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Sample records for active oxygen forms

  1. [Influence of salicylic and succinic acids on formation of active oxygen forms in wheat coleoptiles].

    PubMed

    Kolupaiev, Iu Ie; Iastreb, T O; Shvidenko, M V; Karpets', Iu V

    2011-01-01

    The comparative study of influence of exogenous salicylic (SaA) and succinic (SuA) acids on the production of reactive oxygen species by isolated wheat coleoptiles has been provided. Under the action of both acids the increase of generation of superoxide anion-radical (O2(.-)) was observed. This increase was partially suppressed by treatment of coleoptiles with inhibitors of peroxidase (salicylhydroxamic acid) and NADP H-oxidase (imidazole and alpha-naphthol). The increase of hydrogen peroxide content, activity of peroxidase and superoxide dismutase (SOD) was registered under the influence of SaA and SuA; catalase activity did not change essentially. The treatment of coleoptiles with the indicated acids resulted in the increase of their resistance to abiotic stress (damaging heating, 43 +/- 0,1 degrees C, 10 min). The conclusion is made, that the increase of O2(.-) generation in wheat coleoptiles under the action of SaA and SuA is related, probably, to the increase of apoplast peroxidase and NADP.H-oxidase activity, and the rise of H2O2 content is related to the growth of SOD activity. These enzymatic systems are involved in the induction of plant cells protective reactions to the hyperthermia. PMID:22276431

  2. Oxygen-dependent upstream activation sites of Saccharomyces cerevisiae cytochrome c genes are related forms of the same sequence

    SciTech Connect

    Cerdan, M.E.; Zitomer, R.S.

    1988-06-01

    In Sacchariomyces cerevisiae, the two genes, CYC1 and CYC7, that encode the isoforms of cytochrome c are expressed at different levels. Oxygen regulation is indicated by the expression of the CYP1 gene, and the CYP1 protein interacts with both CYC1 upstream activation sequence 1 (UAS1) and CYC7 UAS/sub 0/. In this study, the homology between the CYP1-binding sites of both genes was investigated. The most noticeable difference between the CYC1 and CYC7 UASs is the presence of GC base pairs at the same positions in a repeated sequence in CYC7 compared with CG base pairs in CYC1. Directed mutagenesis changing these GC residues to CG residues in CYC7 led to CYC1-like expression of CYC7 both in a CYP1 wild-type strain and in a strain carrying the semidominant mutation CYP1-16 which reverses the oxygen-dependent expression of the two genes. The authors' results strongly support the hypothesis that the CYP1-binding sites in CYC1 and CYC7 are related forms of the same sequence and that the CYP1-16 protein has altered specificity for the variant forms of the concensus sequences in both genes.

  3. The Three Forms of Molecular Oxygen.

    ERIC Educational Resources Information Center

    Laing, Michael

    1989-01-01

    Finds that a logical application of the simple rules of the molecular orbital bonding theory for diatomic molecules predicted the existence of three spin isomers of the oxygen molecule: one triplet form with two unpaired electrons and two singlet forms with all electrons paired. (MVL)

  4. Substrate-Mediated Oxygen Activation by Homoprotocatechuate 2,3-Dioxygenase: Intermediates Formed by a Tyrosine 257 Variant

    PubMed Central

    Mbughuni, Michael M.; Meier, Katlyn K.; Münck, Eckard; Lipscomb, John D.

    2012-01-01

    Homoprotocatechuate (HPCA; 3,4-dihydroxyphenylacetate or 4-carboxymethyl catechol) and O2 bind in adjacent ligand sites of the active site FeII of Homoprotocatechuate 2,3-Dioxygenase (FeHPCD). We have proposed that electron transfer from the chelated aromatic substrate through the FeII to O2 gives both substrates radical character. This would promote reaction between the substrates to form an alkylperoxo intermediate as the first step in aromatic ring cleavage. Several active site amino acids are thought to promote these reactions through acid/base chemistry, hydrogen bonding, and electrostatic interactions. Here the role of Tyr257 is explored by using the Tyr257Phe (Y257F) variant, which decreases kcat by about 75%. The crystal structure of the FeHPCD-HPCA complex has shown that Tyr257 hydrogen bonds to the deprotonated C2-hydroxyl of HPCA. Stopped-flow studies show that at least two reaction intermediates, termed Y257FInt1HPCA and Y257FInt2HPCA, accumulate during the Y257F-HPCA + O2 reaction prior to formation of the ring-cleaved product. Y257FInt1HPCA is colorless and is formed as O2 binds reversibly to the HPCA-enzyme complex. Y257FInt2HPCA forms spontaneously from Y257FInt1HPCA and displays a chromophore at 425 nm (ε425 = 10,500 M-1 cm−1). Mössbauer spectra of the intermediates trapped by rapid freeze quench show that both intermediates contain FeII. The lack of a chromophore characteristic of a quinone or semiquinone form of HPCA, the presence of FeII, and the low O2 affinity suggests that Y257FInt1HPCA is an HPCA-FeII-O2 complex with little electron delocalization onto the O2. In contrast, the intense spectrum of Y257FInt2HPCA suggests the intermediate is most likely an HPCA quinone-FeII-(hydro)peroxo species. Steady-state and transient kinetic analyses show that steps of the catalytic cycle are slowed by as much as 100-fold by the mutation. These effects can be rationalized by a failure of Y257F to facilitate the observed distortion of the bound HPCA

  5. Photoadaptation and protection against active forms of oxygen in the symbiotic procaryote Prochloron sp. and its ascidian host

    SciTech Connect

    Lesser, M.P.; Stochaj, W.R. )

    1990-06-01

    Superoxide dismutase, ascorbate, peroxidase, and catalase activities were studied in the symbiotic photosynthetic procaryote Prochloron sp. and its ascidian host Lissoclinum patella. The protein-specific activities of these antioxidant enzymes in the Prochloron sp. and L. patella collected at different depths from the Great Barrier Reef, Australia, were directly proportional to irradiance, whereas the pigment concentrations in the Prochloron sp. were inversely proportional to irradiance. The presence of a cyanide-sensitive superoxide dismutase, presumably a Cu-An metalloprotein, in the Prochloron sp. extends the possible phylogenetic distribution of this protein. The concentration of UV-absorbing mycosporine-like amino acids in inversely proportional to irradiance in both the host and symbiont, suggesting that these compounds may not provide sufficient protection against UV radiation in high-irradiance environments. The significant differences in the specific activities of these antioxidant enzymes, cellular photosynthetic pigment concentrations, and UV-absorbing compounds from high- and low-irradiance habitats constitute an adaptive response to different photic environments. These photoadaptive responses are essential to prevent inhibition of photosynthesis by high fluxes of visible and UV radiation.

  6. Active oxygen doctors the evidence

    NASA Astrophysics Data System (ADS)

    Castelló, Ana; Francès, Francesc; Corella, Dolores; Verdú, Fernando

    2009-02-01

    Investigation at the scene of a crime begins with the search for clues. In the case of bloodstains, the most frequently used reagents are luminol and reduced phenolphthalein (or phenolphthalin that is also known as the Kastle-Meyer colour test). The limitations of these reagents have been studied and are well known. Household cleaning products have evolved with the times, and new products with active oxygen are currently widely used, as they are considered to be highly efficient at removing all kinds of stains on a wide range of surfaces. In this study, we investigated the possible effects of these new cleaning products on latent bloodstains that may be left at a scene of a crime. To do so, various fabrics were stained with blood and then washed using cleaning agents containing active oxygen. The results of reduced phenolphthalein, luminol and human haemoglobin tests on the washed fabrics were negative. The conclusion is that these new products alter blood to such an extent that it can no longer be detected by currently accepted methods employed in criminal investigations. This inability to locate bloodstains means that highly important evidence (e.g. a DNA profile) may be lost. Consequently, it is important that investigators are aware of this problem so as to compensate for it.

  7. [Participation of the active oxygen forms in the induction of ascorbate peroxidase and guaiacol peroxidase under heat hardening of wheat seedlings].

    PubMed

    Kolupaev, Iu E; Oboznyĭ, A I

    2012-01-01

    The influence of one-minute hardening heating at 42 degrees C on the dynamics of hydrogen peroxide generation and activity of antioxidant enzymes in roots of winter wheat seedlings has been investigated. It was shown that the content of hydrogen peroxide increased within the first 30 minutes after heat influence, whereupon it approached the level of control variant. The activity of superoxide dismutase (SOD) increased significantly within 10 min after heating and was maintained at a high level during 24 hours of observation. The activity of ascorbate peroxidase and guaiacol peroxidase increased after 3-6 hours after the hardening and reached its maximum after 24 hours, when there was the most significant increase in heat resistance of seedlings. The short-term increase in hydrogen peroxide content caused by hardening heating was suppressed by treatment of seedlings with H2O2 scavenger dimethylthiourea, inhibitors of NADPH-oxidase (imidazole) and SOD (sodium diethyldithiocarbamate). All these effectors levelled the increase of activity of ascorbate peroxidase and guaiacol peroxidase and significantly inhibited the development of heat resistance of seedlings. The conclusion was made about the role of hydrogen peroxide produced with the participation of NADPH-oxidase and SOD in the induction of antioxidant system by heat hardening of wheat seedlings.

  8. [Participation of the active oxygen forms in the induction of ascorbate peroxidase and guaiacol peroxidase under heat hardening of wheat seedlings].

    PubMed

    Kolupaev, Iu E; Oboznyĭ, A I

    2012-01-01

    The influence of one-minute hardening heating at 42 degrees C on the dynamics of hydrogen peroxide generation and activity of antioxidant enzymes in roots of winter wheat seedlings has been investigated. It was shown that the content of hydrogen peroxide increased within the first 30 minutes after heat influence, whereupon it approached the level of control variant. The activity of superoxide dismutase (SOD) increased significantly within 10 min after heating and was maintained at a high level during 24 hours of observation. The activity of ascorbate peroxidase and guaiacol peroxidase increased after 3-6 hours after the hardening and reached its maximum after 24 hours, when there was the most significant increase in heat resistance of seedlings. The short-term increase in hydrogen peroxide content caused by hardening heating was suppressed by treatment of seedlings with H2O2 scavenger dimethylthiourea, inhibitors of NADPH-oxidase (imidazole) and SOD (sodium diethyldithiocarbamate). All these effectors levelled the increase of activity of ascorbate peroxidase and guaiacol peroxidase and significantly inhibited the development of heat resistance of seedlings. The conclusion was made about the role of hydrogen peroxide produced with the participation of NADPH-oxidase and SOD in the induction of antioxidant system by heat hardening of wheat seedlings. PMID:23387278

  9. Probing Oxygen Activation Sites in Two Flavoprotein Oxidases Using Chloride as an Oxygen Surrogate

    SciTech Connect

    Kommoju, Phaneeswara-Rao; Chen, Zhi-wei; Bruckner, Robert C.; Mathews, F. Scott; Jorns, Marilyn Schuman

    2011-08-16

    A single basic residue above the si-face of the flavin ring is the site of oxygen activation in glucose oxidase (GOX) (His516) and monomeric sarcosine oxidase (MSOX) (Lys265). Crystal structures of both flavoenzymes exhibit a small pocket at the oxygen activation site that might provide a preorganized binding site for superoxide anion, an obligatory intermediate in the two-electron reduction of oxygen. Chloride binds at these polar oxygen activation sites, as judged by solution and structural studies. First, chloride forms spectrally detectable complexes with GOX and MSOX. The protonated form of His516 is required for tight binding of chloride to oxidized GOX and for rapid reaction of reduced GOX with oxygen. Formation of a binary MSOX-chloride complex requires Lys265 and is not observed with Lys265Met. Binding of chloride to MSOX does not affect the binding of a sarcosine analogue (MTA, methylthioactetate) above the re-face of the flavin ring. Definitive evidence is provided by crystal structures determined for a binary MSOX-chloride complex and a ternary MSOX-chloride-MTA complex. Chloride binds in the small pocket at a position otherwise occupied by a water molecule and forms hydrogen bonds to four ligands that are arranged in approximate tetrahedral geometry: Lys265:NZ, Arg49:NH1, and two water molecules, one of which is hydrogen bonded to FAD:N5. The results show that chloride (i) acts as an oxygen surrogate, (ii) is an effective probe of polar oxygen activation sites, and (iii) provides a valuable complementary tool to the xenon gas method that is used to map nonpolar oxygen-binding cavities.

  10. Oxygen isotopes and the moon-forming giant impact.

    PubMed

    Wiechert, U; Halliday, A N; Lee, D C; Snyder, G A; Taylor, L A; Rumble, D

    2001-10-12

    We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.

  11. Electrochemical investigations on the oxygen activation by cytochrome P-450.

    PubMed

    Scheller, F; Renneberg, R; Schwarze, W; Strnad, G; Pommerening, K; Prümke, H J; Mohr, P

    1979-01-01

    The application of cytochrome P-450 in substrate conversion is complicated both due to the limited stability and the cofactor regeneration problems. To overcome the disadvantages of NADPH consumption the transfer of the reduction equivalents from an electrode into the cytochrome P-450-system was studied: 1. NADPH was cathodically reduced at a mercury pool electrode. By immobilization of NADP on dialdehyde Sephadex the reductive recycling was possible. 2. Different forms of reduced oxygen were produced by the cathode: a) The reaction of O2- with deoxycorticosterone yields a carboxylic acid derivative. In contrast the cytochrome P-450 catalyzed NADPH-dependent reaction with the same substrate gives corticosterone, O2- represents only an intermediate in the activation of oxygen and is not the "activated oxygen" species. b) Molecular oxygen was reduced to HO2- and H2O2, respectively. The interaction of adsorbed cytochrome P-450 on the electrode surface with the reduced oxygen species in the absence of NADPH was studied. The electrochemically generated peroxide seems to be more active than added H2O2. 3. In a model of electro-enzyme-reactor several substrates were hydroxylated by microsomal cytochrome P-450 with cathodically reduced oxygen which substitutes NADPH.

  12. Quantifying consumption rates of dissolved oxygen along bed forms

    NASA Astrophysics Data System (ADS)

    Boano, Fulvio; De Falco, Natalie; Arnon, Shai

    2016-04-01

    Streambed interfaces represent hotspots for nutrient transformations because they host different microbial species, and the evaluation of these reaction rates is important to assess the fate of nutrients in riverine environments. In this work we analyze a series of flume experiments on oxygen demand in dune-shaped hyporheic sediments under losing and gaining flow conditions. We employ a new modeling code to quantify oxygen consumption rates from observed vertical profiles of oxygen concentration. The code accounts for transport by molecular diffusion and water advection, and automatically determines the reaction rates that provide the best fit between observed and modeled concentration values. The results show that reaction rates are not uniformly distributed across the streambed, in agreement with the expected behavior predicted by hyporheic exchange theory. Oxygen consumption was found to be highly influenced by the presence of gaining or losing flow conditions, which controlled the delivery of labile DOC to streambed microorganisms.

  13. Biochar activated by oxygen plasma for supercapacitors

    NASA Astrophysics Data System (ADS)

    Gupta, Rakesh Kumar; Dubey, Mukul; Kharel, Parashu; Gu, Zhengrong; Fan, Qi Hua

    2015-01-01

    Biochar, also known as black carbon, is a byproduct of biomass pyrolysis. As a low-cost, environmental-friendly material, biochar has the potential to replace more expensive synthesized carbon nanomaterials (e.g. carbon nanotubes) for use in future supercapacitors. To achieve high capacitance, biochar requires proper activation. A conventional approach involves mixing biochar with a strong base and baking at a high temperature. However, this process is time consuming and energy inefficient (requiring temperatures >900 °C). This work demonstrates a low-temperature (<150 °C) plasma treatment that efficiently activates a yellow pine biochar. Particularly, the effects of oxygen plasma on the biochar microstructure and supercapacitor characteristics are studied. Significant enhancement of the capacitance is achieved: 171.4 F g-1 for a 5-min oxygen plasma activation, in comparison to 99.5 F g-1 for a conventional chemical activation and 60.4 F g-1 for untreated biochar. This enhancement of the charge storage capacity is attributed to the creation of a broad distribution in pore size and a larger surface area. The plasma activation mechanisms in terms of the evolution of the biochar surface and microstructure are further discussed.

  14. Spiral chain O4 form of dense oxygen

    PubMed Central

    Zhu, Li; Wang, Ziwei; Wang, Yanchao; Zou, Guangtian; Mao, Ho-kwang; Ma, Yanming

    2012-01-01

    Oxygen is in many ways a unique element: It is the only known diatomic molecular magnet, and it exhibits an unusual O8 cluster in its high-pressure solid phase. Pressure-induced molecular dissociation as one of the fundamental problems in physical sciences has been reported from theoretical or experimental studies of diatomic solids H2, N2, F2, Cl2, Br2, and I2 but remains elusive for molecular oxygen. We report here the prediction of the dissociation of molecular oxygen into a polymeric spiral chain O4 structure (space group I41/acd, θ-O4) above 1.92-TPa pressure using the particle-swarm search method. The θ-O4 phase has a similar structure as the high-pressure phase III of sulfur. The molecular bonding in the insulating ε-O8 phase or the isostructural superconducting ζ-O8 phase remains remarkably stable over a large pressure range of 0.008–1.92 TPa. The pressure-induced softening of a transverse acoustic phonon mode at the zone boundary V point of O8 phase might be the ultimate driving force for the formation of θ-O4. Stabilization of θ-O4 turns oxygen from a superconductor into an insulator by opening a wide band gap (approximately 5.9 eV) that originates from the sp3-like hybridized orbitals of oxygen and the localization of valence electrons. PMID:22215589

  15. Removal of Biologically Active Organic Contaminants using Atomic Oxygen

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A. (Inventor); Banks, Michael A. (Inventor); Banks, Eric B. (Inventor)

    2003-01-01

    Biomedical devices that are to come into contact with living tissue, such as prosthetic and other implants for the human body and the containers used to store and transport them, are together cleaned of non-living, but biologically active organic materials, including endotoxins such as lipopolysaccharides, and assembled into a hermetically sealed package without recontamination. This is achieved by cleaning both the device and package components together in an apparatus, which includes a hermetically sealed chamber, in which they are contacted with atomic oxygen which biocleans them, by oxidizing the biologically active organic materials. The apparatus also includes means for manipulating the device and container and hermetically sealing the cleaned device into the cleaned container to form the package. A calibrated witness coupon visually indicates whether or not the device and container have received enough exposure to the atomic oxygen to have removed the organic materials from their surfaces. Gamma radiation is then used to sterilize the device in the sealed container.

  16. BIOLOGICALLY ENHANCED OXYGEN TRANSFER IN THE ACTIVATED SLUDGE PROCESS (JOURNAL)

    EPA Science Inventory

    Biologically enhanced oxgyen transfer has been a hypothesis to explain observed oxygen transfer rates in activated sludge systems that were well above that predicted from aerator clean-water testing. The enhanced oxygen transfer rates were based on tests using BOD bottle oxygen ...

  17. Henry's Law Activity of Oxygen in Molten Iron

    NASA Astrophysics Data System (ADS)

    Matousek, J. W.

    2015-09-01

    A model is proposed for the solubility of oxygen in molten iron in dilute solutions in which the oxygen exists in two states, free and associated. Only the free oxygen has thermodynamic activity in the sense of interaction with an electrochemical cell to produce the voltage described by the Nernst equation.

  18. Oxygen consumption along bed forms under losing and gaining streamflow conditions

    NASA Astrophysics Data System (ADS)

    De Falco, Natalie; Arnon, Shai; Boano, Fulvio

    2016-04-01

    Recent studies have demonstrated that bed forms are the most significant geomorphological structure that drives hyporheic exchange and biogeochemical processes in stream networks. Other studies also demonstrated that due to the hyporheic flow patterns within bed form, biogeochemical processes do not occur uniformly along and within the bed forms. The objective of this work was to systematically evaluate how losing or gaining flow conditions affect oxygen consumption by biofilm along sandy bed forms. We measured the effects of losing and gaining flow conditions on oxygen consumption by combining modeling and experiments in a novel laboratory flume system that enable the control of losing and gaining fluxes. Oxygen consumption was measured after growing a benthic biofilm fed with Sodium Benzoate (as a carbon source) and measuring the distribution of oxygen in the streambed with microelectrodes. The experimental results were analyzed using a novel code that calculates vertical profiles of reaction rates in the presence of hyporheic water fluxes. These experimental observations and modeling revealed that oxygen distribution varied along the bed forms. The zone of oxygen consumption (i.e. depth of penetration) was the largest at the upstream side of the bed form and the smallest in the lee side (at the lowest part of the bed form), regardless of the flow conditions. Also, the zone of oxygen consumption was the largest under losing conditions, the smallest under gaining conditions, and in-between under neutral conditions. The distribution of oxygen consumption rates determined with our new model will be also discussed. Our preliminary results enable us to show the importance of the coupling between flow conditions and oxygen consumption along bed forms and are expected to improve our understanding of nutrient cycling in streams.

  19. Multiple forms of soluble monophenol, dihydroxyphenylalanine: oxygen oxidoreductase (EC 1.14.18.1) from potato tubers (Solanum tuberosum). III. Influence of pH on the molecular weight distribution of enzyme activity in potato juice.

    PubMed

    Matheis, G; Belitz, H D

    1979-09-01

    Gel chromatography on Sepharose and on Sephadex was used to separate the soluble phenol oxidase in various potato juices into multiple molecular forms ranging from 36,000 to 800,000 daltons. Adjustment of potato juice from physiological pH (ca. 6) to pH 4.5 or to pH 7.8 resulted in the predominance of low-mol.-wt. (less than 150,000 daltons) or high-mol.-wt. (greater than 150,000 daltons) enzyme forms, respectively. This suggests association phenomena of subunits. In potato juice of physiological pH and in potato juice adjusted to pH 4.5, all enzyme forms exhibited both monophenol and o-diphenol oxidase activities (assayed at pH 6.0). In potato juice adjusted to pH 7.8 considerable loss of monophenol oxidase activity (assayed at pH 6.0) occurred. This suggests that o-diphenol oxidase is more alkali-stable than monophenol oxidase. The significance of these findings for enzyme purifications and for the in vivo action of the enzyme is discussed. PMID:41378

  20. A nondestructive technique to determine the rate of oxygen permeation into solid dosage forms.

    PubMed

    Felton, L A; Timmins, G S

    2006-02-01

    The current study investigated the use of electron paramagnetic resonance (EPR) spectroscopy as a nondestructive method to quantify the partial pressure of oxygen (PO2) in tablets and hard shell capsules. Lithium phthalocyanine crystals (LiPC) were placed inside the dosage forms. The peak-to-peak linewidth of the first derivative of the LiPC EPR spectra was measured and, by calibration tables, the oxygen partial pressure, pO2, within the dosage form was determined. The intra-dosage form pO2 was followed as a function of time after changing the exterior gas stream composition. Results showed initial oxygen concentrations comparable to atmospheric levels in all tablets and capsules investigated. Oxygen rapidly permeated into unsealed gelatin and cellulosic hard shell capsules. Banding at the cap/body joint significantly reduced the oxygen permeation rate. Oxygen also rapidly permeated into tablet compacts, regardless of the compressional force used during tableting, while application of a polymeric film significantly decreased the rate of oxygen permeation. This EPR technique was shown to be a suitable nondestructive method to study oxygen permeation kinetics in solid dosage forms.

  1. Protocyanobacteria: Oxygenic and Anoxygenic photosynthesis in mat-forming bacteria

    NASA Technical Reports Server (NTRS)

    Cohen, Y.

    1985-01-01

    The oldest record of life is preserved in prePhanerozoic stromatolites dated 3500 million years old and is most likely of filamentous mat-forming cyanobacteria. The sedimentary records of cyanobacterial mats in stromatolites are the most abundant record of life throughout the prePhanerozoic. Stromatolites persisted into the Phanerozoic Eon, yet they become much less pronounced relative to earlier ones. The abundance and persistence of cyanobacterial mats throughout most of geological time point to the evolutionary success of these kinds of microbial communities and their possible role in the evolution of the earth and atmosphere.

  2. Electrochemically Formed Ultrafine Metal Oxide Nanocatalysts for High-Performance Lithium-Oxygen Batteries.

    PubMed

    Liu, Bin; Yan, Pengfei; Xu, Wu; Zheng, Jianming; He, Yang; Luo, Langli; Bowden, Mark E; Wang, Chong-Min; Zhang, Ji-Guang

    2016-08-10

    Lithium-oxygen (Li-O2) batteries have an extremely high theoretical specific energy density when compared with conventional energy-storage systems. However, practical application of the Li-O2 battery system still faces significant challenges. In this work, we report a new approach for synthesis of ultrafine metal oxide nanocatalysts through an electrochemical prelithiation process. This process reduces the size of NiCo2O4 (NCO) particles from 20-30 nm to a uniformly distributed domain of ∼2 nm and significantly improves their catalytic activity. Structurally, the prelithiated NCO nanowires feature ultrafine NiO/CoO nanoparticles that are highly stable during prolonged cycles in terms of morphology and particle size, thus maintaining an excellent catalytic effect to oxygen reduction and evolution reactions. A Li-O2 battery using this catalyst demonstrated an initial capacity of 29 280 mAh g(-1) and retained a capacity of >1000 mAh g(-1) after 100 cycles based on the weight of the NCO active material. Direct in situ transmission electron microscopy observations conclusively revealed the lithiation/delithiation process of as-prepared NCO nanowires and provided in-depth understanding for both catalyst and battery chemistries of transition-metal oxides. This unique electrochemical approach could also be used to form ultrafine nanoparticles of a broad range of materials for catalyst and other applications. PMID:27380300

  3. Reactive oxygen species-activated nanomaterials as theranostic agents.

    PubMed

    Kim, Kye S; Lee, Dongwon; Song, Chul Gyu; Kang, Peter M

    2015-01-01

    Reactive oxygen species (ROS) are generated from the endogenous oxidative metabolism or from exogenous pro-oxidant exposure. Oxidative stress occurs when there is excessive production of ROS, outweighing the antioxidant defense mechanisms which may lead to disease states. Hydrogen peroxide (H2O2) is one of the most abundant and stable forms of ROS, implicated in inflammation, cellular dysfunction and apoptosis, which ultimately lead to tissue and organ damage. This review is an overview of the role of ROS in different diseases. We will also examine ROS-activated nanomaterials with emphasis on hydrogen peroxide, and their potential medical implications. Further development of the biocompatible, stimuli-activated agent responding to disease causing oxidative stress, may lead to a promising clinical use. PMID:26328770

  4. Reactive oxygen species-activated nanomaterials as theranostic agents

    PubMed Central

    Kim, Kye S; Lee, Dongwon; Song, Chul Gyu; Kang, Peter M

    2015-01-01

    Reactive oxygen species (ROS) are generated from the endogenous oxidative metabolism or from exogenous pro-oxidant exposure. Oxidative stress occurs when there is excessive production of ROS, outweighing the antioxidant defense mechanisms which may lead to disease states. Hydrogen peroxide (H2O2) is one of the most abundant and stable forms of ROS, implicated in inflammation, cellular dysfunction and apoptosis, which ultimately lead to tissue and organ damage. This review is an overview of the role of ROS in different diseases. We will also examine ROS-activated nanomaterials with emphasis on hydrogen peroxide, and their potential medical implications. Further development of the biocompatible, stimuli-activated agent responding to disease causing oxidative stress, may lead to a promising clinical use. PMID:26328770

  5. Molecular dioxygen enters the active site of 12/15-lipoxygenase via dynamic oxygen access channels.

    PubMed

    Saam, Jan; Ivanov, Igor; Walther, Matthias; Holzhütter, Hermann-Georg; Kuhn, Hartmut

    2007-08-14

    Cells contain numerous enzymes that use molecular oxygen for their reactions. Often, their active sites are buried deeply inside the protein, which raises the question whether there are specific access channels guiding oxygen to the site of catalysis. Choosing 12/15-lipoxygenase as a typical example for such oxygen-dependent enzymes, we determined the oxygen distribution within the protein and defined potential routes for oxygen access. For this purpose, we have applied an integrated strategy of structural modeling, molecular dynamics simulations, site-directed mutagenesis, and kinetic measurements. First, we computed the 3D free-energy distribution for oxygen, which led to identification of four oxygen channels in the protein. All channels connect the protein surface with a region of high oxygen affinity at the active site. This region is localized opposite to the nonheme iron providing a structural explanation for the reaction specificity of this lipoxygenase isoform. The catalytically most relevant path can be obstructed by L367F exchange, which leads to a strongly increased Michaelis constant for oxygen. The blocking mechanism is explained in detail by reordering the hydrogen-bonding network of water molecules. Our results provide strong evidence that the main route for oxygen access to the active site of the enzyme follows a channel formed by transiently interconnected cavities whereby the opening and closure are governed by side chain dynamics. PMID:17675410

  6. Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts.

