copper aluminum oxide (CuAlO2) with delafossite structure is a promising candidate for high temperature thermoelectric applications because of its modest band gap, high stability and low cost. We investigate magnesium doping on the aluminum site as a means of producing higher electrical conductivity and optimized Seebeck coefficient. Powder samples were synthesized using solid-state reaction and bulk samples were prepared using both cold-pressing and hot-pressing techniques. Composition analysis, microstructural examination and transport property measurements were performed, and the results suggest that while hot-pressing can achieve high density samples, secondary phases tend to form and lower the performance of the materials.

  14. Uncertain Recovery: Access and Funding Issues in Public Higher Education. Findings from the 2010 Survey of the National Council of State Directors of Community Colleges

    ERIC Educational Resources Information Center

    Katsinas, Stephen G.; Friedel, Janice N.

    2010-01-01

    There are growing pressures for community colleges and regional universities to accommodate the rise in student enrollment. The purpose of this study was to evaluate access and funding issues across public higher education institutions in the United States. Responses to a survey, conducted by the Education Policy Center at the University of…

  15. Investigation of the Searching Efficiency and Cost of Creating a Remote Access Catalog for the New York State Library. Final Report.

    ERIC Educational Resources Information Center

    Buckland, Lawrence F.; Madden, Mary

    From experimental work performed, and reported upon in this document, it is concluded that converting the New York State Library (NYSL) shelf list sample to machine readable form, and searching this shelf list using a remote access catalog are technically sound concepts though the capital costs of data conversion and system installation will be…

  16. Fatty acid composition of fourteen seashore mallow (Kosteletzkya pentacarpos) seed oil accessions collected from the Atlantic and Gulf coasts of the United States

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seashore mallow (Kosteletzkya pentacarpos) is a flowering perennial halophytic herb belonging to the family Malvaceae that is found in marshes along the Atlantic and Gulf coasts of the United States. Fourteen accessions were collected from wild populations along the Atlantic (n = 8) and Gulf (n = 6)...

  17. Medicaid: State and Federal Actions Have Been Taken to Improve Children's Access to Dental Services, but Gaps Remain. Report to Congressional Requesters. GAO-09-723

    ERIC Educational Resources Information Center

    US Government Accountability Office, 2009

    2009-01-01

    Children's access to Medicaid dental services is a long-standing concern. The tragic case of a 12-year-old boy who died from an untreated infected tooth that led to a fatal brain infection renewed attention to this issue. He was enrolled in Medicaid--a joint federal and state program that provides health care coverage, including dental care, for…

  18. Syringe Disposal among Injection Drug Users in Harlem and the Bronx during the New York State Expanded Syringe Access Demonstration Program

    ERIC Educational Resources Information Center

    Cleland, Charles M.; Deren, Sherry; Fuller, Crystal M.; Blaney, Shannon; McMahon, James M.; Tortu, Stephanie; Des Jarlais, Don C.; Vlahov, David

    2007-01-01

    Effective January 1, 2001, New York State enacted the Expanded Syringe Access Demonstration Program (ESAP), allowing syringes to be sold in pharmacies without a prescription or dispensed through doctors, hospitals, and clinics to adults. A concern in the assessment of ESAP is its effects on syringe disposal practices. Syringe use data regarding…

  19. 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).

  20. 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

  1. 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

  2. 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

  3. Origin of major donor states in In-Ga-Zn oxide

    NASA Astrophysics Data System (ADS)

    Nakashima, Motoki; Oota, Masashi; Ishihara, Noritaka; Nonaka, Yusuke; Hirohashi, Takuya; Takahashi, Masahiro; Yamazaki, Shunpei; Obonai, Toshimitsu; Hosaka, Yasuharu; Koezuka, Junichi

    2014-12-01

    To clarify the origin of the major donor states in indium gallium zinc oxide (IGZO), we report measurement results and an analysis of several physical properties of IGZO thin films. Specifically, the concentration of H atoms and O vacancies (VO), carrier concentration, and conductivity are investigated by hard X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, thermal desorption spectroscopy, and Hall effect measurements. The results of these experiments suggest that the origin of major donor states is H occupancy of VO sites. Furthermore, we use first-principles calculations to investigate the influence of the coexistence of VO and H in crystalline InGaO3(ZnO)m (m = 1). The results indicate that when H is trapped in VO, a stable complex is created that serves as a shallow-level donor.