    PubMed

    Wang, Lu-Cun; Friend, C M; Fushimi, Rebecca; Madix, Robert J

    2016-07-01

    The activation of molecular O2 as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O2 activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O2 dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O2 dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O2 dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction. PMID:27376884

  7. Influence of the oxygen microenvironment on the proangiogenic potential of human endothelial colony forming cells.

    PubMed

    Decaris, Martin L; Lee, Chang I; Yoder, Mervin C; Tarantal, Alice F; Leach, J Kent

    2009-01-01

    Therapeutic angiogenesis is a promising strategy to promote the formation of new or collateral vessels for tissue regeneration and repair. Since changes in tissue oxygen concentrations are known to stimulate numerous cell functions, these studies have focused on the oxygen microenvironment and its role on the angiogenic potential of endothelial cells. We analyzed the proangiogenic potential of human endothelial colony-forming cells (hECFCs), a highly proliferative population of circulating endothelial progenitor cells, and compared outcomes to human dermal microvascular cells (HMVECs) under oxygen tensions ranging from 1% to 21% O2, representative of ischemic or healthy tissues and standard culture conditions. Compared to HMVECs, hECFCs (1) exhibited significantly greater proliferation in both ischemic conditions and ambient air; (2) demonstrated increased migration compared to HMVECs when exposed to chemotactic gradients in reduced oxygen; and (3) exhibited comparable or superior proangiogenic potential in reduced oxygen conditions when assessed using a vessel-forming assay. These data demonstrate that the angiogenic potential of both endothelial populations is influenced by the local oxygen microenvironment. However, hECFCs exhibit a robust angiogenic potential in oxygen conditions representative of physiologic, ischemic, or ambient air conditions, and these findings suggest that hECFCs may be a superior cell source for use in cell-based approaches for the neovascularization of ischemic or engineered tissues.

  8. A ligand field chemistry of oxygen generation by the oxygen-evolving complex and synthetic active sites

    PubMed Central

    Betley, Theodore A; Surendranath, Yogesh; Childress, Montana V; Alliger, Glen E; Fu, Ross; Cummins, Christopher C; Nocera, Daniel G

    2007-01-01

    Oxygen–oxygen bond formation and O2 generation occur from the S4 state of the oxygen-evolving complex (OEC). Several mechanistic possibilities have been proposed for water oxidation, depending on the formal oxidation state of the Mn atoms. All fall under two general classifications: the AB mechanism in which nucleophilic oxygen (base, B) attacks electrophilic oxygen (acid, A) of the Mn4Ca cluster or the RC mechanism in which radical-like oxygen species couple within OEC. The critical intermediate in either mechanism involves a metal oxo, though the nature of this oxo for AB and RC mechanisms is disparate. In the case of the AB mechanism, assembly of an even-electron count, high-valent metal-oxo proximate to a hydroxide is needed whereas, in an RC mechanism, two odd-electron count, high-valent metal oxos are required. Thus the two mechanisms give rise to very different design criteria for functional models of the OEC active site. This discussion presents the electron counts and ligand geometries that support metal oxos for AB and RC O–O bond-forming reactions. The construction of architectures that bring two oxygen functionalities together under the purview of the AB and RC scenarios are described. PMID:17971328

  9. Oxygen requirements for formation and activity of the squalene expoxidase in Saccharomyces cerevisiae

    NASA Technical Reports Server (NTRS)

    Jahnke, L.; Klein, H. P.

    1983-01-01

    The effect of oxygen on squalene epoxidase activity in Saccharomyces cerevisiae was investigated. In cells grown in standing cultures, the epoxidase was localized mainly in the 'mitochondrial' fraction. Upon aeration, enzyme activity increased and the newly formed enzyme was associated with the 'microsomal' fraction. At 0.03 percent (vol/vol) oxygen, epoxidase levels doubled, whereas the ergosterol level was only slightly increased. Cycloheximide inhibited the increase in epoxidase under these conditions. An apparent K sub m for oxygen of 0.38 percent (vol/vol) was determined from a crude particulate preparation for the epoxidase.

  10. Use of oxygen scavengers to stabilize solid pharmaceutical dosage forms: a case study.

    PubMed

    Waterman, Kenneth C; Roy, Michael C

    2002-05-01

    A case study is described where degradation of a solid pharmaceutical dosage form susceptible to oxidation is minimized by incorporation of an oxygen scavenger as part of the packaging. Extremely low oxygen levels are attainable within 24 hr of packaging, even with permeable high-density polyethylene bottles commonly used in the pharmaceutical industry. This packaging methodology allows for a practical formulation-independent pathway for reducing or eliminating oxidative instability. In addition, this technology provides a convenient mechanistic probe for the degradation mechanism of solid dosage forms.

  11. $sup 238$Pu fuel form activities

    SciTech Connect

    Not Available

    1987-06-01

    This report for STYPu Fuel Form Activities has one main section: SRP-PuFF Facility. The SRL portion of this program has been completed. The program status, budget information, and milestone schedules are discussed. The SRP portion of this report summarizes production of STYPuO2 fuel forms for use in radioisotopic thermoelectric generators (RTG's) in the Plutonium Fuel Form (Puff) Facility at the Savannah River Plant. The PuFF Facility has been placed in a production readiness mode of operation pending funding of additional heat source programs.

  12. Oxygen fugacity of basaltic magmas and the role of gas-forming elements

    NASA Technical Reports Server (NTRS)

    Sato, M.

    1978-01-01

    It is suggested that major variations in the relative oxygen fugacity of a basaltic magma are caused primarily by gas-forming elements, especially carbon and hydrogen. According to this theory, carbon, present in the source region of a basaltic magma, reduces the host magma during ascent, as isothermally carbon becomes more reducing with decreasing pressure. For an anhydrous magma such as lunar basalts, this reduction continues through the extrusive phase and the relative oxygen fugacity decreases rapidly until buffered by the precipitation of a metallic phase. For hydrous magmas such as terrestrial basalts, reduction by carbon is eventually superceded by oxidation due to loss of H2 generated by the reaction of C with H2O and by thermal dissociation of H2O. The relative oxygen fugacity of a hydrous magma initially decreases as a magma ascends from the source region and then increases until magnetite crystallization curbs the rising trend of the relative oxygen fugacity.

  13. Kinetic studies on the oxidation of semiquinone and hydroquinone forms of Arabidopsis cryptochrome by molecular oxygen

    PubMed Central

    van Wilderen, Luuk J.G.W.; Silkstone, Gary; Mason, Maria; van Thor, Jasper J.; Wilson, Michael T.

    2015-01-01

    Cryptochromes (crys) are flavoprotein photoreceptors present throughout the biological kingdom that play important roles in plant development and entrainment of the circadian clock in several organisms. Crys non-covalently bind flavin adenine dinucleotide (FAD) which undergoes photoreduction from the oxidised state to a radical form suggested to be active in signalling in vivo. Although the photoreduction reactions have been well characterised by a number of approaches, little is known of the oxidation reactions of crys and their mechanisms. In this work, a stopped-flow kinetics approach is used to investigate the mechanism of cry oxidation in the presence and absence of an external electron donor. This in vitro study extends earlier investigations of the oxidation of Arabidopsis cryptochrome1 by molecular oxygen and demonstrates that, under some conditions, a more complex model for oxidation of the flavin than was previously proposed is required to accommodate the spectral evidence (see P. Müller and M. Ahmad (2011) J. Biol. Chem. 286, 21033–21040 [1]). In the absence of an electron donor, photoreduction leads predominantly to the formation of the radical FADH•. Dark recovery most likely forms flavin hydroperoxide (FADHOOH) requiring superoxide. In the presence of reductant (DTT), illumination yields the fully reduced flavin species (FADH−). Reaction of this with dioxygen leads to transient radical (FADH•) and simultaneous accumulation of oxidised species (FAD), possibly governed by interplay between different cryptochrome molecules or cooperativity effects within the cry homodimer. PMID:26649273

  14. Signal transduction in light-oxygen-voltage receptors lacking the adduct-forming cysteine residue.

    PubMed

    Yee, Estella F; Diensthuber, Ralph P; Vaidya, Anand T; Borbat, Peter P; Engelhard, Christopher; Freed, Jack H; Bittl, Robert; Möglich, Andreas; Crane, Brian R

    2015-12-09

    Light-oxygen-voltage (LOV) receptors sense blue light through the photochemical generation of a covalent adduct between a flavin-nucleotide chromophore and a strictly conserved cysteine residue. Here we show that, after cysteine removal, the circadian-clock LOV-protein Vivid still undergoes light-induced dimerization and signalling because of flavin photoreduction to the neutral semiquinone (NSQ). Similarly, photoreduction of the engineered LOV histidine kinase YF1 to the NSQ modulates activity and downstream effects on gene expression. Signal transduction in both proteins hence hinges on flavin protonation, which is common to both the cysteinyl adduct and the NSQ. This general mechanism is also conserved by natural cysteine-less, LOV-like regulators that respond to chemical or photoreduction of their flavin cofactors. As LOV proteins can react to light even when devoid of the adduct-forming cysteine, modern LOV photoreceptors may have arisen from ancestral redox-active flavoproteins. The ability to tune LOV reactivity through photoreduction may have important implications for LOV mechanism and optogenetic applications.

  15. Active superconducting devices formed of thin films

    DOEpatents

    Martens, Jon S.; Beyer, James B.; Nordman, James E.; Hohenwarter, Gert K. G.

    1991-05-28

    Active superconducting devices are formed of thin films of superconductor which include a main conduction channel which has an active weak link region. The weak link region is composed of an array of links of thin film superconductor spaced from one another by voids and selected in size and thickness such that magnetic flux can propagate across the weak link region when it is superconducting. Magnetic flux applied to the weak link region will propagate across the array of links causing localized loss of superconductivity in the links and changing the effective resistance across the links. The magnetic flux can be applied from a control line formed of a superconducting film deposited coplanar with the main conduction channel and weak link region on a substrate. The devices can be formed of any type to superconductor but are particularly well suited to the high temperature superconductors since the devices can be entirely formed from coplanar films with no overlying regions. The devices can be utilized for a variety of electrical components, including switching circuits, amplifiers, oscillators and modulators, and are well suited to microwave frequency applications.

  16. Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries.

    PubMed

    Lu, Yi-Chun; Gasteiger, Hubert A; Shao-Horn, Yang

    2011-11-30

    We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO(4) 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li(+)-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a "volcano-type" trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O(2) cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li(+)-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications.

  17. Snapshots of enzymatic Baeyer-Villiger catalysis: oxygen activation and intermediate stabilization.

    PubMed

    Orru, Roberto; Dudek, Hanna M; Martinoli, Christian; Torres Pazmiño, Daniel E; Royant, Antoine; Weik, Martin; Fraaije, Marco W; Mattevi, Andrea

    2011-08-19

    Baeyer-Villiger monooxygenases catalyze the oxidation of carbonylic substrates to ester or lactone products using NADPH as electron donor and molecular oxygen as oxidative reactant. Using protein engineering, kinetics, microspectrophotometry, crystallography, and intermediate analogs, we have captured several snapshots along the catalytic cycle which highlight key features in enzyme catalysis. After acting as electron donor, the enzyme-bound NADP(H) forms an H-bond with the flavin cofactor. This interaction is critical for stabilizing the oxygen-activating flavin-peroxide intermediate that results from the reaction of the reduced cofactor with oxygen. An essential active-site arginine acts as anchoring element for proper binding of the ketone substrate. Its positively charged guanidinium group can enhance the propensity of the substrate to undergo a nucleophilic attack by the flavin-peroxide intermediate. Furthermore, the arginine side chain, together with the NADP(+) ribose group, forms the niche that hosts the negatively charged Criegee intermediate that is generated upon reaction of the substrate with the flavin-peroxide. The fascinating ability of Baeyer-Villiger monooxygenases to catalyze a complex multistep catalytic reaction originates from concerted action of this Arg-NADP(H) pair and the flavin subsequently to promote flavin reduction, oxygen activation, tetrahedral intermediate formation, and product synthesis and release. The emerging picture is that these enzymes are mainly oxygen-activating and "Criegee-stabilizing" catalysts that act on any chemically suitable substrate that can diffuse into the active site, emphasizing their potential value as toolboxes for biocatalytic applications.

  18. Microfluidic Platform Generates Oxygen Landscapes for Localized Hypoxic Activation

    PubMed Central

    Rexius, Megan L.; Mauleon, Gerardo; Malik, Asrar B.; Rehman, Jalees; Eddington, David T.

    2014-01-01

    An open-well microfluidic platform generates an oxygen landscape using gas-perfused networks which diffuse across a membrane. The device enables real-time analysis of cellular and tissue responses to oxygen tension to define how cells adapt to heterogeneous oxygen conditions found in the physiological setting. We demonstrate that localized hypoxic activation of cells elicited specific metabolic and gene responses in human microvascular endothelial cells and bone marrow-derived mesenchymal stem cells. A robust demonstration of the compatibility of the device with standard laboratory techniques demonstrates the wide utility of the method. This platform is ideally suited to study real-time cell responses and cell-cell interactions within physiologically relevant oxygen landscapes. PMID:25315003

  19. Excited states in the active media of oxygen - iodine lasers

    SciTech Connect

    Azyazov, V N

    2009-11-30

    A review of investigations of kinetic processes in active media oxygen - iodine lasers (OILs) performed in the last decade is presented. The mechanisms of pumping and quenching of electronically and vibrationally excited O{sub 2} and I{sub 2} molecules are considered, and dissociation mechanisms of I{sub 2} in the active medium of the OIL are analysed. The values of kinetic constants of processes proceeding in the active media of OILs are recommended. (review)

  20. Oxygen saturation during daily activities in chronic obstructive pulmonary disease.

    PubMed

    Soguel Schenkel, N; Burdet, L; de Muralt, B; Fitting, J W

    1996-12-01

    Patients with chronic obstructive pulmonary disease (COPD) frequently develop nocturnal oxygen desturation because of alveolar hypoventilation, worsening of ventilation-perfusion mismatch, and sometimes obstructive sleep apnoeas. In contrast, little is known about their oxygen status during the various activities of daily life. The aim of this study was to compare the oxygen saturation profile during day and night, and to assess the influence of different daily activities in COPD. During a rehabilitation programme, we studied 30 patients with moderate-to-severe COPD (median forced expiratory volume in one second (FEV1) 37% of predicted), without marked hypoxaemia (median arterial oxygen tension (Pa,O2) 9.1 kPa). Arterial oxygen saturation (Sa,O2) was assessed by pulse oximetry during night (8 h) and day (10.5 h). The mean and minimal Sa,O2 were calculated, and desaturations were defined as Sa,O2 falls > 4%.h-1. Daily activities were identified by the patients as resting, eating, washing, nebulization therapy and walking. Mean Sa,O2 was lower during the night (88%) than during the day (89%). In contrast, minimal Sa,O2 was lower during the day (69%) than during the night (72%), and the number of desaturations was higher during the day (8.6 desaturations.h-1) than during the night (6.8 desaturations.h-1). Mean Sa,O2 was 88% during walking, which was lower than during resting (90%), nebulization (90%), and meals (89%). The number of desaturations was higher during walking (13.1 desaturations.h-1), washing (12.6 desaturations.h-1), and eating (9.2 desaturations.h-1) than during resting (5.3 desaturations.h-1). We conclude that daily activities, such as walking, washing and eating, are associated with transient oxygen desaturation in patients with moderate-to-severe chronic obstructive pulmonary disease, even without marked resting hypoxaemia.

  1. Early oxygen-utilization and brain activity in preterm infants.

    PubMed

    Tataranno, Maria Luisa; Alderliesten, Thomas; de Vries, Linda S; Groenendaal, Floris; Toet, Mona C; Lemmers, Petra M A; Vosse van de, Renè E; van Bel, Frank; Benders, Manon J N L

    2015-01-01

    The combined monitoring of oxygen supply and delivery using Near-InfraRed spectroscopy (NIRS) and cerebral activity using amplitude-integrated EEG (aEEG) could yield new insights into brain metabolism and detect potentially vulnerable conditions soon after birth. The relationship between NIRS and quantitative aEEG/EEG parameters has not yet been investigated. Our aim was to study the association between oxygen utilization during the first 6 h after birth and simultaneously continuously monitored brain activity measured by aEEG/EEG. Forty-four hemodynamically stable babies with a GA < 28 weeks, with good quality NIRS and aEEG/EEG data available and who did not receive morphine were included in the study. aEEG and NIRS monitoring started at NICU admission. The relation between regional cerebral oxygen saturation (rScO2) and cerebral fractional tissue oxygen extraction (cFTOE), and quantitative measurements of brain activity such as number of spontaneous activity transients (SAT) per minute (SAT rate), the interval in seconds (i.e. time) between SATs (ISI) and the minimum amplitude of the EEG in μV (min aEEG) were evaluated. rScO2 was negatively associated with SAT rate (β=-3.45 [CI=-5.76- -1.15], p=0.004) and positively associated with ISI (β=1.45 [CI=0.44-2.45], p=0.006). cFTOE was positively associated with SAT rate (β=0.034 [CI=0.009-0.059], p=0.008) and negatively associated with ISI (β=-0.015 [CI=-0.026- -0.004], p=0.007). Oxygen delivery and utilization, as indicated by rScO2 and cFTOE, are directly related to functional brain activity, expressed by SAT rate and ISI during the first hours after birth, showing an increase in oxygen extraction in preterm infants with increased early electro-cerebral activity. NIRS monitored oxygenation may be a useful biomarker of brain vulnerability in high-risk infants. PMID:25965343

  2. Nature of Activated Manganese Oxide for Oxygen Evolution.

    PubMed

    Huynh, Michael; Shi, Chenyang; Billinge, Simon J L; Nocera, Daniel G

    2015-12-01

    Electrodeposited manganese oxide films (MnOx) are promising stable oxygen evolution catalysts. They are able to catalyze the oxygen evolution reaction in acidic solutions but with only modest activity when prepared by constant anodic potential deposition. We now show that the performance of these catalysts is improved when they are "activated" by potential cycling protocols, as measured by Tafel analysis (where lower slope is better): upon activation the Tafel slope decreases from ∼120 to ∼70 mV/decade in neutral conditions and from ∼650 to ∼90 mV/decade in acidic solutions. Electrochemical, spectroscopic, and structural methods were employed to study the activation process and support a mechanism where the original birnessite-like MnOx (δ-MnO2) undergoes a phase change, induced by comproportionation with cathodically generated Mn(OH)2, to a hausmannite-like intermediate (α-Mn3O4). Subsequent anodic conditioning from voltage cycling or water oxidation produces a disordered birnessite-like phase, which is highly active for oxygen evolution. At pH 2.5, the current density of activated MnOx (at an overpotential of 600 mV) is 2 orders of magnitude higher than that of the original MnOx and begins to approach that of Ru and Ir oxides in acid. PMID:26574923

  3. Changes to coral health and metabolic activity under oxygen deprivation.

    PubMed

    Murphy, James W A; Richmond, Robert H

    2016-01-01

    On Hawaiian reefs, the fast-growing, invasive algae Gracilaria salicornia overgrows coral heads, restricting water flow and light, thereby smothering corals. Field data shows hypoxic conditions (dissolved oxygen (DO2) < 2 mg/L) occurring underneath algal mats at night, and concurrent bleaching and partial tissue loss of shaded corals. To analyze the impact of nighttime oxygen-deprivation on coral health, this study evaluated changes in coral metabolism through the exposure of corals to chronic hypoxic conditions and subsequent analyses of lactate, octopine, alanopine, and strombine dehydrogenase activities, critical enzymes employed through anaerobic respiration. Following treatments, lactate and octopine dehydrogenase activities were found to have no significant response in activities with treatment and time. However, corals subjected to chronic nighttime hypoxia were found to exhibit significant increases in alanopine dehydrogenase activity after three days of exposure and strombine dehydrogenase activity starting after one overnight exposure cycle. These findings provide new insights into coral metabolic shifts in extremely low-oxygen environments and point to ADH and SDH assays as tools for quantifying the impact of hypoxia on coral health. PMID:27114888

  4. Changes to coral health and metabolic activity under oxygen deprivation

    PubMed Central

    Richmond, Robert H.

    2016-01-01

    On Hawaiian reefs, the fast-growing, invasive algae Gracilaria salicornia overgrows coral heads, restricting water flow and light, thereby smothering corals. Field data shows hypoxic conditions (dissolved oxygen (DO2) < 2 mg/L) occurring underneath algal mats at night, and concurrent bleaching and partial tissue loss of shaded corals. To analyze the impact of nighttime oxygen-deprivation on coral health, this study evaluated changes in coral metabolism through the exposure of corals to chronic hypoxic conditions and subsequent analyses of lactate, octopine, alanopine, and strombine dehydrogenase activities, critical enzymes employed through anaerobic respiration. Following treatments, lactate and octopine dehydrogenase activities were found to have no significant response in activities with treatment and time. However, corals subjected to chronic nighttime hypoxia were found to exhibit significant increases in alanopine dehydrogenase activity after three days of exposure and strombine dehydrogenase activity starting after one overnight exposure cycle. These findings provide new insights into coral metabolic shifts in extremely low-oxygen environments and point to ADH and SDH assays as tools for quantifying the impact of hypoxia on coral health. PMID:27114888

  5. Changes to coral health and metabolic activity under oxygen deprivation.

    PubMed

    Murphy, James W A; Richmond, Robert H

    2016-01-01

    On Hawaiian reefs, the fast-growing, invasive algae Gracilaria salicornia overgrows coral heads, restricting water flow and light, thereby smothering corals. Field data shows hypoxic conditions (dissolved oxygen (DO2) < 2 mg/L) occurring underneath algal mats at night, and concurrent bleaching and partial tissue loss of shaded corals. To analyze the impact of nighttime oxygen-deprivation on coral health, this study evaluated changes in coral metabolism through the exposure of corals to chronic hypoxic conditions and subsequent analyses of lactate, octopine, alanopine, and strombine dehydrogenase activities, critical enzymes employed through anaerobic respiration. Following treatments, lactate and octopine dehydrogenase activities were found to have no significant response in activities with treatment and time. However, corals subjected to chronic nighttime hypoxia were found to exhibit significant increases in alanopine dehydrogenase activity after three days of exposure and strombine dehydrogenase activity starting after one overnight exposure cycle. These findings provide new insights into coral metabolic shifts in extremely low-oxygen environments and point to ADH and SDH assays as tools for quantifying the impact of hypoxia on coral health.

  6. Iridium Oxide Coatings with Templated Porosity as Highly Active Oxygen Evolution Catalysts: Structure-Activity Relationships.

    PubMed

    Bernicke, Michael; Ortel, Erik; Reier, Tobias; Bergmann, Arno; Ferreira de Araujo, Jorge; Strasser, Peter; Kraehnert, Ralph

    2015-06-01

    Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) . PMID:25958795

  7. Iridium Oxide Coatings with Templated Porosity as Highly Active Oxygen Evolution Catalysts: Structure-Activity Relationships.

    PubMed

    Bernicke, Michael; Ortel, Erik; Reier, Tobias; Bergmann, Arno; Ferreira de Araujo, Jorge; Strasser, Peter; Kraehnert, Ralph

    2015-06-01

    Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) .

  8. Electron Spin Resonance (ESR) detection of active oxygen species and organic phases in Martian soils

    NASA Technical Reports Server (NTRS)

    Tsay, Fun-Dow; Kim, Soon Sam; Liang, Ranty H.

    1989-01-01

    The presence of active oxygen species (O(-), O2(-), O3(-)) and other strong oxidants (Fe2O3 and Fe3O4) was invoked in interpretations of the Viking biological experiments and a model was also suggested for Martian surface chemistry. The non-biological interpretations of the biological results gain futher support as no organic compounds were detected in the Viking pyrolysis-gas chromatography mass spectrometer (GCSM) experiments at concentrations as low as 10 ppb. Electron spin resonance (ESR) measures the absorption of microwaves by a paramagnetic and/or ferromagnetic center in the presence of an external field. In many instances, ESR has the advantage of detailed submicroscopic identification of the transient species and/or unstable reaction intermediates in their environments. Since the higly active oxygen species (O(-), O2(-), O3(-), and R-O-O(-)) are all paramagnetic in nature, they can be readily detected in native form by the ESR method. Active oxygen species likely to occur in the Martian surface samples were detected by ESR in UV-irradiated samples containing MgO. A miniaturized ESR spectrometer system can be developed for the Mars Rover Sample Return Mission. The instrument can perform the following in situ Martian samples analyses: detection of active oxygen species; characterization of Martian surface chemistry and photooxidation processes; and searching for organic compounds in the form of free radicals preserved in subsoils, and detection of microfossils with Martian carbonate sediments.

  9. Thickness independent reduced forming voltage in oxygen engineered HfO{sub 2} based resistive switching memories

    SciTech Connect

    Sharath, S. U. Kurian, J.; Komissinskiy, P.; Hildebrandt, E.; Alff, L.; Bertaud, T.; Walczyk, C.; Calka, P.; Schroeder, T.

    2014-08-18

    The conducting filament forming voltage of stoichiometric hafnium oxide based resistive switching layers increases linearly with layer thickness. Using strongly reduced oxygen deficient hafnium oxide thin films grown on polycrystalline TiN/Si(001) substrates, the thickness dependence of the forming voltage is strongly suppressed. Instead, an almost constant forming voltage of about 3 V is observed up to 200 nm layer thickness. This effect suggests that filament formation and switching occurs for all samples in an oxidized HfO{sub 2} surface layer of a few nanometer thickness while the highly oxygen deficient thin film itself merely serves as a oxygen vacancy reservoir.

  10. Screening of antibacterial activities of twenty-one oxygenated monoterpenes.

    PubMed

    Kotan, Recep; Kordali, Saban; Cakir, Ahmet

    2007-01-01

    Plant essential oils are widely used as fragrances and flavours in the cosmetic, perfume, drug and food industries. Oxygenated monoterpenes are widespread components of the essential oils, usually occurring in high amount. In this paper, the antibacterial activities of twenty-one oxygenated monoterpenes (borneol, borneol acetate, camphor, carvone, 1,8-cineole, citronellal, beta-citronellol, dihydrocarvone, fenchol, fenchone, geraniol acetate, isomenthol, limonene oxide, linalool, linalool acetate, nerol, nerol acetate, terpinen-4-ol, alpha-terpineol, menthol and menthone) and penicillin (standard antibiotic) were determined using a disc diffusion method (in vitro) against 63 bacterial strains, belonging to 37 different genera and 54 species (plant, food and clinic origins). The results showed that the oxygenated monoterpenes exhibited a variable degree of antibacterial activities. These compounds also inhibited the growth of bacterial strains by producing a weak zone of inhibition from 7 to 11 mm in diameter, depending on the susceptibility of the tested bacteria. Among the tested compounds, nerol, linalool alpha-terpineol, fenchol and terpinen-4-ol showed antibacterial activity at a broad spectrum. However, their antibacterial activities were lower than those of penicillin. In contrast to these compounds, camphor and 1,8-cineole exhibited no inhibition effects on the growth of all tested bacteria.

  11. Reactive oxygen scavenging activity of matured whiskey and its active polyphenols.

    PubMed

    Koga, K; Taguchi, A; Koshimizu, S; Suwa, Y; Yamada, Y; Shirasaka, N; Yoshizumi, H

    2007-04-01

    The quality of whiskey is known to improve remarkably by its storage over many years. This process is commonly termed "maturing." In this process, polyphenols derived from lignin and tannin of the barrel have an important role in not only forming the matured flavor and taste but also contributing to the advance of clustering ethanol and water in whiskey. It is also likely that polyphenols generally possess reactive oxygen (RO) scavenging activity. The present study evaluated the RO scavenging activity (free-radical scavenging activity, H(2)O(2) reduction activity under peroxidase coculture, and H(2)O(2)scavenging activity) of 24 single malt whiskeys with a maturation age of 10 to 30 y produced in Japanese, Scotch (Islay), or Scotch (Speyside and Highland) regions. Single malt whiskey not only showed RO scavenging activity but there was also a positive correlation between this activity and the maturation age of whiskey exceeding the difference resulting from the manufacturing region. A nonvolatile fraction derived from the barrel was responsible for RO scavenging activity. In particular, the contents of ellagic and gallic acids and lyoniresinol, the main polyphenolic compounds in whiskey, increased with maturation age. For the free-radical scavenging activity per molecule, each compound was 1.68 to 3.14 times that of trolox (a water-soluble vitamin E). The activities of ellagic acid, gallic acid, and lyoniresinol in the whiskey (Yamazaki 18) were equivalent to that of 80.3, 31.2, and 11.1 ppm trolox, respectively. Accordingly, the total activity of these 3 compounds accounted for about 20% of the activity of the whiskey (630.7 ppm trolox).

  12. Reactive oxygen scavenging activity of matured whiskey and its active polyphenols.

    PubMed

    Koga, K; Taguchi, A; Koshimizu, S; Suwa, Y; Yamada, Y; Shirasaka, N; Yoshizumi, H

    2007-04-01

    The quality of whiskey is known to improve remarkably by its storage over many years. This process is commonly termed "maturing." In this process, polyphenols derived from lignin and tannin of the barrel have an important role in not only forming the matured flavor and taste but also contributing to the advance of clustering ethanol and water in whiskey. It is also likely that polyphenols generally possess reactive oxygen (RO) scavenging activity. The present study evaluated the RO scavenging activity (free-radical scavenging activity, H(2)O(2) reduction activity under peroxidase coculture, and H(2)O(2)scavenging activity) of 24 single malt whiskeys with a maturation age of 10 to 30 y produced in Japanese, Scotch (Islay), or Scotch (Speyside and Highland) regions. Single malt whiskey not only showed RO scavenging activity but there was also a positive correlation between this activity and the maturation age of whiskey exceeding the difference resulting from the manufacturing region. A nonvolatile fraction derived from the barrel was responsible for RO scavenging activity. In particular, the contents of ellagic and gallic acids and lyoniresinol, the main polyphenolic compounds in whiskey, increased with maturation age. For the free-radical scavenging activity per molecule, each compound was 1.68 to 3.14 times that of trolox (a water-soluble vitamin E). The activities of ellagic acid, gallic acid, and lyoniresinol in the whiskey (Yamazaki 18) were equivalent to that of 80.3, 31.2, and 11.1 ppm trolox, respectively. Accordingly, the total activity of these 3 compounds accounted for about 20% of the activity of the whiskey (630.7 ppm trolox). PMID:17995817

  13. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    NASA Astrophysics Data System (ADS)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  14. 76 FR 42129 - Agency Information Collection Activities: Case Submission Form, Case Assistance Form

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-18

    ... SECURITY Agency Information Collection Activities: Case Submission Form, Case Assistance Form (Form DHS-7001), Online Ombudsman Form DHS-7001 AGENCY: Office of the Citizenship and Immigration Service... practices of USCIS to mitigate problems. This form is used by an applicant who is experiencing problems...

  15. Origin of Active Oxygen in a Ternary CuOx /Co3O4–CeO 2 Catalyst for CO Oxidation

    DOE PAGES

    Liu, Zhigang; Wu, Zili; Peng, Xihong; Binder, Andrew; Chai, Songhai; Dai, Sheng

    2014-11-14

    In this paper, we have studied CO oxidation over a ternary CuOx/Co3O4-CeO2 catalyst and employed the techniques of N2 adsorption/desporption, XRD, TPR, TEM, in situ DRIFTS and QMS (Quadrupole mass spectrometer) to explore the origin of active oxygen. DRIFTS-QMS results with labeled 18O2 indicate that the origin of active oxygens in CuOx/Co3O4-CeO2 obeys a model, called as queue mechanism. Namely gas-phase molecular oxygens are dissociated to atomic oxygens and then incorporate in oxygen vacancies located at the interface of Co3O4-CeO2 to form active crystalline oxygens, and these active oxygens diffuse to the CO-Cu+ sites thanks to the oxygen vacancy concentrationmore » magnitude and react with the activated CO to form CO2. This process, obeying a queue rule, provides active oxygens to form CO2 from gas-phase O2 via oxygen vacancies and crystalline oxygen at the interface of Co3O4-CeO2.« less

  16. Exchangeable oxygens in the vicinity of the molybdenum center of the high-pH form of sulfite oxidase and sulfite dehydrogenase†

    PubMed Central

    Klein, Eric L.; Ganyushin, Dmitry; Johnson-Winters, Kayunta; Neese, Frank; Kappler, Ulrike; Enemark, John H.

    2009-01-01

    The electron spin echo envelope modulation (ESEEM) investigation of the high-pH (hpH) form of sulfite oxidase (SO) and sulfite dehydrogenase (SDH) prepared in buffer enriched with H2 17O reveals the presence of three types of exchangeable oxygen atoms at the molybdenum center. Two of these oxygen atoms belong to the equatorial OH ligand and the axial oxo ligand, and are characterized by 17O hyperfine interaction (hfi) constants of about 37 MHz and 6 MHz, respectively. The third oxygen has an isotropic hfi constant of 3–4 MHz and likely belongs to a hydroxyl moiety hydrogen-bonded to the equatorial OH ligand. This exchangeable oxygen atom is not observed in the ESEEM spectra of the Y236F mutant of SDH, where the active site tyrosine has been replaced by phenylalanine. PMID:19639147

  17. Utilization of a BGO detector as an active oxygen target

    NASA Astrophysics Data System (ADS)

    Loveman, R.; Gozani, T.; Bendahan, J.; Krivicich, J.; Elias, E.; Altschuler, E.

    1994-12-01

    The (n, n'γx) cross section for the 6.13 MeV state in oxygen has recently become of general interest because of the possibility of using this process to assay oxygen as a part of non-intrusive inspections. Localized densities of carbon, oxygen, and nitrogen are particularly useful in determining the presence of explosives and/or drugs in containers of all sizes, from suitcases to cargo containers. The presence of oxygen in BGO (Bi 4Ge 3O 12) scintillator makes this detector suitable for use as an active target for the measurement of the energy dependence of the excitation, of the first (6.049 MeV O +) and second (6.130 MeV 3 -) excited states in 16O by fast neutron interactions. An active target functions as both a target and an active device such as a detector. The de-excitations of the 6.049 and 6.130 states take place by nuclear pair production and γ-ray emission respectively. There is a large probability of absorbing all of the de-excitation energy in the scintillator in either of these cases. Since the energies deposited in the scintillator by these transitions are very close, the de-excitations are indistinguishable. However, since the cross section for the excitation of the 6.13 MeV state is believed to be larger than that of the 6.049 MeV, the major measured features of the energy variations are those related to the second state. The validity of the technique was initially tested using (MCNP) calculations. The calculations established that the detected neutron count rate in the crystal was proportional to the cross-sections used as input for the calculations, and that the constant of proportionality did not vary with neutron energy. Subsequently, measurements were made with a BGO detector as an active oxygen target. The results clearly show a strong energy dependence including several resonances.

  18. Development of a novel electrochemical system for oxygen control (ESOC) to examine dissolved oxygen inhibition on algal activity.

    PubMed

    Keymer, Philip C; Pratt, Steven; Lant, Paul A

    2013-09-01

    The development of an Electrochemical System for Oxygen Control (ESOC) for examining algal photosynthetic activity as a function of dissolved oxygen (DO) is outlined. The main innovation of the tool is coulombic titration in order to balance the electrochemical reduction of oxygen with the oxygen input to achieve a steady DO set-point. ESOC allows quantification of algal oxygen production whilst simultaneously maintaining a desired DO concentration. The tool was validated abiotically by comparison with a mass transfer approach for quantifying oxygenation. It was then applied to quantify oxygen inhibition of algal activity. Five experiments, using an enriched culture of Scenedesmus sp. as the inoculum, are presented. For each experiment, ESOC was used to quantify algal activity at a series of DO set-points. In all experiments substantial oxygen inhibition was observed at DO >30 mgO2 L-1. Inhibition was shown to fit a Hill inhibition model, with a common Hill coefficient of 0.22±0.07 L mg-1 and common log10  CI50 of 27.2±0.7 mg L-1. This is the first time that the oxygen inhibition kinetic parameters have been quantified under controlled DO conditions.

  19. Metal oxide nanoparticle growth on graphene via chemical activation with atomic oxygen.

    PubMed

    Johns, James E; Alaboson, Justice M P; Patwardhan, Sameer; Ryder, Christopher R; Schatz, George C; Hersam, Mark C

    2013-12-01

    Chemically interfacing the inert basal plane of graphene with other materials has limited the development of graphene-based catalysts, composite materials, and devices. Here, we overcome this limitation by chemically activating epitaxial graphene on SiC(0001) using atomic oxygen. Atomic oxygen produces epoxide groups on graphene, which act as reactive nucleation sites for zinc oxide nanoparticle growth using the atomic layer deposition precursor diethyl zinc. In particular, exposure of epoxidized graphene to diethyl zinc abstracts oxygen, creating mobile species that diffuse on the surface to form metal oxide clusters. This mechanism is corroborated with a combination of scanning probe microscopy, Raman spectroscopy, and density functional theory and can likely be generalized to a wide variety of related surface reactions on graphene.

  20. Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

    SciTech Connect

    Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

    2012-01-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  1. Trends in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium.

    PubMed

    Dathar, Gopi Krishna Phani; Shelton, William A; Xu, Ye

    2012-04-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O2 on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  2. Catalytic reduction of NO by CO over rhodium catalysts. 2. Effect of oxygen on the nature, population, and reactivity of surface species formed under reaction conditions

    SciTech Connect

    Kondarides, D.I.; Chafik, T.; Verykios, X.E.

    2000-04-01

    The effect of oxygen on the nature, population, and reactivity of surface species formed during reduction of NO by CO over Rh/TiO{sub 2} catalysts has been examined employing FTIR and transient MS techniques. It has been found that the activity of Rh is hindered by accumulation of surface oxygen originating from NO decomposition and gas-phase oxygen in the feed. Adsorbed CO and reduced TiO{sub 2{minus}x} species in the vicinity of Rh particles act as oxygen atom scavengers and, under fuel-rich conditions, remove atomic oxygen from the surface and restore the catalytic properties. Results of the present study provide additional evidence that production of N{sub 2} is related to dissociation of adsorbed Rh-NO{sup {minus}} while production of N{sub 2}O is related to the presence of Rh(NO){sub 2}. The presence of reduced RH{sup 0} sites is necessary for the formation of both reduction products. In the absence of oxygen in the feed, surface isocyanate species are also observed under reaction conditions. Their formation requires the presence of adjacent Rh{sup 0}-CO and reduced Rh{sup 0} sites. Although these species are favored under conditions in which NO conversion to reduction products is observed, there is no evidence that they are catalytically active species.

  3. Device for measuring oxygen activity in liquid sodium

    DOEpatents

    Roy, P.; Young, R.S.

    1973-12-01

    A composite ceramic electrolyte in a configuration (such as a closed end tube or a plate) suitable to separate liquid sodium from a reference electrode with a high impedance voltmeter connected to measure EMF between the sodium and the reference electrode as a measure of oxygen activity in the sodium is described. The composite electrolyte consists of zirconiacalcia with a bonded layer of thoria-yttria. The device is used with a gaseous reference electrode on the zirconia-calcia side and liquid sodium on the thoria-yttria side of the electrolyte. (Official Gazette)

  4. Bioreductively Activated Reactive Oxygen Species (ROS) Generators as MRSA Inhibitors.

    PubMed

    Khodade, Vinayak S; Sharath Chandra, Mallojjala; Banerjee, Ankita; Lahiri, Surobhi; Pulipeta, Mallikarjuna; Rangarajan, Radha; Chakrapani, Harinath

    2014-07-10

    The number of cases of drug resistant Staphylococcus aureus infections is on the rise globally and new strategies to identify drug candidates with novel mechanisms of action are in urgent need. Here, we report the synthesis and evaluation of a series of benzo[b]phenanthridine-5,7,12(6H)-triones, which were designed based on redox-active natural products. We find that the in vitro inhibitory activity of 6-(prop-2-ynyl)benzo[b]phenanthridine-5,7,12(6H)-trione (1f) against methicillin-resistant Staphylococcus aureus (MRSA), including a panel of patient-derived strains, is comparable or better than vancomycin. We show that the lead compound generates reactive oxygen species (ROS) in the cell, contributing to its antibacterial activity. PMID:25050164

  5. Neural network with formed dynamics of activity

    SciTech Connect

    Dunin-Barkovskii, V.L.; Osovets, N.B.

    1995-03-01

    The problem of developing a neural network with a given pattern of the state sequence is considered. A neural network structure and an algorithm, of forming its bond matrix which lead to an approximate but robust solution of the problem are proposed and discussed. Limiting characteristics of the serviceability of the proposed structure are studied. Various methods of visualizing dynamic processes in a neural network are compared. Possible applications of the results obtained for interpretation of neurophysiological data and in neuroinformatics systems are discussed.

  6. Silk Microgels Formed by Proteolytic Enzyme Activity

    PubMed Central

    Samal, Sangram K.; Dash, Mamoni; Chiellini, Federica; Kaplan, David L.; Chiellini, Emo

    2013-01-01

    The proteolytic enzyme α-chymotrypsin selectively cleaves the amorphous regions of silk fibroin protein (SFP) and allows the crystalline regions to self-assemble into silk microgels (SMG) at physiological temperature. These microgels consist of lamellar crystals in the micrometer scale, in contrast to the nanometer scaled crystals in native silkworm fibers. SDS-PAGE and zeta potential results demonstrated that α-chymotrypsin utilized only the nonamorphous domains or segments of the heavy chain of SFP to form negatively charged SMGs. The SMGs were characterized in terms of size, charge, structure, morphology, crystallinity, swelling kinetics, water content and thermal properties. The results suggest that the present technique of preparing SMGs by α-chymotrypsin is simple and efficient potential and that the prepared SMGS have useful features for studies related to biomaterials and pharmaceutical needs. This process is also an easy approach to obtain the amorphous peptide chains for further study. PMID:23756227

  7. Silk microgels formed by proteolytic enzyme activity.

    PubMed

    Samal, Sangram K; Dash, Mamoni; Chiellini, Federica; Kaplan, David L; Chiellini, Emo

    2013-09-01

    The proteolytic enzyme α-chymotrypsin selectively cleaves the amorphous regions of silk fibroin protein (SFP) and allows the crystalline regions to self-assemble into silk microgels (SMGs) at physiological temperature. These microgels consist of lamellar crystals in the micrometer scale, in contrast to the nanometer-scaled crystals in native silkworm fibers. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis and zeta potential results demonstrated that α-chymotrypsin utilized only the non-amorphous domains or segments of the heavy chain of SFP to form negatively charged SMGs. The SMGs were characterized in terms of size, charge, structure, morphology, crystallinity, swelling kinetics, water content and thermal properties. The results suggest that the present technique of preparing SMGs by α-chymotrypsin is simple and efficient, and that the prepared SMGs have useful features for studies related to biomaterial and pharmaceutical needs. This process is also an easy way to obtain the amorphous peptide chains for further study. PMID:23756227

  8. Antioxidative activity of lactobacilli measured by oxygen radical absorbance capacity.

    PubMed

    Saide, J A O; Gilliland, S E

    2005-04-01

    The reducing ability and antioxidative activity of some species of Lactobacillus were compared under in vitro conditions. Cultures of Lactobacillus delbrueckii ssp. lactis, Lactobacillus delbrueckii ssp. bulgaricus, Lactobacillus acidophilus, and Lactobacillus casei were grown at 37 degrees C in de Man, Rogosa, Sharpe (MRS) broth supplemented with 0.5% 2,3,5 triphenyl tetrazolium chloride (TTC) to evaluate reducing activity. Reduced TTC was extracted from the cultures with acetone, and the intensity of the red color measured colorimetrically at 485 nm was an indication of reducing activity. The lactobacilli varied significantly in relative ability to reduce TTC when grown in MRS broth for 15 h. The relative amounts of growth as indicated by pH values at 18 h appeared to influence the amount of reduction. Antioxidative activity was evaluated by the ability of the whole cells or the cell-free extracts from cultures to protect a protein from being attacked by free radicals. These analyses were performed using the oxygen radical absorbance capacity method. All cultures tested exhibited some degree of antioxidative activity. Among the treatments, the cell-free extracts from cells grown in MRS broth exhibited significantly higher values than did whole cells. There was no apparent relationship between the reducing and antioxidative activities of the cultures evaluated. The results from this study show that these cultures can provide a source of dietary antioxidants. Furthermore, selection of cultures that produce antioxidants as starters could provide yet another health or nutritional benefit from cultured or culture-containing dairy products.

  9. Activation of Oxygen by Cytochrome P-450 and Other Haemoproteins

    NASA Astrophysics Data System (ADS)

    Metelitsa, D. I.

    1982-11-01

    Data on the activation of molecular oxygen by the full microsomal hydroxylating system containing cytochrome P-450 as the terminal oxygenase are examined. The nature of the hydroxylating agent, which is the oxenoid Fe3+O, is analysed. The autoxidation reactions of cytochrome P-450 from various sources, haemoglobin, myoglobin, and peroxidases are compared and the role of the axial ligands of the haem iron and the structure of the active centres of the haemoproteins in this process is demonstrated. The possible mechanisms of the oxidation of organic compounds by peroxides with participation of cytochrome P-450, cytochrome c, haemoglobin, and catalase are examined critically. Haemoproteins have been divided into three groups in terms of the type of peroxide oxidation reactions. The relative contributions of the radical and two-electron reactions in the oxidation of compounds by peroxides with participation of different haemoproteins are analysed. The bibliography includes 184 references.

  10. Knee extensor muscle oxygen consumption in relation to muscle activation.

    PubMed

    Kooistra, R D; Blaauboer, M E; Born, J R; de Ruiter, C J; de Haan, A

    2006-12-01

    Recently, fatigability and muscle oxygen consumption (mVO(2)) during sustained isometric contractions were found to be less at shorter (30 degrees knee angle; 0 degrees = full extension) compared to longer knee extensor muscle lengths (90 degrees ) and, at low torques, less in the rectus femoris (RF) muscle than in the vastus lateralis and medialis. In the present study we hypothesized that these findings could be accounted for by a knee angle- and a muscle-dependent activation respectively. On two experimental days rectified surface EMG (rsEMG) was obtained as a measure of muscle activation in nine healthy young males. In addition, on day 1 maximal torque capacity (MTC) was carefully determined using superimposed nerve stimulation on brief high intensity contractions (> 70%MVC) at 30, 60 and 90 degrees knee angles. On day 2, subjects performed longer lasting isometric contractions (10-70%MTC) while mVO(2) was measured using near-infrared spectroscopy (NIRS). At 30 degrees , maximal mVO(2) was reached significantly later (11.0 s +/- 6.5 s) and was 57.9 +/- 8.3% less (average +/- SD, across intensities and muscles) than mVO(2) at 60 and 90 degrees (p < 0.05). However, rsEMG was on average only 18.0 +/- 11.8% (p = 0.062) less at the start of the contraction at 30 degrees . At 10%MTC at all knee angles, maximal mVO(2) of the RF occurred significantly later (28.8 +/- 36.0 s) and showed a significantly smaller increase in rsEMG compared to both vasti. In conclusion, it is unlikely that the tendency for less intense muscle activation could fully account for the approximately 60% lower oxygen consumption at 30 degrees , but the later increase in RFmVO(2) seemed to be caused by a less strong activation of the RF.

  11. Doped LaFeO3 as SOFC Catalysts: Control of Oxygen Mobility Oxidation Activity

    SciTech Connect

    N Lakshminarayanan; J Kuhn; S Rykov; J Millet; U Ozkan; T Rao; J Smedley; E Wang; E Muller; et al.

    2011-12-31

    The bulk structure and surface properties of Fe-based perovskite-type oxides with the formula La{sub 0.6}Sr{sub 0.4}Co{sub y}Fe{sub 1-y}O{sub 3-{delta}} for y = 0.1, 0.2, and 0.3 have been investigated. The properties were found to strongly depend upon Co content, temperature, and environment. The materials were selected due to their potential use as solid oxide fuel cell cathodes. The intermediate Co loading formed oxygen vacancies most easily and several other properties including oxidation activity and surface sites showed a similar non-linear trend. Trends are related to a possible transition in electronic structure. Activity for oxidation of methane, oxygen storage and chemical compatibility was shown to be superior to that of the La{sub 0.6}Sr{sub 0.4}MnO{sub 3}.

  12. The interrelationship between muscle oxygenation, muscle activation, and pulmonary oxygen uptake to incremental ramp exercise: influence of aerobic fitness.

    PubMed

    Boone, Jan; Barstow, Thomas J; Celie, Bert; Prieur, Fabrice; Bourgois, Jan

    2016-01-01

    We investigated whether muscle and ventilatory responses to incremental ramp exercise would be influenced by aerobic fitness status by means of a cross-sectional study with a large subject population. Sixty-four male students (age: 21.2 ± 3.2 years) with a heterogeneous peak oxygen uptake (51.9 ± 6.3 mL·min(-1)·kg(-1), range 39.7-66.2 mL·min(-1)·kg(-1)) performed an incremental ramp cycle test (20-35 W·min(-1)) to exhaustion. Breath-by-breath gas exchange was recorded, and muscle activation and oxygenation were measured with surface electromyography and near-infrared spectroscopy, respectively. The integrated electromyography (iEMG), mean power frequency (MPF), deoxygenated [hemoglobin and myoglobin] (deoxy[Hb+Mb]), and total[Hb+Mb] responses were set out as functions of work rate and fitted with a double linear function. The respiratory compensation point (RCP) was compared and correlated with the breakpoints (BPs) (as percentage of peak oxygen uptake) in muscle activation and oxygenation. The BP in total[Hb+Mb] (83.2% ± 3.0% peak oxygen uptake) preceded (P < 0.001) the BP in iEMG (86.7% ± 4.0% peak oxygen uptake) and MPF (86.3% ± 4.1% peak oxygen uptake), which in turn preceded (P < 0.01) the BP in deoxy[Hb+Mb] (88.2% ± 4.5% peak oxygen uptake) and RCP (87.4% ± 4.5% peak oxygen uptake). Furthermore, the peak oxygen uptake was significantly (P < 0.001) positively correlated to the BPs and RCP, indicating that the BPs in total[Hb+Mb] (r = 0.66; P < 0.001), deoxy[Hb+Mb] (r = 0.76; P < 0.001), iEMG (r = 0.61; P < 0.001), MPF (r = 0.63; P < 0.001), and RCP (r = 0.75; P < 0.001) occurred at a higher percentage of peak oxygen uptake in subjects with a higher peak oxygen uptake. In this study a close relationship between muscle oxygenation, activation, and pulmonary oxygen uptake was found, occurring in a cascade of events. In subjects with a higher aerobic fitness level this cascade occurred at a higher relative intensity.

  13. [Several indicators of tissue oxygen during modeling of extravehicular activity of man].

    PubMed

    Lan'shina, O E; Loginov, V A; Akinfiev, A V; Kovalenko, E A

    1995-01-01

    Investigations of tissue oxygen indices during simulation of extravehicular activity (EVA) of cosmonauts demonstrated that breathing pure oxygen at approximately 280 mmHg elevates oxygen tension in capillary blood, and capillary-tissue gradient during physical work. Physical work alone stimulates tissue oxygenation due to, apparently, intensification of the processes of oxidative phosphorylation. The observed shifts in oxygen status reverse significantly within the first 5 min after completion of the experiment.