  4. 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.

  5. Origin of major donor states in In–Ga–Zn oxide

    SciTech Connect

    Nakashima, Motoki; Oota, Masashi; Ishihara, Noritaka; Nonaka, Yusuke; Hirohashi, Takuya; Takahashi, Masahiro; Yamazaki, Shunpei; Obonai, Toshimitsu; Hosaka, Yasuharu; Koezuka, Junichi

    2014-12-07

    To clarify the origin of the major donor states in indium gallium zinc oxide (IGZO), we report measurement results and an analysis of several physical properties of IGZO thin films. Specifically, the concentration of H atoms and O vacancies (V{sub O}), carrier concentration, and conductivity are investigated by hard X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, thermal desorption spectroscopy, and Hall effect measurements. The results of these experiments suggest that the origin of major donor states is H occupancy of V{sub O} sites. Furthermore, we use first-principles calculations to investigate the influence of the coexistence of V{sub O} and H in crystalline InGaO{sub 3}(ZnO){sub m} (m = 1). The results indicate that when H is trapped in V{sub O}, a stable complex is created that serves as a shallow-level donor.

  6. 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.

  7. Mechanochemical preparation of nanocrystalline BaFCl doped with samarium in the 2+ oxidation state.

    PubMed

    Wang, Xiang-lei; Liu, Zhi-qiang; Stevens-Kalceff, Marion A; Riesen, Hans

    2014-09-01

    We report a facile mechanochemical preparation method for nanocrystalline BaFCl doped with samarium in the 2+ oxidation state by ball milling BaCl2, BaF2, and SmI2 under a nitrogen atmosphere. The resulting phosphors were characterized by powder X-ray diffraction; electron microscopy, X-ray photoelectron spectroscopy; and photoluminescence, photoexcitation, cathodoluminescence, and diffuse reflectance spectroscopy. This is the first report of a direct preparation method of Sm(2+) doped alkaline earth fluorohalides at room temperature and points to a significant potential for the preparation of a wide range of related X-ray storage phosphors containing rare earth ions in divalent and trivalent cationic states by mechanochemical methods.

  8. Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; Knopf, Daniel A.

    2014-07-01

    Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory-generated levoglucosan and methyl-nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl-nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

  9. Localized and itinerant states in lanthanide oxides united by GW @ LDA+U.

    PubMed

    Jiang, Hong; Gomez-Abal, Ricardo I; Rinke, Patrick; Scheffler, Matthias

    2009-03-27

    Many-body perturbation theory in the GW approach is applied to lanthanide oxides, using the local-density approximation plus a Hubbard U correction (LDA+U) as the starting point. Good agreement between the G0W0 density of states and experimental spectra is observed for CeO2 and Ce2O3. Unlike the LDA+U method G0W0 exhibits only a weak dependence on U in a physically meaningful range of U values. For the whole lanthanide sesquioxide (Ln2O3) series G0W0 @ LDA+U reproduces the main features found for the optical experimental band gaps. The relative positions of the occupied and unoccupied f states predicted by G0W0 confirm the experimental conjecture derived from phenomenological arguments.

  10. Solid-State Thermal Reaction of a Molecular Material and Solventless Synthesis of Iron Oxide

    NASA Astrophysics Data System (ADS)

    Roy, Debasis; Roy, Madhusudan; Zubko, Maciej; Kusz, Joachim; Bhattacharjee, Ashis

    2016-09-01

    Solid-state thermal decomposition reaction of a molecular material {As}({C}6{H}5)4[{Fe}^{II}{Fe}^{III} ({C}2{O}4)3]}n has been studied using non-isothermal thermogravimetry (TG) in an inert atmosphere. By analyzing the TG data collected at multiple heating rates in 300 K-1300 K range, the kinetic parameters (activation energy, most probable reaction mechanism function and frequency factor) are determined using different multi-heating rate analysis programs. Activation energy and the frequency factor are found to be strongly dependent on the extent of decomposition. The decomposed material has been characterized to be hematite using physical techniques (FT-IR and powder XRD). Particle morphology has been checked by TEM. A solid-state reaction pathway leading the molecular precursor to hematite has been proposed illustrating an example of solventless synthesis of iron oxides utilizing thermal decomposition as a technique using innocuous materials.