  14. Oxygen Affects Gut Bacterial Colonization and Metabolic Activities in a Gnotobiotic Cockroach Model

    PubMed Central

    Tegtmeier, Dorothee; Thompson, Claire L.; Schauer, Christine

    2015-01-01

    The gut microbiota of termites and cockroaches represents complex metabolic networks of many diverse microbial populations. The distinct microenvironmental conditions within the gut and possible interactions among the microorganisms make it essential to investigate how far the metabolic properties of pure cultures reflect their activities in their natural environment. We established the cockroach Shelfordella lateralis as a gnotobiotic model and inoculated germfree nymphs with two bacterial strains isolated from the guts of conventional cockroaches. Fluorescence microscopy revealed that both strains specifically colonized the germfree hindgut. In diassociated cockroaches, the facultatively anaerobic strain EbSL (a new species of Enterobacteriaceae) always outnumbered the obligately anaerobic strain FuSL (a close relative of Fusobacterium varium), irrespective of the sequence of inoculation, which showed that precolonization by facultatively anaerobic bacteria does not necessarily favor colonization by obligate anaerobes. Comparison of the fermentation products of the cultures formed in vitro with those accumulated in situ indicated that the gut environment strongly affected the metabolic activities of both strains. The pure cultures formed the typical products of mixed-acid or butyrate fermentation, whereas the guts of gnotobiotic cockroaches accumulated mostly lactate and acetate. Similar shifts toward more-oxidized products were observed when the pure cultures were exposed to oxygen, which corroborated the strong effects of oxygen on the metabolic fluxes previously observed in termite guts. Oxygen microsensor profiles of the guts of germfree, gnotobiotic, and conventional cockroaches indicated that both gut tissue and microbiota contribute to oxygen consumption and suggest that the oxygen status influences the colonization success. PMID:26637604

  15. Oxygen Affects Gut Bacterial Colonization and Metabolic Activities in a Gnotobiotic Cockroach Model.

    PubMed

    Tegtmeier, Dorothee; Thompson, Claire L; Schauer, Christine; Brune, Andreas

    2016-02-01

    The gut microbiota of termites and cockroaches represents complex metabolic networks of many diverse microbial populations. The distinct microenvironmental conditions within the gut and possible interactions among the microorganisms make it essential to investigate how far the metabolic properties of pure cultures reflect their activities in their natural environment. We established the cockroach Shelfordella lateralis as a gnotobiotic model and inoculated germfree nymphs with two bacterial strains isolated from the guts of conventional cockroaches. Fluorescence microscopy revealed that both strains specifically colonized the germfree hindgut. In diassociated cockroaches, the facultatively anaerobic strain EbSL (a new species of Enterobacteriaceae) always outnumbered the obligately anaerobic strain FuSL (a close relative of Fusobacterium varium), irrespective of the sequence of inoculation, which showed that precolonization by facultatively anaerobic bacteria does not necessarily favor colonization by obligate anaerobes. Comparison of the fermentation products of the cultures formed in vitro with those accumulated in situ indicated that the gut environment strongly affected the metabolic activities of both strains. The pure cultures formed the typical products of mixed-acid or butyrate fermentation, whereas the guts of gnotobiotic cockroaches accumulated mostly lactate and acetate. Similar shifts toward more-oxidized products were observed when the pure cultures were exposed to oxygen, which corroborated the strong effects of oxygen on the metabolic fluxes previously observed in termite guts. Oxygen microsensor profiles of the guts of germfree, gnotobiotic, and conventional cockroaches indicated that both gut tissue and microbiota contribute to oxygen consumption and suggest that the oxygen status influences the colonization success. PMID:26637604

  16. Oxygen Affects Gut Bacterial Colonization and Metabolic Activities in a Gnotobiotic Cockroach Model.

    PubMed

    Tegtmeier, Dorothee; Thompson, Claire L; Schauer, Christine; Brune, Andreas

    2015-12-04

    The gut microbiota of termites and cockroaches represents complex metabolic networks of many diverse microbial populations. The distinct microenvironmental conditions within the gut and possible interactions among the microorganisms make it essential to investigate how far the metabolic properties of pure cultures reflect their activities in their natural environment. We established the cockroach Shelfordella lateralis as a gnotobiotic model and inoculated germfree nymphs with two bacterial strains isolated from the guts of conventional cockroaches. Fluorescence microscopy revealed that both strains specifically colonized the germfree hindgut. In diassociated cockroaches, the facultatively anaerobic strain EbSL (a new species of Enterobacteriaceae) always outnumbered the obligately anaerobic strain FuSL (a close relative of Fusobacterium varium), irrespective of the sequence of inoculation, which showed that precolonization by facultatively anaerobic bacteria does not necessarily favor colonization by obligate anaerobes. Comparison of the fermentation products of the cultures formed in vitro with those accumulated in situ indicated that the gut environment strongly affected the metabolic activities of both strains. The pure cultures formed the typical products of mixed-acid or butyrate fermentation, whereas the guts of gnotobiotic cockroaches accumulated mostly lactate and acetate. Similar shifts toward more-oxidized products were observed when the pure cultures were exposed to oxygen, which corroborated the strong effects of oxygen on the metabolic fluxes previously observed in termite guts. Oxygen microsensor profiles of the guts of germfree, gnotobiotic, and conventional cockroaches indicated that both gut tissue and microbiota contribute to oxygen consumption and suggest that the oxygen status influences the colonization success.

  17. 76 FR 61725 - Agency Information Collection Activities: Case Submission Form, Case Assistance Form; (Form DHS...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-05

    ... Federal Register on July 18, 2011 at 76 FR 42129, for a 60-day public comment period. No comments were... other forms of information technology, e.g., permitting electronic submissions of responses. FOR FURTHER... to bring to the attention of the CIS Ombudsman (``trend''). For case problems, the CIS Ombudsman...

  18. Immobilised activated sludge based biosensor for biochemical oxygen demand measurement.

    PubMed

    Liu, J; Björnsson, L; Mattiasson, B

    2000-02-01

    A biochemical oxygen demand (BOD) sensor, based on an immobilised mixed culture of microorganisms in combination with a dissolved oxygen electrode, has been developed for the purpose of on-line monitoring of the biological treatment process for waste and wastewater. The sensor was designed for easy replacement of the biomembrane, thereby making it suitable for short-term use. The drawbacks of activated sludge based sensor, such as short sensor lifetime, were thereby circumvented. The sensor BOD measurements were carried out in the kinetic mode using a flow injection system, resulting in 25 s for one measurement followed by 4-8 min recovery time. Based on the results of normalised sensor responses, the OECD synthetic wastewater was considered to be a more suitable calibration solution in comparison with the GGA solution. Good agreement was achieved between the results of the sensor BOD measurement and those obtained from BOD5 analysis of a wastewater sample from a food-processing factory. Reproducibility of responses using one sensor was below +/- 5.6%, standard deviation. Reproducibility of responses using different sensors was within acceptable bias limits, viz. +/- 15% standard deviation.

  19. Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Zeller, Robert August

    Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set

  20. Towards forming-free resistive switching in oxygen engineered HfO{sub 2−x}

    SciTech Connect

    Sharath, S. U. Kurian, J.; Hildebrandt, E.; Alff, L.; Bertaud, T.; Walczyk, C.; Calka, P.; Zaumseil, P.; Sowinska, M.; Walczyk, D.; Gloskovskii, A.; Schroeder, T.

    2014-02-10

    We have investigated the resistive switching behavior in stoichiometric HfO{sub 2} and oxygen-deficient HfO{sub 2−x} thin films grown on TiN electrodes using reactive molecular beam epitaxy. Oxygen defect states were controlled by the flow of oxygen radicals during thin film growth. Hard X-ray photoelectron spectroscopy confirmed the presence of sub-stoichiometric hafnium oxide and defect states near the Fermi level. The oxygen deficient HfO{sub 2−x} thin films show bipolar switching with an electroforming occurring at low voltages and low operating currents, paving the way for almost forming-free devices for low-power applications.

  1. Life form-specific variations in leaf water oxygen-18 enrichment in Amazonian vegetation.

    PubMed

    Lai, Chun-Ta; Ometto, Jean P H B; Berry, Joseph A; Martinelli, Luiz A; Domingues, Tomas F; Ehleringer, James R

    2008-08-01

    Leaf water (18)O enrichment (Delta(o)) influences the isotopic composition of both gas exchange and organic matter, with Delta(o) values responding to changes in atmospheric parameters. In order to examine possible influences of plant parameters on Delta(o) dynamics, we measured oxygen isotope ratios (delta(18)O) of leaf and stem water on plant species representing different life forms in Amazonia forest and pasture ecosystems. We conducted two field experiments: one in March (wet season) and another in September (dry season) 2004. In each experiment, leaf and stem samples were collected at 2-h intervals at night and hourly during the day for 50 h from eight species including upper-canopy forest trees, upper-canopy forest lianas, and lower-canopy forest trees, a C(4) pasture grass and a C(3) pasture shrub. Significant life form-related differences were detected in (18)O leaf water values. Initial modeling efforts to explain these observations over-predicted nighttime Delta(o) values by as much as 10 per thousand. Across all species, errors associated with measured values of the delta(18)O of atmospheric water vapor (delta(v)) appeared to be largely responsible for the over-predictions of nighttime Delta(o) observations. We could not eliminate collection or storage of water vapor samples as a possible error and therefore developed an alternative, plant-based method for estimating the daily average delta(v) value in the absence of direct (reliable) measurements. This approach differs from the common assumption that isotopic equilibrium exists between water vapor and precipitation water, by including transpiration-based contributions from local vegetation through (18)O measurements of bulk leaf water. Inclusion of both modified delta(v) and non-steady state features resulted in model predictions that more reliably predicted both the magnitude and temporal patterns observed in the data. The influence of life form-specific patterns of Delta(o) was incorporated through

  2. Correlation between the sorption of dissolved oxygen onto chitosan and its antimicrobial activity against Esherichia coli.

    PubMed

    Gylienė, Ona; Servienė, Elena; Vepštaitė, Iglė; Binkienė, Rima; Baranauskas, Mykolas; Lukša, Juliana

    2015-10-20

    The ability of chitosan to adsorb dissolved oxygen from solution depends on its physical shape and is related to the surface area. Depending on conditions chitosan is capable of adsorbing or releasing oxygen. Chitosan, modificated by the substances possessing antimicrobial activity, such as succinic acid, Pd(II) ions, metallic Pd or Ag, distinctly increases the ability to adsorb the dissolved oxygen. The additional treatment of chitosan with air oxygen or electrochemically produced oxygen also increases the uptake of dissolved oxygen by chitosan. A strong correlation between the amount of oxygen adsorbed onto chitosan and its antimicrobial activity against Esherichia coli has been observed. This finding suggests that one of the sources of antimicrobial activity of chitosan is the ability to sorb dissolved oxygen, along with other well-known factors such as physical state and chemical composition.

  3. Production and Characterization of Active Transparent PET Films for Oxygen Sensitive Foods Packaging

    NASA Astrophysics Data System (ADS)

    Rosaria Galdi, Maria; Incarnato, Loredana

    2010-06-01

    The aim of this work is to investigate possible solutions to realize active, transparent PET film suitable for packaging oxygen sensitive foods. At this purpose, monolayer active PET films at different oxygen scavenger concentrations and multilayer active ones were produced by cast extrusion laboratory scale equipments. To assess their activity and to verify the efficacy of such solutions, O2 absorption analyses were carried out in continuous by an innovative oxygen meter.

  4. Bleaching in coral reef anthozoans: effects of irradiance, ultraviolet radiation, and temperature on the activities of protective enzymes against active oxygen

    NASA Astrophysics Data System (ADS)

    Lesser, M. P.; Stochaj, W. R.; Tapley, D. W.; Shick, J. M.

    1990-04-01

    Recent widespread bleaching of coral reef anthozoans has been observed on the Great Barrier Reef, the Pacific coast of Panama, and in the Caribbean Sea. Bleaching events have been correlated with anomalously high sea surface temperatures which are presumed to cause the expulsion of zooxanthellae from their hosts. Our experimental results show that increases in temperature significantly reduce the total number of zooxanthellae per polyp. At the same time temperature, irradiance (photosynthetically active radiation=PAR), and ultraviolet radiation (UV) independently increase the activities of the enzymes superoxide dismutase, catalase, and ascorbate peroxidase within the zooxanthellae of the zoanthid Palythoa caribaeorum. Enzyme activities within the host are only suggestive of similar changes. These enzymes are responsible for detoxifying active forms of oxygen, and their elevated activities indirectly indicate an increase in the production of active oxygen species by increases in these environmental factors. Historically, bleaching has been attributed to changes in temperature, salinity, and UV. Increases in temperature or highly energetic UV radiation can increase the flux of active forms of oxygen, particularly at the elevated oxygen concentrations that prevail in the tissues during photosynthesis, with oxygen toxicity potentially mediating the bleaching event. Additionally, the concentration of UV absorbing compounds within the symbiosis is inversely related to temperature, potentially increasing exposure of the host and zooxanthellae to the direct effects of UV.

  5. Effect of surface phosphorus functionalities of activated carbons containing oxygen and nitrogen on electrochemical capacitance

    PubMed Central

    Hulicova-Jurcakova, Denisa; Seredych, Mykola; Lu, Gao Qing; Kodiweera, N.K.A.C.; Stallworth, Phillip E.; Greenbaum, Steven; Bandosz, Teresa J.

    2009-01-01

    Micro/mesoporous activated carbons containing oxygen and phosphorus heteroatoms were modified by incorporation of nitrogen using melamine and urea precursors. The surface chemistry was analyzed by the means of elemental analysis, XPS, and 31P MAS NMR. The results indicate that upon the incorporation of nitrogen at high temperatures not only new species involving carbon/nitrogen/oxygen are formed but also the phosphorous environment is significantly altered. Both urea and melamine precursors have similar effects on formation of P–N and P–C bonds. These compounds, although present in small but measurable quantities seem to affect the performance of carbons in electrochemical capacitors. With an increase in the heterogeneity of phosphorus containing species and with a decrease in the content pyrophosphates the capacitance increases and the retention ratio of the capacitor is improved. PMID:20354586

  6. Molybdenum and tungsten oxygen transferases--and functional diversity within a common active site motif.

    PubMed

    Pushie, M Jake; Cotelesage, Julien J; George, Graham N

    2014-01-01

    Molybdenum and tungsten are the only second and third-row transition elements with a known function in living organisms. The molybdenum and tungsten enzymes show common structural features, with the metal being bound by a pyranopterin-dithiolene cofactor called molybdopterin. They catalyze a variety of oxygen transferase reactions coupled with two-electron redox chemistry in which the metal cycles between the +6 and +4 oxidation states usually with water, either product or substrate, providing the oxygen. The functional roles filled by the molybdenum and tungsten enzymes are diverse; for example, they play essential roles in microbial respiration, in the uptake of nitrogen in green plants, and in human health. Together, the enzymes form a superfamily which is among the most prevalent known, being found in all kingdoms of life. This review discusses what is known of the active site structures and the mechanisms, together with some recent insights into the evolution of these important enzyme systems.

  7. Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

    SciTech Connect

    Popolan, Denisia M.; Bernhardt, Thorsten M.

    2011-03-07

    The oxidation of carbon monoxide with nitrous oxide on mass-selected Au{sub 3}{sup +} and Ag{sub 3}{sup +} clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au{sub 3}{sup +} the cluster itself acts as reactive species that facilitates the formation of CO{sub 2} from N{sub 2}O and CO, for silver the oxidized clusters Ag{sub 3}O{sub x}{sup +} (n= 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N{sub 2}O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

  8. Pu-238 fuel form activities, January 1-31, 1982

    SciTech Connect

    Not Available

    1982-03-01

    This monthly report for /sup 238/Pu fuel form activities has two main sections: SRP-PuFF facility and SRL fuel form activities. The program status, budget information, and milestone schedules are discussed in each main section. The Work Breakdown Structure (WBS) for this program is shown. Only one monthly report per year is processed for EDB.

  9. Pu-238 fuel form activities, January 1-31, 1981

    SciTech Connect

    Not Available

    1981-02-01

    This monthly report for /sup 238/Pu Fuel Form Activities has two main sections: SRP-PuFF facility and SRL Fuel Form Activities. The program status, budget information, and milestone schedules are discussed in each main section. The Work Breakdown Structure (WBS) for this program is shown. Only one monthly report per year is processed for EDB.

  10. Pu-238 fuel form activities, January 1-31, 1983

    SciTech Connect

    Not Available

    1983-03-01

    This monthly report for /sup 238/Pu Fuel Form Activities has two main sections: SRP-PuFF facility and SRL Fuel Form Activities. The program status, budget information, and milestone schedules are discussed in each main section. The Work Breakdown Structure (WBS) for this program is shown. Only one monthly report per year is processed for EDB.

  11. Determination of reactive oxygen species from ZnO micro-nano structures with shape-dependent photocatalytic activity

    SciTech Connect

    He, Weiwei; Zhao, Hongxiao; Jia, Huimin; Yin, Jun-Jie; Zheng, Zhi

    2014-05-01

    Graphical abstract: ZnO micro/nano structures with shape dependent photocatalytic activity were prepared by hydrothermal reaction. The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were identified precisely by electron spin resonance spectroscopy. The type of reactive oxygen species was determined by band gap structure of ZnO. - Highlights: • ZnO micro/nano structures with different morphologies were prepared by solvothermal reaction. • Multi-pod like ZnO structures exhibited superior photocatalytic activity. • The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were characterized precisely by electron spin resonance spectroscopy. • The type of reactive oxygen species was determined by band gap structure of ZnO. - Abstract: ZnO micro/nano structures with different morphologies have been prepared by the changing solvents used during their synthesis by solvothermal reaction. Three typical shapes of ZnO structures including hexagonal, bell bottom like and multi-pod formed and were characterized by scanning electron microscopy and X-ray diffraction. Multi pod like ZnO structures exhibited the highest photocatalytic activity toward degradation of methyl orange. Using electron spin resonance spectroscopy coupled with spin trapping techniques, we demonstrate an effective way to identify precisely the generation of hydroxyl radicals, superoxide and singlet oxygen from the irradiated ZnO multi pod structures. The type of reactive oxygen species formed was predictable from the band gap structure of ZnO. These results indicate that the shape of micro-nano structures significantly affects the photocatalytic activity of ZnO, and demonstrate the value of electron spin resonance spectroscopy for characterizing the type of reactive oxygen species formed during photoexcitation of semiconductors.

  12. Differential production of active oxygen species in photo-symbiotic and non-symbiotic bivalves.

    PubMed

    Nakayama, K; Maruyama, T

    1998-01-01

    We investigated the generation of active oxygen species in the bivalves, Crassostrea gigas, Fulvia mutica and Tridacna crocea in order to understand the defensive mechanisms in giant clams that allow a stable association with symbiotic zooxanthellae. C. gigas produced active oxygens, superoxide anion and nitric oxide upon stimulation by phorbol myristate acetate. F. mutica generated a little amount of superoxide anion and nitric oxide, and contained significant phenoloxidase activity which catalyzes formation of quinones. T. crocea did not generate any apparent active oxygen species or quinones. The importance of lacking rapid cytotoxic responses consisting of active oxygen species to foreign organisms in the symbiotic clam is discussed.

  13. Effect of oxygen on the microbial activities of thermophilic anaerobic biomass.

    PubMed

    Pedizzi, C; Regueiro, L; Rodriguez-Verde, I; Lema, J M; Carballa, M

    2016-07-01

    Low oxygen levels (μgO2L(-1)) in anaerobic reactors are quite common and no relevant consequences are expected. On the contrary, higher concentrations could affect the process. This work aimed to study the influence of oxygen (4.3 and 8.8mgO2L(-1), respectively) on the different microbial activities (hydrolytic, acidogenic and methanogenic) of thermophilic anaerobic biomass and on the methanogenic community structure. Batch tests in presence of oxygen were conducted using specific substrates for each biological activity and a blank (with minimum oxygen) was included. No effect of oxygen was observed on the hydrolytic and acidogenic activities. In contrast, the methane production rate decreased by 40% in all oxygenated batches and the development of active archaeal community was slower in presence of 8.8mgO2L(-1). However, despite this sensitivity of methanogens to oxygen at saturation levels, the inhibition was reversible. PMID:27020398

  14. An ultrastable bimetallic carbide as platinum electrocatalyst support for highly active oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; Zhang, Mingmei; Xie, Jimin; Shen, Pei Kang

    2015-11-01

    Stable bimetallic carbide (Fe2MoC) with graphitized carbon (GC) as matrix has been synthesized through an ion-exchange method. The Pt nanoparticles are loaded on the GC-Fe2MoC composite to form Pt/GC-Fe2MoC electrocatalyst which shows much higher activity and stability than those of commercial Pt/C for oxygen reduction reaction in acidic media. The excellent performances of Pt/GC-Fe2MoC are mainly due to the inherent stability of GC-Fe2MoC and the promotion effect between Fe2MoC and Pt.

  15. Oxygen isotopic evidence for vigorous mixing during the Moon-forming giant impact.

    PubMed

    Young, Edward D; Kohl, Issaku E; Warren, Paul H; Rubie, David C; Jacobson, Seth A; Morbidelli, Alessandro

    2016-01-29

    Earth and the Moon are shown here to have indistinguishable oxygen isotope ratios, with a difference in Δ'(17)O of -1 ± 5 parts per million (2 standard error). On the basis of these data and our new planet formation simulations that include a realistic model for primordial oxygen isotopic reservoirs, our results favor vigorous mixing during the giant impact and therefore a high-energy, high-angular-momentum impact. The results indicate that the late veneer impactors had an average Δ'(17)O within approximately 1 per mil of the terrestrial value, limiting possible sources for this late addition of mass to the Earth-Moon system.

  16. Active oxygen and cell death in cereal aleurone cells.

    PubMed

    Fath, Angelika; Bethke, Paul; Beligni, Veronica; Jones, Russell

    2002-05-01

    The cereal aleurone layer is a secretory tissue whose function is regulated by gibberellic acid (GA) and abscisic acid (ABA). Aleurone cells lack functional chloroplasts, thus excluding photosynthesis as a source of active oxygen species (AOS) in cell death. Incubation of barley aleurone layers or protoplasts in GA initiated the cell death programme, but incubation in ABA delays programmed cell death (PCD). Light, especially blue and UV-A light, and H(2)O(2) accelerate PCD of GA-treated aleurone cells, but ABA-treated aleurone cells are refractory to light and H(2)O(2) and are not killed. It was shown that light elevated intracellular H(2)O(2), and that the rise in H(2)O(2) was greater in GA-treated cells compared to cells in ABA. Experiments with antioxidants show that PCD in aleurone is probably regulated by AOS. The sensitivity of GA-treated aleurone to light and H(2)O(2) is a result of lowered amounts of enzymes that metabolize AOS. mRNAs encoding catalase, ascorbate peroxidase and superoxide dismutase are all reduced during 6-18 h of incubation in GA, but these mRNAs were present in higher amounts in cells incubated in ABA. The amounts of protein and enzyme activities encoded by these mRNAs were also dramatically reduced in GA-treated cells. Aleurone cells store and metabolize neutral lipids via the glyoxylate cycle in response to GA, and glyoxysomes are one potential source of AOS in the GA-treated cells. Mitochondria are another potential source of AOS in GA-treated cells. AOS generated by these organelles bring about membrane rupture and cell death.

  17. Enhanced Surfactant Adsorption on Activated Carbon through Manipulation of Surface Oxygen Groups

    NASA Astrophysics Data System (ADS)

    Collins, John; Qu, Deyang; Foster, Michelle

    2012-02-01

    Passive energy storage is a necessary component for balancing the lifecycle budget with new forms of green energy. The work presented describes how surface oxygen groups (SOG) on granulated activated carbon have been manipulated using Nitric Acid in a controlled, stepwise fashion. The structure and surface functionality of the activated carbon samples were characterized using DRIFTS, Raman Spectroscopy and Porosimetry. Total surface area was found to increase proportionally with the removal of heteroatom material, exposing previously insulated active sites responsible for SOG attachment. Broad oxide peaks were deconvoluted and analyzed, allowing for absolute identification of evolving functionality at each oxidation stage. SOGs were maximized on the third oxidation cycle with the presence of conjugated aromatic, phenol, lactone, and carboxylic acid groups. FSN Zonyl nonionic was applied to all oxidized samples at various concentrations. Total adsorbed surfactant was quantified for each concentration / oxidation scheme using attenuated total reflection. The relative quantity and polarity of chemisorbed surfactant were qualitatively assessed for each equilibrium concentration.

  18. Carbon-Oxygen Bond Forming Mechanisms in Rhenium Oxo-Alkyl Complexes

    SciTech Connect

    Cheng, Mu-Jeng; Nielsen, Robert J.; Ahlquist, Marten; Goddard, William A.

    2010-04-07

    Three C-X bond formation mechanisms observed in the oxidation of (HBpz3)ReO(R)(OTf) [HBpz 3 = hydrotris(1-pyrazolyl)borate; R = Me, Et, and iPr; OTf = OSO2CF3] by dimethyl sulfoxide (DMSO) were investigated using quantum mechanics (M06//B3LYP DFT) combined with solvation (using the PBF Poisson-Boltzmann polarizable continuum solvent model). For R = Et we find the alkyl group is activated through α-hydrogen abstraction by external base OTf- with a free energy barrier of only 12.0 kcal/mol, leading to formation of acetaldehyde. Alternatively, ethyl migration across the M=O bond (leading to the formation of acetaldehyde and ethanol) poses a free energy barrier of 22.1 kcal/mol, and the previously proposed α-hydrogen transfer to oxo (a 2+2 forbidden reaction) poses a barrier of 44.9 kcal/mol. The rate-determining step to formation of the final product acetaldehyde is an oxygen atom transfer from DMSO to the ethylidene, with a free energy barrier of 15.3 kcal/mol. When R = iPr, the alkyl 1,2-migration pathway becomes the more favorable pathway (both kinetically and thermodynamically), with a free energy barrier (ΔG = 11.8 kcal/mol) lower than α-hydrogen abstraction by OTf- (ΔG = 13.5 kcal/mol). This suggests the feasibility of utilizing this type of migration to functionalize M-R to M-OR. We also considered the nucleophilic attack of water and ammonia on the Re-ethylidene α-carbon as a means of recovering two-electron-oxidized products from an alkane oxidation. Nucleophilic attack (with internal deprotonation of the nucleophile) is exothermic. However, the subsequent protonolysis of the Re-alkyl bond (to liberate an alcohol or amine) poses a barrier of 37.0 or 42.4 kcal/mol, respectively. Where comparisons are possible, calculated free energies agree very well with experimental measurements.

  19. Growth enhancement and gene expression of Arabidopsis thaliana irradiated with active oxygen species

    NASA Astrophysics Data System (ADS)

    Watanabe, Satoshi; Ono, Reoto; Hayashi, Nobuya; Shiratani, Masaharu; Tashiro, Kosuke; Kuhara, Satoru; Inoue, Asami; Yasuda, Kaori; Hagiwara, Hiroko

    2016-07-01

    The characteristics of plant growth enhancement effect and the mechanism of the enhancement induced by plasma irradiation are investigated using various active species in plasma. Active oxygen species in oxygen plasma are effective for growth enhancement of plants. DNA microarray analysis of Arabidopsis thaliana indicates that the genes coding proteins that counter oxidative stresses by eliminating active oxygen species are expressed at significantly high levels. The size of plant cells increases owing to oxygen plasma irradiation. The increases in gene expression levels and cell size suggest that the increase in the expression level of the expansin protein is essential for plant growth enhancement phenomena.

  20. Pu-238 fuel form activities, June 1-30, 1980

    SciTech Connect

    Not Available

    1980-07-18

    This monthly report for Pu-238 Fuel Form Activities has two main sections: SRP-PuFF Pu-238 Fuel Form Production Processes and SRL Pu-238 Fuel Form Research and Development. The program status, budget information, and milestone information are discussed in each main section. The Work Breakdown Structures (WBS) for this program is outlined. Only one monthly report per year is processed for EDB.

  1. The large, oxygen-rich halos of star-forming galaxies are a major reservoir of galactic metals.

    PubMed

    Tumlinson, J; Thom, C; Werk, J K; Prochaska, J X; Tripp, T M; Weinberg, D H; Peeples, M S; O'Meara, J M; Oppenheimer, B D; Meiring, J D; Katz, N S; Davé, R; Ford, A B; Sembach, K R

    2011-11-18

    The circumgalactic medium (CGM) is fed by galaxy outflows and accretion of intergalactic gas, but its mass, heavy element enrichment, and relation to galaxy properties are poorly constrained by observations. In a survey of the outskirts of 42 galaxies with the Cosmic Origins Spectrograph onboard the Hubble Space Telescope, we detected ubiquitous, large (150-kiloparsec) halos of ionized oxygen surrounding star-forming galaxies; we found much less ionized oxygen around galaxies with little or no star formation. This ionized CGM contains a substantial mass of heavy elements and gas, perhaps far exceeding the reservoirs of gas in the galaxies themselves. Our data indicate that it is a basic component of nearly all star-forming galaxies that is removed or transformed during the quenching of star formation and the transition to passive evolution.

  2. The large, oxygen-rich halos of star-forming galaxies are a major reservoir of galactic metals.

    PubMed

    Tumlinson, J; Thom, C; Werk, J K; Prochaska, J X; Tripp, T M; Weinberg, D H; Peeples, M S; O'Meara, J M; Oppenheimer, B D; Meiring, J D; Katz, N S; Davé, R; Ford, A B; Sembach, K R

    2011-11-18

    The circumgalactic medium (CGM) is fed by galaxy outflows and accretion of intergalactic gas, but its mass, heavy element enrichment, and relation to galaxy properties are poorly constrained by observations. In a survey of the outskirts of 42 galaxies with the Cosmic Origins Spectrograph onboard the Hubble Space Telescope, we detected ubiquitous, large (150-kiloparsec) halos of ionized oxygen surrounding star-forming galaxies; we found much less ionized oxygen around galaxies with little or no star formation. This ionized CGM contains a substantial mass of heavy elements and gas, perhaps far exceeding the reservoirs of gas in the galaxies themselves. Our data indicate that it is a basic component of nearly all star-forming galaxies that is removed or transformed during the quenching of star formation and the transition to passive evolution. PMID:22096191

  3. P38 activation is more important than ERK activation in lung injury induced by prolonged hyperbaric oxygen.

    PubMed

    Ma, Jun; Fang, Yi-Qun; Gu, Ai-Mei; Wang, Fang-Fang; Zhang, Shi; Li, Kai-Cheng

    2013-01-01

    Prolonged exposure to hyperbaric oxygen can cause pulmonary and nerve system toxicity. Although hyperbaric oxygen treatment has been used for a broad spectrum of ailments, the mechanisms of prolonged hyperbaric oxygen-induced lung injury are not fully understood. The purpose of the present work was to investigate the roles of ERK, p38, and caspase-3 in rat lung tissue exposed to hyperbaric oxygen at 2.3 atmospheres absolute (atm abs) for two, six and 10 hours. The results showed that the ERK and p38 were phosphorylated at two hours and reached a peak at six hours into exposure to hyperbaric oxygen. While the phosphorylation level of ERK decreased, p38 remained at a high level of activation at 10 hours. The activation of ERK and p38 was down-regulated when rats were exposed to normoxic hyperbaric nitrogen for 10 hours. However, caspase-3 was activated at six hours and 10 hours into exposure to hyperbaric oxygen. These results demonstrated different changes of activation of ERK and p38 during lung injury induced by prolonged exposure to hyperbaric oxygen. The time course changes of activated caspase-3 were similar to the process of p38 activation upon exposure to hyperbaric oxygen. In this way, activation of p38, not ERK, seems to be a mechanism associated with prolonged hyperbaric oxygen-induced lung injury.

  4. [Experience in the treatment of severe forms of sepsis by extracorporeal therapy and hyperbaric oxygenation].

    PubMed

    Zhidkov, K P; Klechikov, V Z; Bogatyr', M N

    1997-01-01

    The results of multiple modality treatment of 81 patients with sepsis complicated by multiple organ failure are assessed. In 40 patients the traditional therapy of sepsis was supplemented with extracorporeal methods (hemoperfusion, autotransfusion of UV-exposed blood, and perfusion of xenospleen slices) and hyperbaric oxygenation (HBO) sessions. In the patients treated traditionally the mortality was 94%, whereas addition of extracorporeal treatment and HBO decreased this value to 40%. Hence, extracorporeal treatment and HBO are recommended for the treatment of sepsis.

  5. Oxygen Activation at Mononuclear Nonheme Iron Centers: A Superoxo Perspective

    PubMed Central

    Mukherjee, Anusree; Cranswick, Matthew A.; Chakraborti, Mrinmoy; Paine, Tapan K.; Fujisawa, Kiyoshi; Münck, Eckard; Que, Lawrence

    2010-01-01

    Dioxygen activation by iron enzymes is responsible for many metabolically important transformations in biology. Often a high-valent iron-oxo oxidant is proposed to form upon dioxygen activation at a mononuclear nonheme iron center, presumably via intervening iron-superoxo and iron-peroxo species. While iron(IV)-oxo intermediates have been trapped and characterized in enzymes and models, less is known of the putative iron(III)-superoxo species. Utilizing a synthetic model for the 2-oxoglutarate-dependent monoiron enzymes, [(TpiPr2)FeII(O2CC(O)CH3)], we have obtained indirect evidence for the formation of the putative iron(III)-superoxo species, which can undergo one-electron reduction, hydrogen-atom transfer, or conversion to an iron(IV)-oxo species, depending on the reaction conditions. These results demonstrate the various roles the iron(III)-superoxo species can play in the course of dioxygen activation at a nonheme iron center. PMID:20380464

  6. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  7. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  8. Form-Focused Discovery Activities in English Classes

    ERIC Educational Resources Information Center

    Ogeyik, Muhlise Cosgun

    2011-01-01

    Form-focused discovery activities allow language learners to grasp various aspects of a target language by contributing implicit knowledge by using discovered explicit knowledge. Moreover, such activities can assist learners to perceive and discover the features of their language input. In foreign language teaching environments, they can be used…

  9. Activated carbon fibers and engineered forms from renewable resources

    DOEpatents

    Baker, Frederick S.

    2010-06-01

    A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

  10. Activated carbon fibers and engineered forms from renewable resources

    DOEpatents

    Baker, Frederick S

    2013-02-19

    A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

  11. Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

    PubMed

    Zhang, Ning; Li, Xiyu; Ye, Huacheng; Chen, Shuangming; Ju, Huanxin; Liu, Daobin; Lin, Yue; Ye, Wei; Wang, Chengming; Xu, Qian; Zhu, Junfa; Song, Li; Jiang, Jun; Xiong, Yujie

    2016-07-20

    Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials.

  12. Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

    PubMed

    Zhang, Ning; Li, Xiyu; Ye, Huacheng; Chen, Shuangming; Ju, Huanxin; Liu, Daobin; Lin, Yue; Ye, Wei; Wang, Chengming; Xu, Qian; Zhu, Junfa; Song, Li; Jiang, Jun; Xiong, Yujie

    2016-07-20

    Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials. PMID:27351805

  13. Fast oxygen atom studies related to low Earth orbit activities

    NASA Astrophysics Data System (ADS)

    Caledonia, G. E.; Krech, R. H.; Holtzclaw, K. W.; Sonnenfroh, D.

    1993-06-01

    The technique of laser induced gas breakdown to develop a high flux pulsed source of fast oxygen atoms (v = 5 to 12 km/s) is considered. The technique is also used to produce high velocity beams of N/N2 mixtures and can be extended to produce beams of other species. The fast oxygen atoms are of particular current interest since this is the dominant atmospheric species encountered by spacecraft operating in Low Earth Orbit (LEO). The fast oxygen atom source has proven extremely versatile and is used to study a variety of gas-surface and gas-gas collision phenomena. The fast atom facility has reproducibly provided good comparison with LEO observations. Expanded programs involving material testing and measurement of O atom momentum and energy accommodation coefficients with surfaces are presently underway.

  14. Phosphate oxygen isotopic evidence for a temperate and biologically active Archaean ocean.

    PubMed

    Blake, Ruth E; Chang, Sae Jung; Lepland, Aivo

    2010-04-15

    Oxygen and silicon isotope compositions of cherts and studies of protein evolution have been interpreted to reflect ocean temperatures of 55-85 degrees C during the early Palaeoarchaean era ( approximately 3.5 billion years ago). A recent study combining oxygen and hydrogen isotope compositions of cherts, however, makes a case for Archaean ocean temperatures being no greater than 40 degrees C (ref. 5). Ocean temperature can also be assessed using the oxygen isotope composition of phosphate. Recent studies show that (18)O:(16)O ratios of dissolved inorganic phosphate (delta(18)O(P)) reflect ambient seawater temperature as well as biological processing that dominates marine phosphorus cycling at low temperature. All forms of life require and concentrate phosphorus, and as a result of biological processing, modern marine phosphates have delta(18)O(P) values typically between 19-26 per thousand (VSMOW), highly evolved from presumed source values of approximately 6-8 per thousand that are characteristic of apatite in igneous rocks and meteorites. Here we report oxygen isotope compositions of phosphates in sediments from the 3.2-3.5-billion-year-old Barberton Greenstone Belt in South Africa. We find that delta(18)O(P) values range from 9.3 per thousand to 19.9 per thousand and include the highest values reported for Archaean rocks. The temperatures calculated from our highest delta(18)O(P) values and assuming equilibrium with sea water with delta(18)O = 0 per thousand (ref. 12) range from 26 degrees C to 35 degrees C. The higher delta(18)O(P) values are similar to those of modern marine phosphate and suggest a well-developed phosphorus cycle and evolved biologic activity on the Archaean Earth. PMID:20393560

  15. Phosphate oxygen isotopic evidence for a temperate and biologically active Archaean ocean.

    PubMed

    Blake, Ruth E; Chang, Sae Jung; Lepland, Aivo

    2010-04-15

    Oxygen and silicon isotope compositions of cherts and studies of protein evolution have been interpreted to reflect ocean temperatures of 55-85 degrees C during the early Palaeoarchaean era ( approximately 3.5 billion years ago). A recent study combining oxygen and hydrogen isotope compositions of cherts, however, makes a case for Archaean ocean temperatures being no greater than 40 degrees C (ref. 5). Ocean temperature can also be assessed using the oxygen isotope composition of phosphate. Recent studies show that (18)O:(16)O ratios of dissolved inorganic phosphate (delta(18)O(P)) reflect ambient seawater temperature as well as biological processing that dominates marine phosphorus cycling at low temperature. All forms of life require and concentrate phosphorus, and as a result of biological processing, modern marine phosphates have delta(18)O(P) values typically between 19-26 per thousand (VSMOW), highly evolved from presumed source values of approximately 6-8 per thousand that are characteristic of apatite in igneous rocks and meteorites. Here we report oxygen isotope compositions of phosphates in sediments from the 3.2-3.5-billion-year-old Barberton Greenstone Belt in South Africa. We find that delta(18)O(P) values range from 9.3 per thousand to 19.9 per thousand and include the highest values reported for Archaean rocks. The temperatures calculated from our highest delta(18)O(P) values and assuming equilibrium with sea water with delta(18)O = 0 per thousand (ref. 12) range from 26 degrees C to 35 degrees C. The higher delta(18)O(P) values are similar to those of modern marine phosphate and suggest a well-developed phosphorus cycle and evolved biologic activity on the Archaean Earth.

  16. PROCESS FOR THE PRODUCTION OF AN ACTIVATED FORM OF UO$sub 2$

    DOEpatents

    Polissar, M.J.

    1957-09-24

    A process for producing a highly active form of UO/sub 2/ characterized both by rapid oxidation in air and by rapid chlorination with CCl/sub 4/ vapor at an elevated temperature is reported. In accordance with the process, commercial UO/sub 2/, is subjected to a series of oxidation-reduction operations to produce a form of UC/sub 2/ of enhanced reactivity. By treatimg commercial UO/sub 2/ at a temperature between 335 and 485 deg C with methane, then briefly with an oxygen containing gas and followimg this by a second treatment with a methane containing gas, the original relatively stable charge of UO/sub 2/ will be transformed into an active form of UO/sub 2/.

  17. Carbothermal synthesis of titanium oxycarbide as electrocatalyst support with high oxygen evolution reaction activity

    SciTech Connect

    Huang, K; Li, YF; Xing, YC

    2012-11-09

    Carbothermal reduction of semiconducting TiO2 into highly conductive titanium oxycarbide (TiOxCy) was investigated. The thermally produced uniform carbon layer on TiO2 (Degussa P25) protects the TiO2 nanoparticles from sintering and, at the same time, supplies the carbon source for doping TiO2 with carbon. At low temperatures (e. g., 700 degrees C), carbon only substitutes part of the oxide and distorts the TiO2 lattice to form TiO2-xCx with only substitutional carbon. When the carbon-doped TiO2 is annealed at a higher temperature (1100 degrees C), x-ray diffraction and x-ray photoelectron spectroscopy results showed that TiOxCy, a solid solution of TiO and TiC, was formed, which displays different diffraction peaks and binding energies. It was shown that TiOxCy has much better oxygen revolution reaction activity than TiO2 or TiO2-xCx. Further studies showed that the TiOxCy obtained can be used as a support for metal electrocatalyst, leading to a bifunctional catalyst effective for both oxygen reduction and evolution reactions.

  18. The active form of cytochrome c oxidase: effects of detergent, the intact membrane, and radiation inactivation

    SciTech Connect

    Thompson, D.A.; Suarez-Villafane, M.; Ferguson-Miller, S.

    1982-01-01

    Cytochrome oxidase is a multisubunit, intrinsic membrane protein with a complex function that includes oxidation of cytochrome c, reduction of oxygen and generation of a membrane potential. To clarify the relationship of its normal function to protein and membrane structure, we have examined the kinetic behavior of rat liver cytochrome oxidase in the intace inner mitochondrial membrane and in detergent solubilized states. Dissolution of rat liver mitochondrial membranes alters the kinetic parameters of the oxidase in a manner dependent in part on the dispersing agent, and characterized by a large increase in maximal activity which is not attributable to exposure of more oxidase or diminished affinity for cytochrome c. The most profound effect of solubilization of the membrane is seen on the low affinity reaction of cytochrome c, suggesting that the electron transfer pathway from this site to oxygen is sensitive to alterations in hydrophobic interactions within the oxidase. Purified rat liver and beef heart oxidase exists predominantly in a monodisperse, 300 kilodalton form in laurylmaltoside (Rosevear et al., 1980). However, a smaller, 130 kd species that exhibits high turnover rates equal to the 300 kd form is detected in some beef heart preparations, implying that the dimer may not be essential for high activity. Radiation inactivation studies on purified oxidase reveal a molecular weight for the functional unit of approx.70 kd. It is concluded that less than a complete set of subunits may be sufficient for both normal bindings of cytochrome c and rapid electron transfer to oxygen.

  19. Active form of cytochrome c oxidase: effects of detergent, the intact membrane, and radiation inactivation

    SciTech Connect

    Thompson, D.A.; Suarez-Villafane, M.; Ferguson-Miller, S.

    1982-01-01

    Cytochrome oxidase is a multisubunit, intrinsic membrane protein with a complex function that includes oxidation of cytochrome c, reduction of oxygen and generation of a membrane potential. To clarify the relationship of its normal function to protein and membrane structure, we have examined the kinetic behavior of rat liver cytochrome oxidase in the intact inner mitochondrial membrane and in detergent solubilized states. Dissolution of rat liver mitochondrial membranes alters the kinetic parameters of the oxidase in a manner dependent in part on the dispersing agent, and characterized by a large increase in maximal activity which is not attributable to exposure of more oxidase or diminished affinity for cytochrome c. The most profound effect of solubilization of the membrane is seen on the low affinity reaction of cytochrome c, suggesting that the electron transfer pathway from this site to oxygen is sensitive to alterations in hydrophobic interactions within the oxidase. Purified rat liver and beef heart oxidase exists predominantly in a monodisperse, 300 kilodalton form in laurylmaltoside (Rosevear et al., 1980). However, a smaller, 130 kd species that exhibits high turnover rates equal to the 300 kd form is detected in some beef heart preparations, implying that the dimer may not be essential for high activity. Radiation inactivation studies on purified oxidase reveal a molecular weight for the functional unit of approx.70 kd. It is concluded that less than a complete set of subunits may be sufficient for both normal binding of cytochrome c and rapid electron transfer to oxygen.

  20. Mechanism of Oxygen Reduction in Cytochrome c Oxidase and the Role of the Active Site Tyrosine.

    PubMed

    Blomberg, Margareta R A

    2016-01-26

    Cytochrome c oxidase, the terminal enzyme in the respiratory chain, reduces molecular oxygen to water and stores the released energy through electrogenic chemistry and proton pumping across the membrane. Apart from the heme-copper binuclear center, there is a conserved tyrosine residue in the active site (BNC). The tyrosine delivers both an electron and a proton during the O-O bond cleavage step, forming a tyrosyl radical. The catalytic cycle then occurs in four reduction steps, each taking up one proton for the chemistry (water formation) and one proton to be pumped. It is here suggested that in three of the reduction steps the chemical proton enters the center of the BNC, leaving the tyrosine unprotonated with radical character. The reproprotonation of the tyrosine occurs first in the final reduction step before binding the next oxygen molecule. It is also suggested that this reduction mechanism and the presence of the tyrosine are essential for the proton pumping. Density functional theory calculations on large cluster models of the active site show that only the intermediates with the proton in the center of the BNC and with an unprotonated tyrosyl radical have a high electron affinity of similar size as the electron donor, which is essential for the ability to take up two protons per electron and thus for the proton pumping. This type of reduction mechanism is also the only one that gives a free energy profile in accordance with experimental observations for the amount of proton pumping in the working enzyme.

  1. Oxide scales formed on Fe-Cr-Al-based model alloys exposed to oxygen containing molten lead

    NASA Astrophysics Data System (ADS)

    Weisenburger, A.; Jianu, A.; Doyle, S.; Bruns, M.; Fetzer, R.; Heinzel, A.; DelGiacco, M.; An, W.; Müller, G.

    2013-06-01

    Based on the state of the art oxide maps concerning oxidation behavior of Fe-Cr-Al model alloys at 800 and 1000 °C in oxygen atmosphere, ten compositions, belonging to this alloy system, were designed in order to tap the borders of the alumina stability domain, during their exposure to oxygen (10-6 wt.%) containing lead, at 400, 500 and 600 °C. Eight alloys, Fe-6Cr-6Al, Fe-8Cr-6Al, Fe-10Cr-5Al, Fe-14Cr-4Al, Fe-16Cr-4Al, Fe-6Cr-8Al, Fe-10Cr-7Al and Fe-12Cr-5Al, were found to be protected against corrosion in oxygen containing lead, either by a duplex layer (Fe3O4 + (Fe1-x-yCrxAly)3O4) or by (Fe1-x-yCrxAly)3O4, depending on the temperature at which they were exposed. Two alloys namely Fe-12Cr-7Al and Fe-16Cr-6Al were found to form transient aluminas, κ-Al2O3 (at 400 and 500 °C) and θ-Al2O3 (at 600 °C), as protective oxide scale against corrosion in oxygen containing lead. An oxide map illustrating the stability domain of alumina, grown on Fe-Cr-Al alloys when exposed to molten, oxygen containing lead, was drawn. The map includes also additional points, extracted from literature and corresponding to alumina forming alloys, when exposed to HLMs, which fit very well with our findings. Chromium and aluminium contents of 12.5-17 wt.% and 6-7.5 wt.%, respectively, are high enough to obtain thin, stable and protective alumina scales on Fe-Cr-Al-based alloys exposed to oxygen containing lead at 400, 500 and 600 °C. For the temperature range and exposure times used during the current evaluation, the growth rate of the alumina scale was low. No area with detached scale was observed and no trace of α-Al2O3 was detected.

  2. Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

    PubMed

    Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

    2012-04-18

    An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. PMID:22417283

  3. Origin of Active Oxygen in a Ternary CuOx /Co3O4–CeO 2 Catalyst for CO Oxidation

    SciTech Connect

    Liu, Zhigang; Wu, Zili; Peng, Xihong; Binder, Andrew; Chai, Songhai; Dai, Sheng

    2014-11-14

    In this paper, we have studied CO oxidation over a ternary CuOx/Co3O4-CeO2 catalyst and employed the techniques of N2 adsorption/desporption, XRD, TPR, TEM, in situ DRIFTS and QMS (Quadrupole mass spectrometer) to explore the origin of active oxygen. DRIFTS-QMS results with labeled 18O2 indicate that the origin of active oxygens in CuOx/Co3O4-CeO2 obeys a model, called as queue mechanism. Namely gas-phase molecular oxygens are dissociated to atomic oxygens and then incorporate in oxygen vacancies located at the interface of Co3O4-CeO2 to form active crystalline oxygens, and these active oxygens diffuse to the CO-Cu+ sites thanks to the oxygen vacancy concentration magnitude and react with the activated CO to form CO2. This process, obeying a queue rule, provides active oxygens to form CO2 from gas-phase O2 via oxygen vacancies and crystalline oxygen at the interface of Co3O4-CeO2.

  4. Method of Separating Oxygen From Spacecraft Cabin Air to Enable Extravehicular Activities

    NASA Technical Reports Server (NTRS)

    Graf, John C.

    2013-01-01

    Extravehicular activities (EVAs) require high-pressure, high-purity oxygen. Shuttle EVAs use oxygen that is stored and transported as a cryogenic fluid. EVAs on the International Space Station (ISS) presently use the Shuttle cryo O2, which is transported to the ISS using a transfer hose. The fluid is compressed to elevated pressures and stored as a high-pressure gas. With the retirement of the shuttle, NASA has been searching for ways to deliver oxygen to fill the highpressure oxygen tanks on the ISS. A method was developed using low-pressure oxygen generated onboard the ISS and released into ISS cabin air, filtering the oxygen from ISS cabin air using a pressure swing absorber to generate a low-pressure (high-purity) oxygen stream, compressing the oxygen with a mechanical compressor, and transferring the high-pressure, high-purity oxygen to ISS storage tanks. The pressure swing absorber (PSA) can be either a two-stage device, or a single-stage device, depending on the type of sorbent used. The key is to produce a stream with oxygen purity greater than 99.5 percent. The separator can be a PSA device, or a VPSA device (that uses both vacuum and pressure for the gas separation). The compressor is a multi-stage mechanical compressor. If the gas flow rates are on the order of 5 to 10 lb (.2.3 to 4.6 kg) per day, the compressor can be relatively small [3 16 16 in. (.8 41 41 cm)]. Any spacecraft system, or other remote location that has a supply of lowpressure oxygen, a method of separating oxygen from cabin air, and a method of compressing the enriched oxygen stream, has the possibility of having a regenerable supply of highpressure, high-purity oxygen that is compact, simple, and safe. If cabin air is modified so there is very little argon, the separator can be smaller, simpler, and use less power.

  5. The Effect of 30% Oxygen on Visuospatial Performance and Brain Activation: An Fmri Study

    ERIC Educational Resources Information Center

    Chung, S.C.; Tack, G.R.; Lee, B.; Eom, G.M.; Lee, S.Y.; Sohn, J.H.

    2004-01-01

    This study aimed to investigate the hypothesis that administration of the air with 30% oxygen compared with normal air (21% oxygen) enhances cognitive functioning through increased activation in the brain. A visuospatial task was presented while brain images were scanned by a 3 T fMRI system. The results showed that there was an improvement in…

  6. Activation of oxygen-mediating pathway using copper ions: fine-tuning of growth kinetics in gold nanorod overgrowth.

    PubMed

    Liu, Wenqi; Zhang, Hui; Wen, Tao; Yan, Jiao; Hou, Shuai; Shi, Xiaowei; Hu, Zhijian; Ji, Yinglu; Wu, Xiaochun

    2014-10-21

    Growth kinetics plays an important role in the shape control of nanocrystals (NCs). Herein, we presented a unique way to fine-tune the growth kinetics via oxidative etching activated by copper ions. For the overgrowth of gold nanorods (Au NRs), competitive adsorption of dissolved oxygen on rod surface was found to slow down the overgrowth rate. Copper ions were able to remove the adsorbed oxygen species from the Au surface via oxidative etching, thus exposing more reaction sites for Au deposition. In this way, copper ions facilitated the overgrowth process. Furthermore, Cu(2+) rather than Cu(+) acted as the catalyst for the oxidative etching. Comparative study with Ag(+) indicated that Cu(2+) cannot regulate NC shapes via an underpotential deposition mechanism. In contrast, Ag(+) led to the formation of Au tetrahexahedra (THH) and a slight decrease of the growth rate at similar growth conditions. Combining the distinct roles of the two ions enabled elongated THH to be produced. Copper ions activating the O2 pathway suggested that dissolved oxygen has a strong affinity for the Au surface. Moreover, the results of NC-sensitized singlet oxygen ((1)O2) indicated that the absorbed oxygen species on the surface of Au NCs bounded with low-index facets mainly existed in the form of molecular O2. PMID:25244407

  7. Effect of surface area and chemisorbed oxygen on the SO2 adsorption capacity of activated char

    USGS Publications Warehouse

    Lizzio, A.A.; DeBarr, J.A.

    1996-01-01

    The objective of this study was to determine whether activated char produced from Illinois coal could be used effectively to remove sulfur dioxide from coal combustion flue gas. Chars were prepared from a high-volatile Illinois bituminous coal under a wide range of pyrolysis and activation conditions. A novel char preparation technique was developed to prepare chars with SO2 adsorption capacities significantly greater than that of a commercial activated carbon. In general, there was no correlation between SO2 adsorption capacity and surface area. Temperature-programmed desorption (TPD) was used to determine the nature and extent of carbon-oxygen (C-O) complexes formed on the char surface. TPD data revealed that SO2 adsorption was inversely proportional to the amount of C-O complex. The formation of a stable C-O complex during char preparation may have served only to occupy carbon sites that were otherwise reactive towards SO2 adsorption. A fleeting C(O) complex formed during SO2 adsorption is postulated to be the reaction intermediate necessary for conversion of SO2 to H2SO4. Copyright ?? 1996 Elsevier Science Ltd.

  8. Design of high pressure oxygen filter for extravehicular activity life support system, volume 1

    NASA Technical Reports Server (NTRS)

    Wilson, B. A.

    1977-01-01

    The experience of the National Aeronautics and Space Administration (NASA) with extravehicular activity life support emergency oxygen supply subsystems has shown a large number of problems associated with particulate contamination. These problems have resulted in failures of high pressure oxygen component sealing surfaces. A high pressure oxygen filter was designed which would (a) control the particulate contamination level in the oxygen system to a five-micron glass bead rating, ten-micron absolute condition (b) withstand the dynamic shock condition resulting from the sudden opening of 8000 psi oxygen system shutoff valve. Results of the following program tasks are reported: (1) contaminant source identification tests, (2) dynamic system tests, (3) high pressure oxygen filter concept evaluation, (4) design, (5) fabrication, (6) test, and (7) application demonstration.

  9. Planar and channel waveguides on Na:CBN formed by oxygen ion implantation

    NASA Astrophysics Data System (ADS)

    Guo, Sha-Sha; Zhao, Jin-Hua; Huang, Qing; Liu, Peng; Liu, Tao; Zhang, Lian; Wang, Xue-Lin

    2012-09-01

    We reported the fabrication of the planar and channel waveguides in Na-doped calcium barium niobate (CBN) with multiple-energy oxygen-ion implantation. Multiple-energy implants can broaden the barrier width to reduce light leakage from the waveguide to the substrate through the barrier wall. The guiding modes and the near-field intensity distribution of the light were measured by the prism-coupling method and the end-facing coupling arrangement separately. The refractive index profiles of planar and channel waveguides were both typical "well + barrier" distribution, and we used the finite-difference beam propagation method (FD-BPM) to simulate the light propagation. After annealing at 200 °C for 30 min, the waveguide propagation loss of the planar and channel waveguides could be reduced down to ˜3.7 dB/cm and ˜3.5 dB/cm. The calculated results were in excellent agreement with the measured waveguide modes, indicating the feasibility of designing these devices.

  10. Effects of carbohydrate on the internal oxygen concentration, oxygen uptake, and nitrogenase activity in detached pea nodules

    SciTech Connect

    Monroe, J.D. ); LaRue, T.A. )

    1989-10-01

    The interaction between carbon substrates and O{sub 2} and their effects on nitrogenase activity (C{sub 2}H{sub 2}) were examined in detached nodules of pea (Pisum sativum L. cv Sparkle). The internal O{sub 2} concentration was estimated from the fractional oxygenation of leghemoglobin measured by reflectance spectroscopy. Lowering the endogenous carbohydrate content of nodules by excising the shoots 16 hours before nodule harvest or by incubating detached nodules at 100 kPa O{sub 2} for 2 hours resulted in a 2- to 10-fold increase in internal O{sub 2}, and a decline in nitrogenase activity. Conversely, when detached nodules were supplied with 100 millimolar succinate, the internal O{sub 2} was lowered. Nitrogenase activity was stimulated by succinate but only at high external O{sub 2}. Oxygen uptake increased linearly with external O{sub 2} but was affected only slightly by the carbon treatments. The apparent diffusion resistance in the nodule cortex was similar in all of the treatments. Carbon substrates can thus affect nitrogenase activity indirectly by affecting the O{sub 2} concentration within detached nodules.