  11. 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

  12. Restricting Access to ART on the Basis of Criminal Record : An Ethical Analysis of a State-Enforced "Presumption Against Treatment" With Regard to Assisted Reproductive Technologies.

    PubMed

    Thompson, Kara; McDougall, Rosalind

    2015-09-01

    As assisted reproductive technologies (ART) become increasingly popular, debate has intensified over the ethical justification for restricting access to ART based on various medical and non-medical factors. In 2010, the Australian state of Victoria enacted world-first legislation that denies access to ART for all patients with certain criminal or child protection histories. Patients and their partners are identified via a compulsory police and child protection check prior to commencing ART and, if found to have a previous relevant conviction or child protection order, are given a "presumption against treatment." This article reviews the legislation and identifies arguments that may be used to justify restricting access to ART for various reasons. The arguments reviewed include limitations of reproductive rights, inheriting undesirable genetic traits, distributive justice, and the welfare of the future child. We show that none of these arguments justifies restricting access to ART in the context of past criminal history. We show that a "presumption against treatment" is an unjustified infringement on reproductive freedom and that it creates various inconsistencies in current social, medical, and legal policy. We argue that a state-enforced policy of restricting access to ART based on the non-medical factor of past criminal history is an example of unjust discrimination and cannot be ethically justified, with one important exception: in cases where ART treatment may be considered futile on the basis that the parents are not expected to raise the resulting child.

  13. Restricting Access to ART on the Basis of Criminal Record : An Ethical Analysis of a State-Enforced "Presumption Against Treatment" With Regard to Assisted Reproductive Technologies.

    PubMed

    Thompson, Kara; McDougall, Rosalind

    2015-09-01

    As assisted reproductive technologies (ART) become increasingly popular, debate has intensified over the ethical justification for restricting access to ART based on various medical and non-medical factors. In 2010, the Australian state of Victoria enacted world-first legislation that denies access to ART for all patients with certain criminal or child protection histories. Patients and their partners are identified via a compulsory police and child protection check prior to commencing ART and, if found to have a previous relevant conviction or child protection order, are given a "presumption against treatment." This article reviews the legislation and identifies arguments that may be used to justify restricting access to ART for various reasons. The arguments reviewed include limitations of reproductive rights, inheriting undesirable genetic traits, distributive justice, and the welfare of the future child. We show that none of these arguments justifies restricting access to ART in the context of past criminal history. We show that a "presumption against treatment" is an unjustified infringement on reproductive freedom and that it creates various inconsistencies in current social, medical, and legal policy. We argue that a state-enforced policy of restricting access to ART based on the non-medical factor of past criminal history is an example of unjust discrimination and cannot be ethically justified, with one important exception: in cases where ART treatment may be considered futile on the basis that the parents are not expected to raise the resulting child. PMID:25701147

  14. Effect of dielectric stoichiometry and interface chemical state on band alignment between tantalum oxide and platinum

    NASA Astrophysics Data System (ADS)

    Lebedinskii, Yu. Yu.; Chernikova, A. G.; Markeev, A. M.; Kuzmichev, D. S.

    2015-10-01

    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 Ta2O5/Pt and Ta2O5-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 Ta2O5/Pt and Ta2O5-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 Ta2O5/Pt and Ta2O5-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 Ta2O5+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 PtO2 interfacing layer formation at Ta2O5+x/Pt, blocking the charging of the surface states and associated dipole formation.