  11. Copper(I)-catalyzed aryl bromides to form intermolecular and intramolecular carbon-oxygen bonds.

    PubMed

    Niu, Jiajia; Guo, Pengran; Kang, Juntao; Li, Zhigang; Xu, Jingwei; Hu, Shaojing

    2009-07-17

    A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K(3)PO(4) as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

  12. Oxygen isotope composition of Holocene dolomite formed in humid hypersaline setting

    SciTech Connect

    Major, R.P.; Lucia, F.J. ); Lloyd, R.M.

    1992-07-01

    Holocene dolomite forming in supratidal carbonate sediments of Bonaire, Netherlands Antilles, is precipitated from hypersaline fluids in which the Mg:Ca ratio is elevated by evaporation and gypsum precipitation. Kinetic effects and water-vapor exchange between the humid atmosphere and hypersaline brines limit the {delta}{sup 18}O{sub water} values of the brines between +0.7{per thousand} and +2.1{per thousand} standard mean ocean water. The mean {delta}{sup 18}O value of dolomite is +1.0{per thousand} Peedee belemnite (n = 8), which is lower than values of dolomite precipitated from hypersaline brines in less humid environments. Bonaire dolomite is also isotopically lighter than dolomites interpreted to have formed in normal marine waters and mixed marine and/or meteoric waters. Calculated fractionation between dolomite and calcite formed from Bonaire brines is between 1.5{per thousand} and 3.5{per thousand}. The high end of this range is consistent with previously proposed mineralogic fractionations of 3{per thousand} {plus minus} 1{per thousand} and 3.2{per thousand} between dolomite and calcite.

  13. Charge separation promoted activation of molecular oxygen by neutral gold clusters.

    PubMed

    Woodham, Alex P; Meijer, Gerard; Fielicke, André

    2013-02-01

    Gold nanoparticles and sub-nanoparticles famously act as highly efficient and selective low-temperature oxidation catalysts with molecular oxygen, in stark contrast to the nobility of the bulk phase. The origins of this activity and the nature of the active species remain open questions. Gas-phase studies of isolated gold clusters hold promise for disentangling these problems. Here we address the interaction of neutral gold clusters (Au(n); 4 ≤ n ≤ 21) with molecular oxygen by probing the highly characteristic O-O vibrational stretch frequencies. This reveals that for selected cluster sizes the oxygen is highly activated with respect to the free moiety. Complementary quantum chemical calculations provide evidence for substantial electron transfer to the O(2) unit and concomitant rearrangement of the parent gold cluster structure upon binding and activation. This gives evidence for a model of the interaction between neutral gold clusters and molecular oxygen.

  14. Process for forming a homogeneous oxide solid phase of catalytically active material

    DOEpatents

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  15. Study of oxygen scavenging PET-based films activated by water

    NASA Astrophysics Data System (ADS)

    Rossi, Gabriella; Scarfato, Paola; Incarnato, Loredana

    2016-05-01

    In this work an active barrier system consisting of a thin and transparent film based on polyethylene terephthalate (PET) was studied. Dynamic oxygen absorption measurements were performed at different values of relative humidity and temperature, pointing out that humidity is a key factor in activating the oxidation of the polymer sample. Moreover, the thermal and optical properties of the films were investigated and a good correlation was found between the crystallinity increase and the consequent transparency reduction occurring after the oxygen absorption.

  16. 75 FR 51093 - Agency Information Collection Activities: Form I-864, Form I-864A, Form I-864EZ, and Form I-864W...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... on May 12, 2010, at 75 FR 26782, allowing for a 60-day public comment period. USCIS received 2... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-864.... Citizenship and Immigration Services (USCIS) will be submitting the following information collection...

  17. 75 FR 26782 - Agency Information Collection Activities: Form I-864, Form I-864A, Form I-864EZ, and Form I-864W...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-05-12

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-864... Exemption; OMB Control No. 1615-0075. The Department of Homeland Security, U.S. Citizenship and Immigration...-864W; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will be asked...

  18. Effect of arsenic on the activity of oxygen dissolved in dilute liquid copper solutions

    NASA Astrophysics Data System (ADS)

    Walqui, H.; Seetharaman, S.; Staffansson, L. I.

    1985-06-01

    The influence of arsenic additions on the activity of oxygen in liquid copper was studied by the solid-electrolyte galvanic cell (-) Pt, W/Cu-O-As ∥ ZrO2-CaO ∥ NiO-Ni/Pt (+) in the temperature range 1373 to 1473 K. The activity coefficient of oxygen in liquid copper was found to be unaffected by the addition of arsenic. The interaction parameter values for group V B elements in the periodic table with respect to oxygen are discussed in the light of the solute interactions in copper.

  19. The role of beaded activated carbon's surface oxygen groups on irreversible adsorption of organic vapors.

    PubMed

    Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

    2016-11-01

    The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials. PMID:27295065

  20. Activated human neutrophil response to perfluorocarbon nanobubbles: oxygen-dependent and -independent cytotoxic responses.

    PubMed

    Hwang, Tsong-Long; Fang, Chia-Lang; Al-Suwayeh, Saleh A; Yang, Li-Jia; Fang, Jia-You

    2011-06-10

    Nanobubbles, a type of nanoparticles with acoustically active properties, are being utilized as diagnostic and therapeutic nanoparticles to better understand, detect, and treat human diseases. The objective of this work was to prepare different nanobubble formulations and investigate their physicochemical characteristics and toxic responses to N-formyl-methionyl-leucyl-phenylalanine (fMLP)-activated human neutrophils. The nanobubbles were prepared using perfluoropentane and coconut oil as the respective core and shell, with soybean phosphatidylcholine (SPC) and/or cationic surfactants as the interfacial layers. The cytotoxic effect of the nanobubbles on neutrophils was determined by extracellular O₂(.)⁻ release, intracellular reactive oxygen species (ROS), lactate dehydrogenase (LDH), and elastase release. Particle sizes of the nanobubbles with different percentages of perfluorocarbon, oil, and surfactants in ranged 186-432 nm. The nanobubbles were demonstrated to inhibit the generation of superoxide and intracellular ROS. The cytotoxicity of nanobubbles may be mainly associated with membrane damage, as indicated by the high LDH leakage. Systems with Forestall (FE), a cationic surfactant, or higher SPC contents exhibited the greatest LDH release by 3-fold compared to the control. The further addition of an oil component reduced the cytotoxicity induced by the nanobubbles. Exposure to most of the nanobubble formulations upregulated elastase release by activated neutrophils. Contrary to this result, stearylamine (SA)-containing systems slightly but significantly suppressed elastase release. FE and SA in a free form caused stronger responses by neutrophils than when they were incorporated into nanobubbles. In summary, exposure to nanobubbles resulted in a formulation-dependent toxicity toward human neutrophils that was associated with both oxygen-dependent and -independent pathways. Clinicians should therefore exercise caution when using nanobubbles in patients

  1. Multiple forms of soluble monophenol, dihydroxyphenylalanine: oxygen-oxidoreductase (EC 1.14.18.1) from potato tubers (Solanum tuberosum).

    PubMed

    Matheis, G; Belitz, H D

    1975-04-01

    Upon polyacrylamide gel electrophoresis, a soluble phenoloxidase from potatoes (var. Maritta) revealed 17 multiple forms with activity towards dopa and almost all other o-diphenols tested, but only 5 of the forms reacted with monophenols. Isoelectric focusing of the crude enzyme resulted in 2 main peaks with activity towards dopa, having isoelectric points at pH ranges 4.0-4.7 and 5.1-5.4: smaller amounts of the enzyme at higher pI values were also detected. When activity peaks were controlled by polyacrylamide gel electrophoresis, all bands previously detected by electrophoresis of the crude enzyme were recovered, but all peaks were electrophoretically heterogeneous. Gel chromatography of the crude enzyme showed different molecular forms. Their molecular weights indicated monomer, dimer, tetramer, octamer and polymer (at least hexadecamer) forms with a monomer molecular weight of about 36000. PMID:820122

  2. Multiple forms of acid phosphatase activity in Gaucher's disease.

    PubMed

    Chambers, J P; Peters, S P; Glew, R H; Lee, R E; McCafferty, L R; Mercer, D W; Wenger, D A

    1978-07-01

    Although the primary genetic defect in all individuals with Gaucher's disease is a deficiency in glucocerebrosidase activity, the finding of marked elevations in splenic and serum acid phosphatase activity is almost as consistent a finding. Gaucher spleen and serum contain at least two forms of acid phosphatase that can be readily separated by chromatography on columns containing the cation exchange resin Sulphopropyl Sephadex. The major species of acid phosphatase (designated SP-I) contained in Triton X-100 (1% v/v) extracts of Gaucher spleen accounts for 65%--95% of the total activity and has the following properties: (1) it does not bind to the cation exchange column; (2) it exhibitis a pH optimum of 4.5--5.0; (3) it is inhibited by sodium fluoride (15 mM), L(+)-tartaric acid (20 mM), and beta-mercaptoethanol (2.1 M), and (4) it is resistant to inhibition by sodium dithionite (10 mM). The minor acid phosphatase activity (designated SP-II) present in extracts of Gaucher spleen has properties similar to those of the major species of acid phosphatase activity contained in serum from patients with Gaucher's disease: (1) it binds firmly to cation exchange columns (eluted by 0.5 M sodium chloride); (2) it exhibits a pH optimum of 5.0--6.0; (3) it is inhibited by sodium fluoride and sodium dithionite; and (4) it is resistant to inhibition by beta-mercaptoethanol (2.1 M) and L(+)-tartaric acid (20 mM). In addition, a second form of acid phosphatase that is tartrate resistant was found to be elevated in Gaucher serum. This form of serum acid phosphatase did not bind to Sulphopropyl Sephadex, was found to be significantly resistant to beta-mercaptoethanol (2.1 M), and was only partially inhibited by sodium dithionite (10 mM). The findings reported here indicate that at least three distinct forms of acid phosphatase activity are elevated in Gaucher's disease. Furthermore, the minor acid phosphatase activity contained in spleen homogenates has properties very similar to

  3. Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study.

    PubMed

    Zhang, Libo; Zhou, Gang

    2016-04-14

    The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO2 is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximate to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs. PMID:27083744

  4. Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

    NASA Astrophysics Data System (ADS)

    Zhang, Libo; Zhou, Gang

    2016-04-01

    The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO2 is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximate to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.

  5. Rubisco in marine symbiotic dinoflagellates: form II enzymes in eukaryotic oxygenic phototrophs encoded by a nuclear multigene family.

    PubMed

    Rowan, R; Whitney, S M; Fowler, A; Yellowlees, D

    1996-03-01

    Genes encoding ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) were cloned from dinoflagellate symbionts (Symbiodinium spp) of the giant clam Tridacna gigas and characterized. Strikingly, Symbiodinium Rubisco is completely different from other eukaryotic (form I) Rubiscos: it is a form II enzyme that is approximately 65% identical to Rubisco from Rhodospirillum rubrum (Rubisco forms I and II are approximately 25 to 30% identical); it is nuclear encoded by a multigene family; and the predominantly expressed Rubisco is encoded as a precursor polyprotein. One clone appears to contain a predominantly expressed Rubisco locus (rbcA), as determined by RNA gel blot analysis of Symbiodinium RNA and sequencing of purified Rubisco protein. Another contains an enigmatic locus (rbcG) that exhibits an unprecedented pattern of amino acid replacement but does not appear to be a pseudogene. The expression of rbcG has not been analyzed; it was detected only in the minor of two taxa of Symbiodinium that occur together in T. gigas. This study confirms and describes a previously unrecognized branch of Rubisco's evolution: a eukaryotic form II enzyme that participates in oxygenic photosynthesis and is encoded by a diverse, nuclear multigene family.

  6. Solar Abundances of Rock Forming Elements, Extreme Oxygen and Hydrogen in a Young Polluted White Dwarf

    NASA Astrophysics Data System (ADS)

    Farihi, J.; Koester, D.; Zuckerman, B.; Vican, L.; Gänsicke, B. T.; Smith, N.; Walth, G.; Breedt, E.

    2016-09-01

    The Teff = 20 800 K white dwarf WD 1536+520 is shown to have broadly solar abundances of the major rock forming elements O, Mg, Al, Si, Ca, and Fe, together with a strong relative depletion in the volatile elements C and S. In addition to the highest metal abundances observed to date, including log (O/He) =-3.4, the helium-dominated atmosphere has an exceptional hydrogen abundance at log (H/He) =-1.7. Within the uncertainties, the metal-to-metal ratios are consistent with the accretion of an H2O-rich and rocky parent body, an interpretation supported by the anomalously high trace hydrogen. The mixed atmosphere yields unusually short diffusion timescales for a helium atmosphere white dwarf, of no more than a few hundred yr, and equivalent to those in a much cooler, hydrogen-rich star. The overall heavy element abundances of the disrupted parent body deviate modestly from a bulk Earth pattern, and suggest the deposition of some core-like material. The total inferred accretion rate is 4.2 × 109 g s-1, and at least 4 times higher than any white dwarf with a comparable diffusion timescale. Notably, when accretion is exhausted in this system, both metals and hydrogen will become undetectable within roughly 300 Myr, thus supporting a scenario where the trace hydrogen is related to the ongoing accretion of planetary debris.

  7. The effect of mayfly (Hexagenia spp.) burrowing activity on sediment oxygen demand in western Lake Erie

    USGS Publications Warehouse

    Edwards, William J.; Soster, Frederick M.; Matisoff, Gerald; Schloesser, Donald W.

    2009-01-01

    Previous studies support the hypothesis that large numbers of infaunal burrow-irrigating organisms in the western basin of Lake Erie may increase significantly the sediment oxygen demand, thus enhancing the rate of hypolimnetic oxygen depletion. We conducted laboratory experiments to quantify burrow oxygen dynamics and increased oxygen demand resulting from burrow irrigation using two different year classes of Hexagenia spp. nymphs from western Lake Erie during summer, 2006. Using oxygen microelectrodes and hot film anemometry, we simultaneously determined oxygen concentrations and burrow water flow velocities. Burrow oxygen depletion rates ranged from 21.7 mg/nymph/mo for 15 mm nymphs at 23 °C to 240.7 mg/nymph/mo for 23 mm nymphs at 13 °C. Sealed microcosm experiments demonstrated that mayflies increase the rate of oxygen depletion by 2-5 times that of controls, depending on size of nymph and water temperature, with colder waters having greater impact. At natural population densities, nymph pumping activity increased total sediment oxygen demand 0.3-2.5 times compared to sediments with no mayflies and accounted for 22-71% of the total sediment oxygen demand. Extrapolating laboratory results to the natural system suggest that Hexagenia spp. populations may exert a significant control on oxygen depletion during intermittent stratification. This finding may help explain some of the fluctuations in Hexagenia spp. population densities in western Lake Erie and suggests that mayflies, by causing their own population collapse irrespective of other environmental conditions, may need longer term averages when used as a bio-indicator of the success of pollution-abatement programs in western Lake Erie and possibly throughout the Great Lakes.

  8. Aerobic deterioration stimulates outgrowth of spore-forming Paenibacillus in corn silage stored under oxygen-barrier or polyethylene films.

    PubMed

    Borreani, Giorgio; Dolci, Paola; Tabacco, Ernesto; Cocolin, Luca

    2013-08-01

    The occurrence of Bacillus and Paenibacillus spores in silage is of great concern to dairy producers because their spores can survive pasteurization and some strains are capable of subsequently germinating and growing under refrigerated conditions in pasteurized milk. The objectives of this study were to verify the role of aerobic deterioration of corn silage on the proliferation of Paenibacillus spores and to evaluate the efficacy of oxygen-barrier films used to cover silage during fermentation and storage to mitigate these undesirable bacterial outbreaks. The trial was carried out on whole-crop maize (Zea mays L.) inoculated with a mixture of Lactobacillus buchneri, Lactobacillus plantarum, and Enterococcus faecium. A standard polyethylene film and a polyethylene-polyamide film with an enhanced oxygen barrier were used to produce the silage bags for this experiment. The silos were stored indoors at ambient temperature (18 to 22°C) and opened after 110 d. The silage was sampled after 0, 2, 5, 7, 9, and 14 d of aerobic exposure to quantify the growth of endospore-forming bacteria during the exposure of silages to air. Paenibacillus macerans (gram-positive, facultatively anaerobic bacteria) was able to develop during the aerobic exposure of corn silage. This species was present in the herbage at harvesting, together with clostridial spores, and survived ensiling fermentation; it constituted more than 60% of the anaerobic spore formers at silage opening. During silage spoilage, the spore concentration of P. macerans increased to values greater than 7.0 log10 cfu/g of silage. The use of different plastic films to seal silages affected the growth of P. macerans and the number of spores during aerobic exposure of silages. These results indicate that the number of Paenibacillus spores could greatly increase in silage after exposure to air, and that oxygen-barrier films could help to reduce the potential for silage contamination of this important group of milk spoilage

  9. Singlet oxygen scavenging activity and cytotoxicity of essential oils from rutaceae.

    PubMed

    Ao, Yoko; Satoh, Kazue; Shibano, Katsushige; Kawahito, Yukari; Shioda, Seiji

    2008-07-01

    Since we have been exposed to excessive amounts of stressors, aromatherapy for the relaxation has recently become very popular recently. However, there is a problem which responds to light with the essential oil used by aromatherapy. It is generally believed that singlet oxygen is implicated in the pathogenesis of various diseases such as light-induced skin disorders and inflammatory responses. Here we studied whether essential oils can effectively scavenge singlet oxygen upon irradiation, using the electron spin resonance (ESR) method. Green light was used to irradiate twelve essential oils from rutaceae. Among these twelve essential oils, eight were prepared by the expression (or the compression) method (referred to as E oil), and four samples were prepared by the steam distillation method (referred to as SD oil). Five E oils enhanced singlet oxygen production. As these essential oils may be phototoxic, it should be used for their use whit light. Two E oils and three SD oils showed singlet oxygen scavenging activity. These results may suggest that the antioxidant activity of essential oils are judged from their radical scavenging activity. Essential oils, which enhance the singlet oxygen production and show higher cytotoxicity, may contain much of limonene. These results suggest that limonene is involved not only in the enhancement of singlet oxygen production but also in the expression of cytotoxic activity, and that attention has to be necessary for use of blended essential oils.

  10. Chemical forms of the fluorine, chlorine, oxygen and carbon in coal fly ash and their correlations with mercury retention.

    PubMed

    Deng, Shuang; Shu, Yun; Li, Songgeng; Tian, Gang; Huang, Jiayu; Zhang, Fan

    2016-01-15

    Fly ashes recovered from the particulate control devices at six pulverized coal boiler unites of China, are studied using an X-ray photoelectron spectroscopy (XPS) with a particular focus on the functionalities of fluorine (F), chlorine (Cl), carbon and oxygen on fly ash. It is found that the inorganic forms of F and Cl are predominant on the ash surface in comparison with their organics, and the proportion of organic Cl is relatively higher than that of organic F. Similar results are also obtained in the bulk by correlating the F and Cl contents with those of the unburnt carbon and other compositions in ash. Strong correlations of mercury retention with surface carbon-oxygen functional groups indicate that the C=O, OH/C-O and (O-C=O)-O on surface are of significant importance for mercury retention in fly ash. Their surface concentrations are related to coal type. The presence of Cl in fly ash helps with mercury retention. No obvious effect of F is observed. PMID:26410268

  11. Channel-Forming Activities in the Glycosomal Fraction from the Bloodstream Form of Trypanosoma brucei

    PubMed Central

    Miinalainen, Ilkka J.; Hiltunen, J. Kalervo; Michels, Paul A. M.; Antonenkov, Vasily D.

    2012-01-01

    Background Glycosomes are a specialized form of peroxisomes (microbodies) present in unicellular eukaryotes that belong to the Kinetoplastea order, such as Trypanosoma and Leishmania species, parasitic protists causing severe diseases of livestock and humans in subtropical and tropical countries. The organelles harbour most enzymes of the glycolytic pathway that is responsible for substrate-level ATP production in the cell. Glycolysis is essential for bloodstream-form Trypanosoma brucei and enzymes comprising this pathway have been validated as drug targets. Glycosomes are surrounded by a single membrane. How glycolytic metabolites are transported across the glycosomal membrane is unclear. Methods/Principal Findings We hypothesized that glycosomal membrane, similarly to membranes of yeast and mammalian peroxisomes, contains channel-forming proteins involved in the selective transfer of metabolites. To verify this prediction, we isolated a glycosomal fraction from bloodstream-form T.brucei and reconstituted solubilized membrane proteins into planar lipid bilayers. The electrophysiological characteristics of the channels were studied using multiple channel recording and single channel analysis. Three main channel-forming activities were detected with current amplitudes 70–80 pA, 20–25 pA, and 8–11 pA, respectively (holding potential +10 mV and 3.0 M KCl as an electrolyte). All channels were in fully open state in a range of voltages ±150 mV and showed no sub-conductance transitions. The channel with current amplitude 20–25 pA is anion-selective (PK+/PCl−∼0.31), while the other two types of channels are slightly selective for cations (PK+/PCl− ratios ∼1.15 and ∼1.27 for the high- and low-conductance channels, respectively). The anion-selective channel showed an intrinsic current rectification that may suggest a functional asymmetry of the channel's pore. Conclusions/Significance These results indicate that the membrane of glycosomes apparently

  12. Activity and Stability of Nanoscale Oxygen Reduction Catalysts

    SciTech Connect

    Shao-Horn, Yang

    2015-07-28

    Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

  13. Temperature dependence of oxygen evolution through catalase-like activity of horseradish peroxidase

    NASA Astrophysics Data System (ADS)

    Popović-Bijelić, A.; Bijelić, G.; Kolar-Anić, Lj.; Vukojević, V.

    2007-09-01

    By experimental investigations of the temperature dependence of catalase-like activity of horseradish peroxidase in the temperature range 278 328 K, different kinetic profiles for oxygen evolution were found below and above 298 K. Extension of the model is proposed to account for these observations. By numeric simulations of the reaction kinetics at different temperatures, it was found that enhanced evaporation of molecular oxygen from the reaction solution is the main root through which oxygen is lost at elevated temperatures in laboratory conditions.

  14. Activation energies to characterize ease of removal of various kinds of oxygen from bismuth molybdate

    SciTech Connect

    Dadyburjor, D.B.; Ruckenstein, E.

    1980-06-01

    Calculations by the method of minimum energy paths showed that oxygen(-2) anions are more easily displaced from molybdenum(VI) or from the layer between molybdenum and bismuth than from bismuth(III) of a 2:1 bismuth molybdate (Bi/sub 2/MoO/sub 6/). However, available experimental evidence suggests that the oxygen of the bismuth layer is active in the selective oxidation of hydrocarbons; apparently the presence of the hydrocarbon decreases the energy barrier required for transfer of the oxygen anion, and anion vacancies generated, e.g., in a prereduction of the catalyst, also decrease the energy barrier.

  15. Cytotoxic and Antitumor Activity of Sulforaphane: The Role of Reactive Oxygen Species

    PubMed Central

    Sestili, Piero; Fimognari, Carmela

    2015-01-01

    According to recent estimates, cancer continues to remain the second leading cause of death and is becoming the leading one in old age. Failure and high systemic toxicity of conventional cancer therapies have accelerated the identification and development of innovative preventive as well as therapeutic strategies to contrast cancer-associated morbidity and mortality. In recent years, increasing body of in vitro and in vivo studies has underscored the cancer preventive and therapeutic efficacy of the isothiocyanate sulforaphane. In this review article, we highlight that sulforaphane cytotoxicity derives from complex, concurring, and multiple mechanisms, among which the generation of reactive oxygen species has been identified as playing a central role in promoting apoptosis and autophagy of target cells. We also discuss the site and the mechanism of reactive oxygen species' formation by sulforaphane, the toxicological relevance of sulforaphane-formed reactive oxygen species, and the death pathways triggered by sulforaphane-derived reactive oxygen species. PMID:26185755

  16. NUCLEAR ACTIVITY IS MORE PREVALENT IN STAR-FORMING GALAXIES

    SciTech Connect

    Rosario, D. J.; Lutz, D.; Berta, S.; Popesso, P.; Genzel, R.; Saintonge, A.; Tacconi, L.; Wuyts, S. E-mail: lutz@mpe.mpg.de E-mail: popesso@mpe.mpg.de E-mail: amelie@mpe.mpg.de E-mail: swuyts@mpe.mpg.de; and others

    2013-07-01

    We explore the question of whether low and moderate luminosity active galactic nuclei (AGNs) are preferentially found in galaxies that are undergoing a transition from active star formation (SF) to quiescence. This notion has been suggested by studies of the UV-optical colors of AGN hosts, which find them to be common among galaxies in the so-called Green Valley, a region of galaxy color space believed to be composed mostly of galaxies undergoing SF quenching. Combining the deepest current X-ray and Herschel/PACS far-infrared (FIR) observations of the two Chandra Deep Fields with redshifts, stellar masses, and rest-frame photometry derived from the extensive and uniform multi-wavelength data in these fields, we compare the rest-frame U - V color distributions and star formation rate distributions of AGNs and carefully constructed samples of inactive control galaxies. The UV-to-optical colors of AGNs are consistent with equally massive inactive galaxies at redshifts out to z {approx} 2, but we show that such colors are poor tracers of SF. While the FIR distributions of both star-forming AGNs and star-forming inactive galaxies are statistically similar, we show that AGNs are preferentially found in star-forming host galaxies, or, in other words, AGNs are less likely to be found in weakly star-forming or quenched galaxies. We postulate that, among X-ray-selected AGNs of low and moderate accretion luminosities, the supply of cold gas primarily determines the accretion rate distribution of the nuclear black holes.

  17. Oxygen control of breathing by an olfactory receptor activated by lactate

    PubMed Central

    Chang, Andy J.; Ortega, Fabian E.; Riegler, Johannes; Madison, Daniel V.; Krasnow, Mark A.

    2015-01-01

    Summary Animals have evolved homeostatic responses to changes in oxygen availability that act on different time scales. Although the hypoxia-inducible factor (HIF) transcriptional pathway that controls long term responses to low oxygen (hypoxia) has been established1, the pathway that mediates acute responses to hypoxia in mammals is not well understood. Here we show that the olfactory receptor Olfr78 is highly and selectively expressed in oxygen-sensitive glomus cells of the carotid body, a chemosensory organ at the carotid artery bifurcation that monitors blood oxygen and stimulates breathing within seconds when oxygen declines2. Olfr78 mutants fail to increase ventilation in hypoxia but respond normally to hypercapnia. Glomus cells are present in normal numbers and appear structurally intact, but hypoxia-induced carotid body activity is diminished. Lactate, a metabolite that rapidly accumulates in hypoxia and induces hyperventilation3–6, activates Olfr78 in heterologous expression experiments, induces calcium transients in glomus cells, and stimulates carotid sinus nerve activity through Olfr78. We propose that in addition to its role in olfaction, Olfr78 acts as a hypoxia sensor in the breathing circuit by sensing lactate produced when oxygen levels decline. PMID:26560302

  18. Reporter cell activity within hydrogel constructs quantified from oxygen-independent bioluminescence.

    PubMed

    Lambrechts, Dennis; Roeffaers, Maarten; Kerckhofs, Greet; Hofkens, Johan; Van de Putte, Tom; Schrooten, Jan; Van Oosterwyck, Hans

    2014-09-01

    By providing a three-dimensional (3D) support to cells, hydrogels offer a more relevant in vivo tissue-like environment as compared to two-dimensional cell cultures. Hydrogels can be applied as screening platforms to investigate in 3D the role of biochemical and biophysical cues on cell behaviour using bioluminescent reporter cells. Gradients in oxygen concentration that result from the interplay between molecular transport and cell metabolism can however cause substantial variability in the observed bioluminescent reporter cell activity. To assess the influence of these oxygen gradients on the emitted bioluminescence for various hydrogel geometries, a combined experimental and modelling approach was implemented. We show that the applied model is able to predict oxygen gradient independent bioluminescent intensities which correlate better to the experimentally determined viable cell numbers, as compared to the experimentally measured bioluminescent intensities. By analysis of the bioluminescence reaction dynamics we obtained a quantitative description of cellular oxygen metabolism within the hydrogel, which was validated by direct measurements of oxygen concentration within the hydrogel. Bioluminescence peak intensities can therefore be used as a quantitative measurement of reporter cell activity within a hydrogel, but an unambiguous interpretation of these intensities requires a compensation for the influence of cell-induced oxygen gradients on the luciferase activity.

  19. Reporter cell activity within hydrogel constructs quantified from oxygen-independent bioluminescence.

    PubMed

    Lambrechts, Dennis; Roeffaers, Maarten; Kerckhofs, Greet; Hofkens, Johan; Van de Putte, Tom; Schrooten, Jan; Van Oosterwyck, Hans

    2014-09-01

    By providing a three-dimensional (3D) support to cells, hydrogels offer a more relevant in vivo tissue-like environment as compared to two-dimensional cell cultures. Hydrogels can be applied as screening platforms to investigate in 3D the role of biochemical and biophysical cues on cell behaviour using bioluminescent reporter cells. Gradients in oxygen concentration that result from the interplay between molecular transport and cell metabolism can however cause substantial variability in the observed bioluminescent reporter cell activity. To assess the influence of these oxygen gradients on the emitted bioluminescence for various hydrogel geometries, a combined experimental and modelling approach was implemented. We show that the applied model is able to predict oxygen gradient independent bioluminescent intensities which correlate better to the experimentally determined viable cell numbers, as compared to the experimentally measured bioluminescent intensities. By analysis of the bioluminescence reaction dynamics we obtained a quantitative description of cellular oxygen metabolism within the hydrogel, which was validated by direct measurements of oxygen concentration within the hydrogel. Bioluminescence peak intensities can therefore be used as a quantitative measurement of reporter cell activity within a hydrogel, but an unambiguous interpretation of these intensities requires a compensation for the influence of cell-induced oxygen gradients on the luciferase activity. PMID:24957291

  20. Aerobic composting of waste activated sludge: Kinetic analysis for microbiological reaction and oxygen consumption

    SciTech Connect

    Yamada, Y.; Kawase, Y. . E-mail: bckawase@mail.eng.toyo.ac.jp

    2006-07-01

    In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%.

  1. Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2013-03-14

    We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, induced by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.

  2. Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2012-10-10

    We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, induced by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.

  3. Identification and absolute configuration of dihydroxy-arachidonic acids formed by oxygenation of 5S-HETE by native and aspirin-acetylated COX-2.

    PubMed

    Mulugeta, Surafel; Suzuki, Takashi; Hernandez, Noemi Tejera; Griesser, Markus; Boeglin, William E; Schneider, Claus

    2010-03-01

    Biosynthesis of the prostaglandin endoperoxide by the cyclooxygenase (COX) enzymes is accompanied by formation of a small amount of 11R-hydroxyeicosatetraenoic acid (HETE), 15R-HETE, and 15S-HETE as by-products. Acetylation of COX-2 by aspirin abrogates prostaglandin synthesis and triggers formation of 15R-HETE as the sole product of oxygenation of arachidonic acid. Here, we investigated the formation of by-products of the transformation of 5S-HETE by native COX-2 and by aspirin-acetylated COX-2 using HPLC-ultraviolet, GC-MS, and LC-MS analysis. 5S,15S- dihydroxy (di)HETE, 5S,15R-diHETE, and 5S,11R-diHETE were identified as by-products of native COX-2, in addition to the previously described di-endoperoxide (5S,15S-dihydroxy-9S,11R,8S,12S-diperoxy-6E,13E-eicosadienoic acid) as the major oxygenation product. 5S,15R-diHETE was the only product formed by aspirin-acetylated COX-2. Both 5,15-diHETE and 5,11-diHETE were detected in CT26 mouse colon carcinoma cells as well as in lipopolysaccharide-activated RAW264.7 cells incubated with 5S-HETE, and their formation was attenuated in the presence of the COX-2 specific inhibitor, NS-398. Aspirin-treated CT26 cells gave 5,15-diHETE as the most prominent product formed from 5S-HETE. 5S,15S-diHETE has been described as a product of the cross-over of 5-lipoxygenase (5-LOX) and 15-LOX activities in elicited rat mononuclear cells and human leukocytes, and our studies implicate cross-over of the 5-LOX and COX-2 pathways as an additional biosynthetic route.

  4. Active curcumin nanoparticles formed from a volatile microemulsion template.

    PubMed

    Margulis, K; Srinivasan, S; Ware, M J; Summers, H D; Godin, B; Magdassi, S

    2014-01-01

    We report on biological performance of organic nanoparticles formed by a simple method based on rapid solvent removal from a volatile microemulsion. The particular focus of the study was on testing the suitability of the method for substances soluble in partially water-miscible organic solvents as well as on evaluating the therapeutic activity of the resultant nanoparticles. Curcumin was employed as a model for hydrophobic drug, and, as it is soluble in water-miscible organic solvents, it was successfully incorporated into a new cyclopentanone-water microemulsion system. During rapid solvent removal by spray-drying, the nanometric droplets of the microemulsion were converted into nanoparticles containing amorphous curcumin with the average size of 20.2±3.4 nm, having ζ potential of -36.2 ±1.8 mV. These nanoparticles were dispersible in water and retained the high loading of the active substance. The therapeutic activity of the resulting nanoparticles was demonstrated in a pancreatic cancer cell line Panc-1. The effective concentration for reducing the metabolic activity was found to be 11.5 μM for nanoparticles compared with 19.5 μM for free curcumin. PMID:25485110

  5. Higher respiratory activity decreases mitochondrial reactive oxygen release and increases life span in Saccharomyces cerevisiae.

    PubMed

    Barros, Mario H; Bandy, Brian; Tahara, Erich B; Kowaltowski, Alicia J

    2004-11-26

    Increased replicative longevity in Saccharomyces cerevisiae because of calorie restriction has been linked to enhanced mitochondrial respiratory activity. Here we have further investigated how mitochondrial respiration affects yeast life span. We found that calorie restriction by growth in low glucose increased respiration but decreased mitochondrial reactive oxygen species production relative to oxygen consumption. Calorie restriction also enhanced chronological life span. The beneficial effects of calorie restriction on mitochondrial respiration, reactive oxygen species release, and replicative and chronological life span could be mimicked by uncoupling agents such as dinitrophenol. Conversely, chronological life span decreased in cells treated with antimycin (which strongly increases mitochondrial reactive oxygen species generation) or in yeast mutants null for mitochondrial superoxide dismutase (which removes superoxide radicals) and for RTG2 (which participates in retrograde feedback signaling between mitochondria and the nucleus). These results suggest that yeast aging is linked to changes in mitochondrial metabolism and oxidative stress and that mild mitochondrial uncoupling can increase both chronological and replicative life span.

  6. Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts

    NASA Astrophysics Data System (ADS)

    Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay; Fabbri, Emiliana; Levecque, Pieter; Kötz, Rüdiger; Schmidt, Thomas J.

    2015-07-01

    In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts.

  7. Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts

    PubMed Central

    Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay; Fabbri, Emiliana; Levecque, Pieter; Kötz, Rüdiger; Schmidt, Thomas J.

    2015-01-01

    In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts. PMID:26178185

  8. Evaluation of the Catalytic Activity and Cytotoxicity of Palladium Nanocubes. The Role of Oxygen

    PubMed Central

    Dahal, Eshan; Curtiss, Jessica; Subedi, Deepak; Chen, Gen; Houston, Jessica P.; Smirnov, Sergei

    2015-01-01

    Recently it has been reported that palladium nanocubes (PdNC) are capable of generating singlet oxygen without photo-excitation simply via chemisorption of molecular oxygen on its surface. Such a trait would make PdNC a highly versatile catalyst suitable in organic synthesis and a Reactive Oxygen Species (ROS) inducing cancer treatment reagent. Here we thoroughly investigated the catalytic activity of PdNC with respect to their ability to produce singlet oxygen and to oxidize 3,5,3′,5′-tetramethyl-benzidine (TMB), as well as, analyzed the cytotoxic properties of PdNC on HeLa cells. Our findings showed no evidence of singlet oxygen production by PdNC. The nanocubes’ activity is not necessarily linked to activation of oxygen. The oxidation of substrate on PdNC can be a first step followed by PdNC regeneration with oxygen or other oxidant. The catalytic activity of PdNC towards oxidation of TMB is very high and shows direct two-electrons oxidation when the surface of PdNC is clean and the ratio of TMB/PdNC is not very high. Sequential one electron oxidation is observed when the pristine quality of PdNC surface is compromised by serum or uncontrolled impurities and/or the ratio of TMB/PdNC is high. Clean PdNC in serum-free media efficiently induce apoptosis of HeLa cells. It is the primary route of cell death and is associated with hyperpolarization of mitochondria, contrary to a common mitochondrial depolarization initiated by ROS. Again, the effects are very sensitive to how well the pristine surface of PdNC is preserved, suggesting that PdNC can be used as an apoptosis inducing agent but only with appropriate drug delivery system. PMID:25886644

  9. Switching on oxygen activation by cobalt complexes of pentadentate ligands.

    PubMed

    Vad, Mads S; Nielsen, Anne; Lennartson, Anders; Bond, Andrew D; McGrady, John E; McKenzie, Christine J

    2011-10-28

    The monoanionic N(4)O ligand N-methyl-N,N'-bis(2-pyridylmethyl)ethylenediamine-N'-acetate (mebpena(-)) undergoes oxidative C-N bond cleavage in the presence of Co(II) and O(2). The two resultant fragments are coordinated to the metal ion in the product [Co(III)(2-pyridylformate)(mepena)]ClO(4) (mepena(-) = N-methyl-N'-(2-pyridylmethyl)ethylenediamine-N'-acetato). Bond cleavage does not occur in the presence of chloride ions and [Co(III)(mebpena)Cl](+), containing intact mebpena(-), can be isolated. The oxidative instability of the mebpena(-) in the presence of Co(II) and air stands in contrast to the oxidative stability of the family of very closely related penta- and hexa-dentate ligands in their cobalt complexes. Cyclic voltammetry on the matched pair [Co(III)Cl(mebpena)](+) and [Co(II)Cl(bztpen)](+), bztpen = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine, shows that substitution of a pyridine donor for a carboxylato donor results in a relatively small cathodic shift of 150 mV in the E°(Co(II)/Co(III)) oxidation potential, presumably this is enough to determine the contrasting metal oxidation state in the complexes isolated under ambient conditions. DFT calculations support a proposal that [Co(II)(mebpena)](+) reacts with O(2) to form a Co(III)-superoxide complex which can abstract an H atom from a ligand methylene C atom as the initial step towards the observed oxidative C-N bond cleavage.

  10. Screening nitrogen-rich bases and oxygen-rich acids by theoretical calculations for forming highly stable salts.

    PubMed

    Zhang, Xueli; Gong, Xuedong

    2014-08-01

    Nitrogen-rich heterocyclic bases and oxygen-rich acids react to produce energetic salts with potential application in the field of composite explosives and propellants. In this study, 12 salts formed by the reaction of the bases 4-amino-1,2,4-trizole (A), 1-amino-1,2,4-trizole (B), and 5-aminotetrazole (C), upon reaction with the acids HNO3 (I), HN(NO2 )2 (II), HClO4 (III), and HC(NO2 )3 (IV), are studied using DFT calculations at the B97-D/6-311++G** level of theory. For the reactions with the same base, those of HClO4 are the most exothermic and spontaneous, and the most negative Δr Gm in the formation reaction also corresponds to the highest decomposition temperature of the resulting salt. The ability of anions and cations to form hydrogen bonds decreases in the order NO3 (-) >N(NO2 )2 (-) >ClO4 (-) >C(NO2 )3 (-) , and C(+) >B(+) >A(+) . In particular, those different cation abilities are mainly due to their different conformations and charge distributions. For the salts with the same anion, the larger total hydrogen-bond energy (EH,tot ) leads to a higher melting point. The order of cations and anions on charge transfer (q), second-order perturbation energy (E2 ), and binding energy (Eb ) are the same to that of EH,tot , so larger q leads to larger E2 , Eb , and EH,tot . All salts have similar frontier orbitals distributions, and their HOMO and LUMO are derived from the anion and the cation, respectively. The molecular orbital shapes are kept as the ions form a salt. To produce energetic salts, 5-aminotetrazole and HClO4 are the preferred base and acid, respectively.

  11. Antioxidative activity and growth regulation of Brassicaceae induced by oxygen radical irradiation

    NASA Astrophysics Data System (ADS)

    Hayashi, Nobuya; Ono, Reoto; Shiratani, Masaharu; Yonesu, Akira

    2015-06-01

    The growth regulation characteristics of plants are investigated when plant seeds are irradiated with atmospheric discharge plasma. Enhancement of the germination and lengths of the stem and root of plants are observed after seeding. The total length of the stem and root increases approximately 1.6 times after a cultivation period of 72 h. The growth regulation effect is found to be maintained for 80 h of cultivation after seeding. The growth regulation originates from the change in the antioxidative activity of plant cells induced by active oxygen species generated in the oxygen plasma, which leads to the production of growth factor in plants.

  12. On-Orbit Checkout and Activation of the ISS Oxygen Generation System

    NASA Technical Reports Server (NTRS)

    Bagdigian, Robert M.; Prokhorov, Kimberlee S.

    2007-01-01

    NASA has developed and; deployed an Oxygen Generation System (OGS) into the Destiny Module of the International Space Station (ISS). The major. assembly; included in this system is the Oxygen Generator Assembly. (OGA) which was developed under NASA contract by Hamilton Sundstrand Space Systems International (HSSSI), Inc. This paper summarizes the installation of the system into the Destiny Module, its initial checkout and periodic preventative maintenance activities, and its operational activation. Trade studies and analyses that were conducted with the goal of mitigating on-orbit operational risks are also discussed.

  13. Mass spectrometric study on inactivation mechanism of spore-forming bacteria by low-pressure surface-wave excited oxygen plasma

    NASA Astrophysics Data System (ADS)

    Zhao, Ying; Ogino, Akihisa; Nagatsu, Masaaki

    2011-05-01

    In this letter, the etching phenomena of the spore-forming bacteria by oxygen plasma were investigated by using quadrupole mass spectrometry. The etching by-products of H2O and CO2 were obviously detected during the oxygen plasma irradiation by the multiple ion detection measurement. Inactivation of roughly 106 spores population was achieved under almost the same reduced spore shapes for three different incident microwave powers. It is considered from the present results that the oxygen radical etching could cause damage to the germinant receptors located in the inner membrane inevitable for germination of spores, without any damage of the DNA in the cores.

  14. Mass spectrometric study on inactivation mechanism of spore-forming bacteria by low-pressure surface-wave excited oxygen plasma

    SciTech Connect

    Zhao Ying; Ogino, Akihisa; Nagatsu, Masaaki

    2011-05-09

    In this letter, the etching phenomena of the spore-forming bacteria by oxygen plasma were investigated by using quadrupole mass spectrometry. The etching by-products of H{sub 2}O and CO{sub 2} were obviously detected during the oxygen plasma irradiation by the multiple ion detection measurement. Inactivation of roughly 10{sup 6} spores population was achieved under almost the same reduced spore shapes for three different incident microwave powers. It is considered from the present results that the oxygen radical etching could cause damage to the germinant receptors located in the inner membrane inevitable for germination of spores, without any damage of the DNA in the cores.

  15. Oxygen reduction and evolution at single-metal active sites: Comparison between functionalized graphitic materials and protoporphyrins

    NASA Astrophysics Data System (ADS)

    Calle-Vallejo, F.; Martínez, J. I.; García-Lastra, J. M.; Abad, E.; Koper, M. T. M.

    2013-01-01

    A worldwide spread of clean technologies such as low-temperature fuel cells and electrolyzers depends strictly on their technical reliability and economic affordability. Currently, both conditions are hardly fulfilled mainly due to the same reason: the oxygen electrode, which has large overpotentials and is made of precious materials. A possible solution is the use of non-noble electrocatalysts with single-metal active sites. Here, on the basis of DFT calculations of adsorbed intermediates and a thermodynamic analysis, we compare the oxygen reduction (ORR) and evolution (OER) activities of functionalized graphitic materials and gas-phase porphyrins with late transition metals. We find that both kinds of materials follow approximately the same activity trends, and active sites with transition metals from groups 7 to 9 may be good ORR and OER electrocatalysts. However, spin analyses show more flexibility in the possible oxidation states of the metal atoms in solid electrocatalysts, while in porphyrins they must be + 2. These observations reveal that the catalytic activity of these materials is mainly due to nearest-neighbor interactions. Based on this, we propose that this class of electrocatalysts may be improved by careful selections of the support and the ligand properties close to the active sites and/or the ramifications near them, so that charge is transferred back and forth during adsorption and selective hydrogen bonds are formed.

  16. Oxygenated drinking water enhances immune activity in pigs and increases immune responses of pigs during Salmonella typhimurium infection.

    PubMed

    Jung, Bock-Gie; Lee, Jin-A; Lee, Bong-Joo

    2012-12-01

    It has been considered that drinking oxygenated water improves oxygen availability, which may increase vitality and improve immune functions. The present study evaluated the effects of oxygenated drinking water on immune function in pigs. Continuous drinking of oxygenated water markedly increased peripheral blood mononuclear cell proliferation, interleukin-1β expression level and the CD4(+):CD8(+) cell ratio in pigs. During Salmonella Typhimurium infection, total leukocytes and relative cytokines expression levels were significantly increased in pigs consuming oxygenated water compared with pigs consuming tap water. These findings suggest that oxygenated drinking water enhances immune activity in pigs and increases immune responses of pigs during S. Typhimurium Infection.

  17. The relationship between brain cortical activity and brain oxygenation in the prefrontal cortex during hypergravity exposure.

    PubMed

    Smith, Craig; Goswami, Nandu; Robinson, Ryan; von der Wiesche, Melanie; Schneider, Stefan

    2013-04-01

    Artificial gravity has been proposed as a method to counteract the physiological deconditioning of long-duration spaceflight; however, the effects of hypergravity on the central nervous system has had little study. The study aims to investigate whether there is a relationship between prefrontal cortex brain activity and prefrontal cortex oxygenation during exposure to hypergravity. Twelve healthy participants were selected to undergo hypergravity exposure aboard a short-arm human centrifuge. Participants were exposed to hypergravity in the +Gz axis, starting from 0.6 +Gz for women, and 0.8 +Gz for men, and gradually increasing by 0.1 +Gz until the participant showed signs of syncope. Brain cortical activity was measured using electroencephalography (EEG) and localized to the prefrontal cortex using standard low-resolution brain electromagnetic tomography (LORETA). Prefrontal cortex oxygenation was measured using near-infrared spectroscopy (NIRS). A significant increase in prefrontal cortex activity (P < 0.05) was observed during hypergravity exposure compared with baseline. Prefrontal cortex oxygenation was significantly decreased during hypergravity exposure, with a decrease in oxyhemoglobin levels (P < 0.05) compared with baseline and an increase in deoxyhemoglobin levels (P < 0.05) with increasing +Gz level. No significant correlation was found between prefrontal cortex activity and oxy-/deoxyhemoglobin. It is concluded that the increase in prefrontal cortex activity observed during hypergravity was most likely not the result of increased +Gz values resulting in a decreased oxygenation produced through hypergravity exposure. No significant relationship between prefrontal cortex activity and oxygenation measured by NIRS concludes that brain activity during exposure to hypergravity may be difficult to measure using NIRS. Instead, the increase in prefrontal cortex activity might be attributable to psychological stress, which could pose a problem for the use of a

  18. Nonstoichiometric perovskite CaMnO(3-δ) for oxygen electrocatalysis with high activity.

    PubMed

    Du, Jing; Zhang, Tianran; Cheng, Fangyi; Chu, Wangsheng; Wu, Ziyu; Chen, Jun

    2014-09-01

    Perovskite oxides offer efficient and cheap electrocatalysts for both oxygen reduction reactions and oxygen evolution reactions (ORR/OER) in diverse oxygen-based electrochemical technologies. In this study, we report a facile strategy to enhance the electrocatalytic activity of CaMnO3 by introducing oxygen defects. The nonstoichiometric CaMnO(3-δ) (0 < δ ≤ 0.5) was prepared through thermal reduction of pristine perovskite microspheres and nanoparticles, which were synthesized from thermal-decomposition of carbonate precursors and the Pechini route, respectively. The as-prepared samples were analyzed by chemical titration, structural refinement, thermogravimetric analysis, and energy spectrometry. In 0.1 M KOH aqueous solution, the nonstoichiometric CaMnO(3-δ) with δ near 0.25 and an average Mn valence close to 3.5 exhibited the highest ORR activity (36.7 A g(-1) at 0.70 V vs RHE, with onset potential of 0.96 V), which is comparable to that of benchmark Pt/C. Density functional theory (DFT) studies and electrical conductivity measurement revealed that the enhanced ORR kinetics is due to facilitated oxygen activation and improved electrical properties. Besides high activity, the nonstoichiometric perovskite oxides showed respectable catalytic stability. Furthermore, the moderate oxygen-defective CaMnO(3-δ) (δ ≈ 0.25) favored the OER because of the improved electrical conductivity. This study makes nonstoichiometric CaMnO(3-δ) a promising active, inexpensive bifunctional catalytic material for reversible ORR and OER.

  19. 76 FR 27077 - Agency Information Collection Activities: Form AR-11 and Form AR-11SR, Extension of an Existing...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-10

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  20. 75 FR 16492 - Agency Information Collection Activities: Form G-28, and Form G-28I, Revision of an Existing...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-01

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form G-28, and... Department of Homeland Security, U.S. Citizenship and Immigration Services (USCIS) has submitted the... sponsoring the collection: Form G-28, and Form G-28I. U.S. Citizenship and Immigration Services (USCIS)....

  1. New Active Optical Technique Developed for Measuring Low-Earth-Orbit Atomic Oxygen Erosion of Polymers

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A.; deGroh, Kim K.; Demko, Rikako

    2003-01-01

    Polymers such as polyimide Kapton (DuPont) and Teflon FEP (DuPont, fluorinated ethylene propylene) are commonly used spacecraft materials because of desirable properties such as flexibility, low density, and in the case of FEP, a low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low-Earth-orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen reaction with polymers causes erosion, which is a threat to spacecraft performance and durability. It is, therefore, important to understand the atomic oxygen erosion yield E (the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. The most common technique for determining E is a passive technique based on mass-loss measurements of samples exposed to LEO atomic oxygen during a space flight experiment. There are certain disadvantages to this technique. First, because it is passive, data are not obtained until after the flight is completed. Also, obtaining the preflight and postflight mass measurements is complicated by the fact that many polymers absorb water and, therefore, the mass change due to water absorption can affect the E data. This is particularly true for experiments that receive low atomic oxygen exposures or for samples that have a very low E. An active atomic oxygen erosion technique based on optical measurements has been developed that has certain advantages over the mass-loss technique. This in situ technique can simultaneously provide the erosion yield data on orbit and the atomic oxygen exposure fluence, which is needed for erosion yield determination. In the optical technique, either sunlight or artificial light can be used to measure the erosion of semitransparent or opaque polymers as a result of atomic oxygen attack. The technique is simple and adaptable to a rather wide range of polymers, providing that they have a sufficiently high optical absorption coefficient. If one covers a photodiode with a

  2. Benzene's metabolites alter c-MYB activity via reactive oxygen species in HD3 cells

    SciTech Connect

    Wan, Joanne; Winn, Louise M. . E-mail: winnl@queensu.ca

    2007-07-15

    Benzene is a known leukemogen that is metabolized to form reactive intermediates and reactive oxygen species (ROS). The c-Myb oncoprotein is a transcription factor that has a critical role in hematopoiesis. c-Myb transcript and protein have been overexpressed in a number of leukemias and cancers. Given c-Myb's role in hematopoiesis and leukemias, it is hypothesized that benzene interferes with the c-Myb signaling pathway and that this involves ROS. To investigate our hypothesis, we evaluated whether benzene, 1,4-benzoquinone, hydroquinone, phenol, and catechol generated ROS in chicken erythroblast HD3 cells, as measured by 5-(and-6)-chloromethyl-2',7'-dichlorodihydrofluorescein diacetate (DCFDA) and dihydrorhodamine-123 (DHR-123), and whether the addition of 100 U/ml of the antioxidating enzyme superoxide dismutase (SOD) could prevent ROS generation. Reduced to oxidized glutathione ratios (GSH:GSSG) were also assessed as well as hydroquinone and benzoquinone's effects on c-Myb protein levels and activation of a transiently transfected reporter construct. Finally we attempted to abrogate benzene metabolite mediated increases in c-Myb activity with the use of SOD. We found that benzoquinone, hydroquinone, and catechol increased DCFDA fluorescence, increased DHR-123 fluorescence, decreased GSH:GSSG ratios, and increased reporter construct expression after 24 h of exposure. SOD was able to prevent DCFDA fluorescence and c-Myb activity caused by benzoquinone and hydroquinone only. These results are consistent with other studies, which suggest metabolite differences in benzene-mediated toxicity. More importantly, this study supports the hypothesis that benzene may mediate its toxicity through ROS-mediated alterations in the c-Myb signaling pathway.

  3. Mercuric ions inhibit mitogen-activated protein kinase dephosphorylation by inducing reactive oxygen species

    SciTech Connect

    Haase, Hajo; Engelhardt, Gabriela; Hebel, Silke; Rink, Lothar

    2011-01-01

    Mercury intoxication profoundly affects the immune system, in particular, signal transduction of immune cells. However, the mechanism of the interaction of mercury with cellular signaling pathways, such as mitogen activated protein kinases (MAPK), remains elusive. Therefore, the objective of this study is to investigate three potential ways in which Hg{sup 2+} ions could inhibit MAPK dephosphorylation in the human T-cell line Jurkat: (1) by direct binding to phosphatases; (2) by releasing cellular zinc (Zn{sup 2+}); and (3) by inducing reactive oxygen species (ROS). Hg{sup 2+} causes production of ROS, measured by dihydrorhodamine 123, and triggers ROS-mediated Zn{sup 2+} release, detected with FluoZin-3. Yet, phosphatase-inhibition is not mediated by binding of Zn{sup 2+} or Hg{sup 2+}. Rather, phosphatases are inactivated by at least two forms of thiol oxidation; initial inhibition is reversible with reducing agents such as Tris(2-carboxyethyl)phosphine. Prolonged inhibition leads to non-reversible phosphatase oxidation, presumably oxidizing the cysteine thiol to sulfinic- or sulfonic acid. Notably, phosphatases are a particularly sensitive target for Hg{sup 2+}-induced oxidation, because phosphatase activity is inhibited at concentrations of Hg{sup 2+} that have only minor impact on over all thiol oxidation. This phosphatase inhibition results in augmented, ROS-dependent MAPK phosphorylation. MAPK are important regulators of T-cell function, and MAPK-activation by inhibition of phosphatases seems to be one of the molecular mechanisms by which mercury affects the immune system.