  15. Fully delocalized (ethynyl)(vinyl)phenylene bridged triruthenium complexes in up to five different oxidation states.

    PubMed

    Wuttke, Evelyn; Pevny, Florian; Hervault, Yves-Marie; Norel, Lucie; Drescher, Malte; Winter, Rainer F; Rigaut, Stéphane

    2012-02-01

    Triruthenium [(dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2)](n+) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){μ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){μ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

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

    PubMed Central

    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

  17. Fast Solid-State Li Ion Conducting Garnet-Type Structure Metal Oxides for Energy Storage.

    PubMed

    Thangadurai, Venkataraman; Pinzaru, Dana; Narayanan, Sumaletha; Baral, Ashok Kumar

    2015-01-15

    Lithium ion batteries are the most promising energy storage system on the market today; however, safety issues associated with the use of flammable organic polymer-based electrolytes with poor electrochemical and chemical stabilities prevent this technology from reaching maturity. Solid lithium ion electrolytes (SLIEs) are being considered as potential replacements for the organic electrolytes to develop all-solid-state Li ion batteries. Out of the recently discovered SLIEs, the garnet-related structured Li-stuffed metal oxides are the most promising electrolytes due to their high total (bulk + grain boundary) Li ion conductivity, high electrochemical stability window (∼6 V versus Li(+)/Li at room temperature), and chemical stability against reaction with an elemental Li anode and high-voltage metal oxide Li cathodes. This Perspective discusses the structural-chemical composition-ionic conductivity relationship of Li-stuffed garnets, followed by a discussion on the Li ion conduction mechanism, as well as the electrochemical and chemical stability of these materials. The performance of a number of all-solid-state batteries employing garnet-type Li ion electrolytes is also discussed.

  18. 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.

  19. 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.

  20. 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

  1. Quantized conductance coincides with state instability and excess noise in tantalum oxide memristors.

    PubMed

    Yi, Wei; Savel'ev, Sergey E; Medeiros-Ribeiro, Gilberto; Miao, Feng; Zhang, M-X; Yang, J Joshua; Bratkovsky, Alexander M; Williams, R Stanley

    2016-04-04

    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/f(2) (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=2e(2)/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.

  2. 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

  3. Quantized conductance coincides with state instability and excess noise in tantalum oxide memristors.

    PubMed

    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/f(2) (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=2e(2)/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

  4. Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

    SciTech Connect

    Fazleev, N. G.; Weiss, A. H.

    2013-04-19

    In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

  5. 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

  6. Do minority and poor neighborhoods have higher access to fast-food restaurants in the United States?

    PubMed Central

    James, Peter; Arcaya, Mariana C.; Parker, Devin M.; Tucker-Seeley, Reginald

    2016-01-01

    Background Disproportionate access to unhealthy foods in poor or minority neighborhoods may be a primary determinant of obesity disparities. We investigated whether fast-food access varies by Census block group (CBG) percent black and poverty. Methods We measured the average driving distance from each CBG population-weighted centroid to the five closest top ten fast-food chains and CBG percent black and percent below poverty Results Among 209,091 CBGs analyzed (95.1% of all US CBGs), CBG percent black was positively associated with fast-food access controlling for population density and percent poverty (average distance to fast food was 3.56 miles closer (95% CI: -3.64, -3.48) in CBGs with the highest versus lowest quartile of percentage of black residents). Poverty was not independently associated with fast-food access. The relationship between fast-food access and race was stronger in CBGs with higher levels of poverty (p for interaction <0.0001). Conclusions Predominantly black neighborhoods had higher access to fast-food while poverty was not an independent predictor of fast-food access. PMID:24945103

  7. Child- and state-level characteristics associated with preventive dental care access among U.S. children 5-17 years of age.

    PubMed

    Lin, Mei; Sappenfield, William; Hernandez, Leticia; Clark, Cheryl; Liu, Jihong; Collins, Jennifer; Carle, Adam C

    2012-12-01

    The objectives of this study is to identify factors associated with lack of preventive dental care among U.S. children and state-level factors that explain variation in preventive dental care access across states. We performed bivariate analyses and multilevel regression analyses among 68,350 children aged 5-17 years using the 2007 National Survey of Children's Health data and relevant state-level data. Odds ratios (ORs) for child- and state-level variables were calculated to estimate associations with preventive dental care. We calculated interval odds ratios (IOR), median odds ratios (MOR), and intraclass correlation coefficients (ICC) to quantify variation in preventive dental care across states. Lack of preventive dental care was associated with various child-level factors. For state-level factors, a higher odds of lack of preventive dental care was associated with a higher percentage of Medicaid-enrolled children not receiving dental services (OR = 1.30, 95 % confidence interval (CI): 1.15-1.47); higher percentage of children uninsured (OR = 1.48, 95 % CI: 1.29-1.69); lower dentist-to-population ratio (OR = 1.36, 95 % CI: 1.03-1.80); and lower percentage of dentists submitting Medicaid/State Children's Health Insurance Program claims (OR = 1.04, 95 % CI: 1.01-1.06). IORs for the first three state-level factors did not contain one, indicating that these state-level characteristics were important in understanding variation across states. Lack of preventive dental care varied by state (MOR = 1.40). The state-level variation (ICC = 3.66 %) accounted for a small percentage of child- and state-level variation combined. Child- and state-level characteristics were associated with preventive dental care access among U.S. children aged 5-17 years. State-level factors contribute to variation in dental care access across states and need to be considered in state-level planning.

  8. 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.

  9. 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

    2016-01-01

    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

  10. 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

    2014-07-01

    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. PMID:24930767

  11. 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

  12. 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

    2016-01-01

    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.

  13. 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.

  14. 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.

  15. Improved yield of high molecular weight DNA coincides with increased microbial diversity access from iron oxide cemented sub-surface clay environments.

    PubMed

    Hurt, Richard A; Robeson, Michael S; Shakya, Migun; Moberly, James G; Vishnivetskaya, Tatiana A; Gu, Baohua; Elias, Dwayne A

    2014-01-01

    Despite over three decades of progress, extraction of high molecular weight (HMW) DNA from high clay soils or iron oxide cemented clay has remained challenging. HMW DNA is desirable for next generation sequencing as it yields the most comprehensive coverage. Several DNA extraction procedures were compared from samples that exhibit strong nucleic acid adsorption. pH manipulation or use of alternative ion solutions offered no improvement in nucleic acid recovery. Lysis by liquid N2 grinding in concentrated guanidine followed by concentrated sodium phosphate extraction supported HMW DNA recovery from clays high in iron oxides. DNA recovered using 1 M sodium phosphate buffer (PB) as a competitive desorptive wash was 15.22±2.33 µg DNA/g clay, with most DNA consisting of >20 Kb fragments, compared to 2.46±0.25 µg DNA/g clay with the Powerlyzer system (MoBio). Increasing PB concentration in the lysis reagent coincided with increasing DNA fragment length during initial extraction. Rarefaction plots of 16S rRNA (V1-V3 region) pyrosequencing from A-horizon and clay soils showed an ∼80% and ∼400% larger accessed diversity compared to the Powerlyzer soil DNA system, respectively. The observed diversity from the Firmicutes showed the strongest increase with >3-fold more operational taxonomic units (OTU) recovered.

  16. Scanning transmission X-ray microscopy probe for in situ mechanism study of graphene-oxide-based resistive random access memory.

    PubMed

    Nho, Hyun Woo; Kim, Jong Yun; Wang, Jian; Shin, Hyun-Joon; Choi, Sung-Yool; Yoon, Tae Hyun

    2014-01-01

    Here, an in situ probe for scanning transmission X-ray microscopy (STXM) has been developed and applied to the study of the bipolar resistive switching (BRS) mechanism in an Al/graphene oxide (GO)/Al resistive random access memory (RRAM) device. To perform in situ STXM studies at the C K- and O K-edges, both the RRAM junctions and the I0 junction were fabricated on a single Si3N4 membrane to obtain local XANES spectra at these absorption edges with more delicate I0 normalization. Using this probe combined with the synchrotron-based STXM technique, it was possible to observe unique chemical changes involved in the BRS process of the Al/GO/Al RRAM device. Reversible oxidation and reduction of GO induced by the externally applied bias voltages were observed at the O K-edge XANES feature located at 538.2 eV, which strongly supported the oxygen ion drift model that was recently proposed from ex situ transmission electron microscope studies.

  17. 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.

  18. 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

  19. 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.

  20. Revealing the role of oxidation state in interaction between nitro/amino-derived particulate matter and blood proteins.

    PubMed

    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 10(3) 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