  4. Oxidized low density lipoprotein increases acetylcholinesterase activity correlating with reactive oxygen species production.

    PubMed

    Yamchuen, Panit; Aimjongjun, Sathid; Limpeanchob, Nanteetip

    2014-12-01

    Hyperlipidemia, low density lipoproteins (LDL) and their oxidized forms, and oxidative stress are suspected to be a key combination in the onset of AD and acetylcholinesterase (AChE) plays a part in this pathology. The present study aimed to link these parameters using differentiated SH-SY5Y human neuroblastoma cells in culture. Both mildly and fully oxidized human LDL (mox- and fox-LDL), but not native (non-oxidized) LDL were cytotoxic in dose- and time-dependent patterns and this was accompanied by an increased production of intracellular reactive oxygen species (ROS). Oxidized LDL (10-200 μg/mL) augmented AChE activity after 4 and 24h treatments, respectively while the native LDL was without effect. The increased AChE with oxidized LDLs was accompanied by a proportionate increase in intracellular ROS formation (R=0.904). These findings support the notion that oxidized LDLs are cytotoxic and that their action on AChE may reduce central cholinergic transmission in AD and affirm AChE as a continued rational for anticholinesterase therapy but in conjunction with antioxidant/antihyperlipidemic cotreatments.

  5. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-08-01

    Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  6. Gold-doped graphene: A highly stable and active electrocatalysts for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Stolbov, Sergey; Alcántara Ortigoza, Marisol

    2015-04-01

    In addressing the growing need of renewable and sustainable energy resources, hydrogen-fuel-cells stand as one of the most promising routes to transform the current energy paradigm into one that integrally fulfills environmental sustainability. Nevertheless, accomplishing this technology at a large scale demands to surpass the efficiency and enhance the cost-effectiveness of platinum-based cathodes, which catalyze the oxygen reduction reaction (ORR). In this work, our first-principles calculations show that Au atoms incorporated into graphene di-vacancies form a highly stable and cost-effective electrocatalyst that is, at the same time, as or more (dependently of the dopant concentration) active toward ORR than the best-known Pt-based electrocatalysts. We reveal that partial passivation of defected-graphene by gold atoms reduces the reactivity of C dangling bonds and increases that of Au, thus optimizing them for catalyzing the ORR and yielding a system of high thermodynamic and electrochemical stabilities. We also demonstrate that the linear relation among the binding energies of the reaction intermediates assumed in computational high-throughput material screening does not hold, at least for this non-purely transition-metal material. We expect Au-doped graphene to finally overcome the cathode-related challenge hindering the realization of hydrogen-fuel cells as the leading means of powering transportation and portable devices.

  7. Reactive Oxygen Species Affect Transglutaminase Activity and Regulate Hematopoiesis in a Crustacean.

    PubMed

    Junkunlo, Kingkamon; Söderhäll, Kenneth; Söderhäll, Irene; Noonin, Chadanat

    2016-08-19

    Reactive oxygen species (ROS) serve as a prime signal in the commitment to hematopoiesis in both mammals and Drosophila In this study, the potential function of ROS during hematopoiesis in the crayfish Pacifastacus leniusculus was examined. The antioxidant N-acetylcysteine (NAC) was used to decrease ROS in both in vivo and in vitro experiments. An increase in ROS was observed in the anterior proliferation center (APC) after LPS injection. In the absence of NAC, the LPS-induced increase in ROS levels resulted in the rapid restoration of the circulating hemocyte number. In the presence of NAC, a delay in the recovery rate of the hemocyte number was observed. NAC treatment also blocked the spread of APC and other hematopoietic tissue (HPT) cells, maintaining these cells at an undifferentiated stage. Extracellular transglutaminase (TGase) has been shown previously to play a role in maintaining HPT cells in an undifferentiated form. In this study, we show that extracellular TGase activity increased when the ROS level in HPT or APC cells was reduced after NAC treatment. In addition, collagen, a major component of the extracellular matrix and a TGase substrate were co-localized on the HPT cell surface. Taken together, the results of this study show that ROS are involved in crayfish hematopoiesis, in which a low ROS level is required to maintain hematopoietic progenitor cells in the tissue and to reduce hemocyte release. The potential roles of TGase in this process are investigated and discussed. PMID:27339892

  8. Gold-doped graphene: A highly stable and active electrocatalysts for the oxygen reduction reaction

    SciTech Connect

    Stolbov, Sergey Alcántara Ortigoza, Marisol

    2015-04-21

    In addressing the growing need of renewable and sustainable energy resources, hydrogen-fuel-cells stand as one of the most promising routes to transform the current energy paradigm into one that integrally fulfills environmental sustainability. Nevertheless, accomplishing this technology at a large scale demands to surpass the efficiency and enhance the cost-effectiveness of platinum-based cathodes, which catalyze the oxygen reduction reaction (ORR). In this work, our first-principles calculations show that Au atoms incorporated into graphene di-vacancies form a highly stable and cost-effective electrocatalyst that is, at the same time, as or more (dependently of the dopant concentration) active toward ORR than the best-known Pt-based electrocatalysts. We reveal that partial passivation of defected-graphene by gold atoms reduces the reactivity of C dangling bonds and increases that of Au, thus optimizing them for catalyzing the ORR and yielding a system of high thermodynamic and electrochemical stabilities. We also demonstrate that the linear relation among the binding energies of the reaction intermediates assumed in computational high-throughput material screening does not hold, at least for this non-purely transition-metal material. We expect Au-doped graphene to finally overcome the cathode-related challenge hindering the realization of hydrogen-fuel cells as the leading means of powering transportation and portable devices.

  9. Zinc release from protein kinase C as the common event during activation by lipid second messenger or reactive oxygen.

    PubMed

    Korichneva, Irina; Hoyos, Beatrice; Chua, Ramon; Levi, Ester; Hammerling, Ulrich

    2002-11-15

    Zinc is a structural component of many regulatory molecules including transcription factors and signaling molecules. We report that two alternate signaling pathways of protein kinase C (PKC) activation involving either the lipid second messengers (diacylglycerol and its mimetics, the phorbol esters) or reactive oxygen converge at the zinc finger of the regulatory domain. They all trigger the release of zinc ions. An increase in intracellular free Zn(2+) was observed by confocal microscopy in intact cells treated with phorbol ester or by mild oxidation. The source of liberated Zn(2+) was traced to PKC and particularly the zinc finger domains. The activated form of native PKCalpha contained significantly less Zn(2+) than the resting form. Furthermore, purified recombinant PKC protein fragments shed stoichiometric amounts of Zn(2+) upon reaction with diacylglycerol, phorbol ester, or reactive oxygen in vitro. Our results offer new insight into the regulation of PKC. Far from cementing rigid structures, zinc actually is the linchpin that orchestrates dynamic changes in response to specific signals, allowing kinase activity to be turned on or off.

  10. Absence of the cbb3 Terminal Oxidase Reveals an Active Oxygen-Dependent Cyclase Involved in Bacteriochlorophyll Biosynthesis in Rhodobacter sphaeroides

    PubMed Central

    Chen, Guangyu E.; Martin, Elizabeth C.; Hunter, C. Neil

    2016-01-01

    ABSTRACT The characteristic green color associated with chlorophyll pigments results from the formation of an isocyclic fifth ring on the tetrapyrrole macrocycle during the biosynthesis of these important molecules. This reaction is catalyzed by two unrelated cyclase enzymes employing different chemistries. Oxygenic phototrophs such as plants and cyanobacteria utilize an oxygen-dependent enzyme, the major component of which is a diiron protein named AcsF, while BchE, an oxygen-sensitive [4Fe-4S] cluster protein, dominates in phototrophs inhabiting anoxic environments, such as the purple phototrophic bacterium Rhodobacter sphaeroides. We identify a potential acsF in this organism and assay for activity of the encoded protein in a strain lacking bchE under various aeration regimes. Initially, cells lacking bchE did not demonstrate AcsF activity under any condition tested. However, on removal of a gene encoding a subunit of the cbb3-type respiratory terminal oxidase, cells cultured under regimes ranging from oxic to micro-oxic exhibited cyclase activity, confirming the activity of the oxygen-dependent enzyme in this model organism. Potential reasons for the utilization of an oxygen-dependent enzyme in anoxygenic phototrophs are discussed. IMPORTANCE The formation of the E ring of bacteriochlorophyll pigments is the least well characterized step in their biosynthesis, remaining enigmatic for over 60 years. Two unrelated enzymes catalyze this cyclization step; O2-dependent and O2-independent forms dominate in oxygenic and anoxygenic phototrophs, respectively. We uncover the activity of an O2-dependent enzyme in the anoxygenic purple phototrophic bacterium Rhodobacter sphaeroides, initially by inactivation of the high-affinity terminal respiratory oxidase, cytochrome cbb3. We propose that the O2-dependent form allows for the biosynthesis of a low level of bacteriochlorophyll under oxic conditions, so that a rapid initiation of photosynthetic processes is possible for

  11. SOA Formation form the NO3 radicals Chemistry of Isoprene, Monoterpenes, Sesquiterpenes, Biogenic Oxygenated Compounds, and Aromatics

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Jaoui, M.; Docherty, K.; Corse, E.; Offenberg, J. H.; Lewandowski, M.

    2011-12-01

    analysis was carried out for SOA formed from the oxidation of these hydrocarbons by OH both in the presence and absence of nitrogen oxides. Results indicate the presence of a wide range of polar oxygenated organic products in resulting SOA, including organic nitro and nitrates. For some systems, compounds previously observed only from OH reactions were also detected in SOA from NO3 reactions. SOA yields, effective enthalpy of vaporization, EC/OC ratio as well as tentative reaction schemes leading to some of the reaction products are presented. We are currently investigating whether compounds are present in both chamber SOA and ambient aerosol that could serve as indicators for nighttime reactions in atmospheric particulate matter.

  12. Oxygenated drinking water enhances immune activity in broiler chicks and increases survivability against Salmonella Gallinarum in experimentally infected broiler chicks.

    PubMed

    Jung, Bock-Gie; Lee, Jin-A; Nam, Kyoung-Woo; Lee, Bong-Joo

    2012-03-01

    It has been suggested that drinking oxygenated water may improve oxygen availability, which may increase vitality and improving immune activity. The present study evaluated the immune enhancing effects of oxygenated drinking water in broiler chicks and demonstrated the protective efficacy of oxygenated drinking water against Salmonella Gallinarum in experimentally infected broiler chicks. Continuous drinking of oxygenated water markedly increased serum lysozyme activity, peripheral blood mononuclear cell proliferation and the CD4(+)/CD8(+) splenocyte ratio in broiler chicks. In the chicks experimentally infected with S. Gallinarum, oxygenated drinking water alleviated symptoms and increased survival. These findings suggest that oxygenated drinking water enhances immune activity in broiler chicks, and increases survivability against S. Gallinarum in experimentally infected broiler chicks.

  13. The Role of Biofilms in the Sedimentology of Actively Forming Gypsum Deposits at Guerrero Negro, Mexico

    NASA Astrophysics Data System (ADS)

    Vogel, Marilyn B.; Des Marais, David J.; Turk, Kendra A.; Parenteau, Mary N.; Jahnke, Linda L.; Kubo, Michael D. Y.

    2009-11-01

    Actively forming gypsum deposits at the Guerrero Negro sabkha and saltern system provided habitats for stratified, pigmented microbial communities that exhibited significant morphological and phylogenetic diversity. These deposits ranged from meter-thick gypsum crusts forming in saltern seawater concentration ponds to columnar microbial mats with internally crystallized gypsum granules developing in natural anchialine pools. Gypsum-depositing environments were categorized as forming precipitation surfaces, biofilm-supported surfaces, and clastic surfaces. Each surface type was described in terms of depositional environment, microbial diversity, mineralogy, and sedimentary fabrics. Precipitation surfaces developed in high-salinity subaqueous environments where rates of precipitation outpaced the accumulation of clastic, organic, and/or biofilm layers. These surfaces hosted endolithic biofilms comprised predominantly of oxygenic and anoxygenic phototrophs, sulfate-reducing bacteria, and bacteria from the phylum Bacteroidetes. Biofilm-supported deposits developed in lower-salinity subaqueous environments where light and low water-column turbulence supported dense benthic microbial communities comprised mainly of oxygenic phototrophs. In these settings, gypsum granules precipitated in the extracellular polymeric substance (EPS) matrix as individual granules exhibiting distinctive morphologies. Clastic surfaces developed in sabkha mudflats that included gypsum, carbonate, and siliclastic particles with thin gypsum/biofilm components. Clastic surfaces were influenced by subsurface brine sheets and capillary evaporation and precipitated subsedimentary gypsum discs in deeper regions. Biofilms appeared to influence both chemical and physical sedimentary processes in the various subaqueous and subaerially exposed environments studied. Biofilm interaction with chemical sedimentary processes included dissolution and granularization of precipitation surfaces, formation of

  14. The role of biofilms in the sedimentology of actively forming gypsum deposits at Guerrero Negro, Mexico.

    PubMed

    Vogel, Marilyn B; Des Marais, David J; Turk, Kendra A; Parenteau, Mary N; Jahnke, Linda L; Kubo, Michael D Y

    2009-11-01

    Actively forming gypsum deposits at the Guerrero Negro sabkha and saltern system provided habitats for stratified, pigmented microbial communities that exhibited significant morphological and phylogenetic diversity. These deposits ranged from meter-thick gypsum crusts forming in saltern seawater concentration ponds to columnar microbial mats with internally crystallized gypsum granules developing in natural anchialine pools. Gypsum-depositing environments were categorized as forming precipitation surfaces, biofilm-supported surfaces, and clastic surfaces. Each surface type was described in terms of depositional environment, microbial diversity, mineralogy, and sedimentary fabrics. Precipitation surfaces developed in high-salinity subaqueous environments where rates of precipitation outpaced the accumulation of clastic, organic, and/or biofilm layers. These surfaces hosted endolithic biofilms comprised predominantly of oxygenic and anoxygenic phototrophs, sulfate-reducing bacteria, and bacteria from the phylum Bacteroidetes. Biofilm-supported deposits developed in lower-salinity subaqueous environments where light and low water-column turbulence supported dense benthic microbial communities comprised mainly of oxygenic phototrophs. In these settings, gypsum granules precipitated in the extracellular polymeric substance (EPS) matrix as individual granules exhibiting distinctive morphologies. Clastic surfaces developed in sabkha mudflats that included gypsum, carbonate, and siliclastic particles with thin gypsum/biofilm components. Clastic surfaces were influenced by subsurface brine sheets and capillary evaporation and precipitated subsedimentary gypsum discs in deeper regions. Biofilms appeared to influence both chemical and physical sedimentary processes in the various subaqueous and subaerially exposed environments studied. Biofilm interaction with chemical sedimentary processes included dissolution and granularization of precipitation surfaces, formation of

  15. The role of biofilms in the sedimentology of actively forming gypsum deposits at Guerrero Negro, Mexico.

    PubMed

    Vogel, Marilyn B; Des Marais, David J; Turk, Kendra A; Parenteau, Mary N; Jahnke, Linda L; Kubo, Michael D Y

    2009-11-01

    Actively forming gypsum deposits at the Guerrero Negro sabkha and saltern system provided habitats for stratified, pigmented microbial communities that exhibited significant morphological and phylogenetic diversity. These deposits ranged from meter-thick gypsum crusts forming in saltern seawater concentration ponds to columnar microbial mats with internally crystallized gypsum granules developing in natural anchialine pools. Gypsum-depositing environments were categorized as forming precipitation surfaces, biofilm-supported surfaces, and clastic surfaces. Each surface type was described in terms of depositional environment, microbial diversity, mineralogy, and sedimentary fabrics. Precipitation surfaces developed in high-salinity subaqueous environments where rates of precipitation outpaced the accumulation of clastic, organic, and/or biofilm layers. These surfaces hosted endolithic biofilms comprised predominantly of oxygenic and anoxygenic phototrophs, sulfate-reducing bacteria, and bacteria from the phylum Bacteroidetes. Biofilm-supported deposits developed in lower-salinity subaqueous environments where light and low water-column turbulence supported dense benthic microbial communities comprised mainly of oxygenic phototrophs. In these settings, gypsum granules precipitated in the extracellular polymeric substance (EPS) matrix as individual granules exhibiting distinctive morphologies. Clastic surfaces developed in sabkha mudflats that included gypsum, carbonate, and siliclastic particles with thin gypsum/biofilm components. Clastic surfaces were influenced by subsurface brine sheets and capillary evaporation and precipitated subsedimentary gypsum discs in deeper regions. Biofilms appeared to influence both chemical and physical sedimentary processes in the various subaqueous and subaerially exposed environments studied. Biofilm interaction with chemical sedimentary processes included dissolution and granularization of precipitation surfaces, formation of

  16. GAS PHASE SELECTIVE PHOTOXIDATION OF ALCOHOLS USING LIGHT-ACTIVATED TITANIUM DIOXIDE AND MOLECULAR OXYGEN

    EPA Science Inventory

    Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen

    Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

  17. Active oxygen species as mediators of plant immunity: three case studies.

    PubMed

    Sandermann, H

    2000-08-01

    A burst of active oxygen species (AOS) is known to be involved in local cell death as part of plant defence against pathogens. It is, however, under dispute to what extent AOS can induce pathogen resistance and immunity throughout the plant. Three experimental strategies that reveal a primary role for AOS and a surprisingly low chemical and spatial specificity are now described for tobacco and Arabidopsis thaliana plants. Ozone is a gaseous AOS that was applied to non-transgenic plants. Hydrogen peroxide or singlet oxygen are AOS that were induced by high-light treatment of transgenic plants that contained antisense constructs inhibiting catalase activity or chlorophyll biosynthetic enzymes. In all cases, activated oxygen species, cellular lesions, ethylene and salicylic acid, and components of major plant defence systems (systemic acquired resistance, hypersensitive response) were induced, as was resistance towards pathogens (tobacco mosaic virus, Pseudomonas syringae or Peronospora parasitica). It is concluded that active oxygen species can act as mediators of plant immunity so that new non-pesticidal plant protection strategies could be developed.

  18. Activation of Methanogenesis in Arid Biological Soil Crusts Despite the Presence of Oxygen

    PubMed Central

    Angel, Roey; Matthies, Diethart; Conrad, Ralf

    2011-01-01

    Methanogenesis is traditionally thought to occur only in highly reduced, anoxic environments. Wetland and rice field soils are well known sources for atmospheric methane, while aerated soils are considered sinks. Although methanogens have been detected in low numbers in some aerated, and even in desert soils, it remains unclear whether they are active under natural oxic conditions, such as in biological soil crusts (BSCs) of arid regions. To answer this question we carried out a factorial experiment using microcosms under simulated natural conditions. The BSC on top of an arid soil was incubated under moist conditions in all possible combinations of flooding and drainage, light and dark, air and nitrogen headspace. In the light, oxygen was produced by photosynthesis. Methane production was detected in all microcosms, but rates were much lower when oxygen was present. In addition, the δ13C of the methane differed between the oxic/oxygenic and anoxic microcosms. While under anoxic conditions methane was mainly produced from acetate, it was almost entirely produced from H2/CO2 under oxic/oxygenic conditions. Only two genera of methanogens were identified in the BSC-Methanosarcina and Methanocella; their abundance and activity in transcribing the mcrA gene (coding for methyl-CoM reductase) was higher under anoxic than oxic/oxygenic conditions, respectively. Both methanogens also actively transcribed the oxygen detoxifying gene catalase. Since methanotrophs were not detectable in the BSC, all the methane produced was released into the atmosphere. Our findings point to a formerly unknown participation of desert soils in the global methane cycle. PMID:21655270

  19. Assessments of Muscle Oxygenation and Cortical Activity Using Functional Near-infrared Spectroscopy in Healthy Adults During Hybrid Activation.

    PubMed

    Lin, Tai-You; Wu, Jin-Shang; Lin, Linda L; Ho, Ting-Chuan; Lin, Pei-Yi; Chen, Jia-Jin J

    2016-01-01

    Hybrid activation (HA), patterned electrical stimulation (ES) superimposed on attempted voluntary movement in close synchrony, can augment muscle force output. It has been proposed for limb function restoration and neuromodulation. Limited studies have been performed to investigate the influences of HA on muscle oxygenation and brain cortical activity. The present study investigates muscle oxygenation and cortical activity during isometric knee extension tasks with voluntary contraction (VOL) only, ES only, and with HA at three stimulation intensities, namely 10 mA (HA-I), 30 mA (HA-II), and 50 mA (HA-III). A frequency-domain near-infrared spectroscopy system was employed to assess the muscle oxygenation in the vastus lateralis as well as the cortical activity from the bilateral sensorimotor cortices (SMCs), premotor cortices (PMCs), and supplementary motor areas (SMAs). Our results show that the increased ES contribution during HA significantly increased O2 demand in working muscle, implying that the intervention of ES accelerates the muscle metabolism during muscle contraction. For cortical activation, ES only had a similar cortical activation pattern to that during VOL but with lower activation in SMCs, PMCs, and SMAs. Augmented sensorimotor activation was observed during the HA-II condition. The enhanced level of cortical activation during HA was not only affected by the ES contribution within HA but also related to the functional specificity of cortical areas. Our results suggest that HA can effectively enhance the muscle oxygen demand as well as the activation of cortical regions, and that the ES contribution within HA is a key factor.

  20. In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity.

    PubMed

    Trześniewski, Bartek J; Diaz-Morales, Oscar; Vermaas, David A; Longo, Alessandro; Bras, Wim; Koper, Marc T M; Smith, Wilson A

    2015-12-01

    Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni(Fe)-B(i)) and nickel oxyhydroxide (Ni(Fe)OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO(-)), which can be described as adsorbed "active oxygen". Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV-vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs.

  1. Common catabolic enzyme patterns in a microplankton community of the Humboldt Current System off northern and central-south Chile: Malate dehydrogenase activity as an index of water-column metabolism in an oxygen minimum zone

    NASA Astrophysics Data System (ADS)

    González, R. R.; Quiñones, R. A.

    2009-07-01

    An extensive subsurface oxygen minimum zone off northern and central-south Chile, associated with the Peru-Chile undercurrent, has important effects on the metabolism of the organisms inhabiting therein. Planktonic species deal with the hypoxic and anoxic environments by relying on biochemical as well as physiological processes related to their anaerobic metabolisms. Here we characterize, for the first time, the potential enzymatic activities involved in the aerobic and anaerobic energy production pathways of microplanktonic organisms (<100 μm), their relationship, and this relationship's association with the oxygen concentration and microplanktonic biomass in the oxygen minimum zone and adjacent areas of the Humboldt Current System water column. Our results demonstrate significant potential enzymatic activity of catabolic pathways in the oxygen minimum zone. Malate dehydrogenase had the highest oxidizing activity of nicotinamide adenine dinucleotide (reduced form) in the batch of catabolic enzymatic activities assayed, including potential pyruvate oxidoreductases activity, the electron transport system, and dissimilatory nitrate reductase. Malate dehydrogenase correlated significantly with almost all the enzymes analyzed within and above the oxygen minimum zone, and also with the oxygen concentration and microplankton biomass in the water column of the Humboldt Current System, especially in the oxygen minimum zone off Iquique. These results suggest a possible specific pattern for the catabolic activity of the microplanktonic realm associated with the oxygen minimum zone spread along the Humboldt Current System off Chile. We hypothesize that malate dehydrogenase activity could be an appropriate indicator of microplankton catabolism in the oxygen minimum zone and adjacent areas.

  2. Unciaphenol, an Oxygenated Analogue of the Bergman Cyclization Product of Uncialamycin Exhibits Anti-HIV Activity.

    PubMed

    Williams, David E; Bottriell, Helen; Davies, Julian; Tietjen, Ian; Brockman, Mark A; Andersen, Raymond J

    2015-11-01

    Unciaphenol (2), an oxygenated analogue of the Bergman cyclization product of the enediyne uncialamycin (1), has been isolated along with 1 from cultures of the actinomycete Streptomyces uncialis. It is proposed that the C-22 OH substituent in 2 might arise from the attack of a nucleophilic oxygen species on the p-benzyne diradical intermediate IA in the Bergman cyclization of 1. 2 shows in vitro anti-HIV activity against viral strains that are resistant to clinically utilized anti-retroviral therapies.

  3. Pu-238 fuel form activities, January 1-31, 1985

    SciTech Connect

    Not Available

    1985-07-01

    This monthly report summarizes production of /sup 238/PuO/sub 2/ fuel forms for use in radioisotopic thermoelectric generators (RTG's) in the Plutonium Fuel Form (PuFF) Facility at the Savannah River Plant.

  4. Highly oxygenated triterpenoids from the roots of Schisandra chinensis and their anti-inflammatory activities.

    PubMed

    Song, Qiu-Yan; Gao, Kun; Nan, Zhi-Biao

    2016-01-01

    A new highly oxygenated triterpenoid, schinchinenlactone D (1), and three known compounds (2-4) were isolated from the roots of Schisandra chinensis. Their structures were determined by combining the spectroscopic analysis with the theoretical computations. The anti-inflammatory activities of compounds 1-4 were evaluated, and compound 3 exhibits the most significant activity in the inhibition of NO production with an IC50 value of 10.6 μM.

  5. Endothelial cell apoptosis induced by bacteria-activated platelets requires caspase-8 and -9 and generation of reactive oxygen species.

    PubMed

    Kuckleburg, Christopher J; Tiwari, Raksha; Czuprynski, Charles J

    2008-02-01

    A common feature of severe sepsis is vascular inflammation and damage to the endothelium. Because platelets can be directly activated by bacteria and endotoxin, these cells may play an important role in determining the outcome of sepsis. For example, inhibiting platelet interactions with the endothelium has been shown to attenuate endothelial cell damage and improve survival during sepsis. Although not entirely understood, the interactions between bacteria-activated platelets and the endothelium may play a key role in the vascular pathology of bacterial sepsis. Haemophilus somnus is a bacterial pathogen that causes diffuse vascular inflammation and endothelial damage. In some cases H. somnus infection results in an acute and fatal form of vasculitis in the cerebral microvasculature known as thrombotic meningoencephalitis (TME). In this study, we have characterized the mechanisms involved in endothelial cell apoptosis induced by activated platelets. We observed that direct contact between H. somnus-activated platelets and endothelial cells induced significant levels of apoptosis; however, Fas receptor activation on bovine endothelial cells was not able to induce apoptosis unless protein synthesis was disrupted. Endothelial cell apoptosis by H. somnus-activated platelets required activation of both caspase-8 and caspase-9, as inhibitors of either caspase inhibited apoptosis. Furthermore, activated platelets induced endothelial cell production of reactive oxygen species (ROS) and disrupting ROS activity in endothelial cells significantly inhibited apoptosis. These findings suggest that bacterial activation of platelets may contribute to endothelial cell dysfunction observed during sepsis, specifically by inducing endothelial cell apoptosis.

  6. Tectonic activity on Pluto after the Charon-forming impact

    NASA Astrophysics Data System (ADS)

    Barr, Amy C.; Collins, Geoffrey C.

    2015-01-01

    The Pluto-Charon system, likely formed from an impact, has reached the endpoint of its tidal evolution. During its evolution into the dual-synchronous state, the equilibrium tidal figures of Pluto and Charon would have also evolved as angular momentum was transferred from Pluto's spin to Charon's orbit. The rate of tidal evolution is controlled by Pluto's interior physical and thermal state. We examine three interior models for Pluto: an undifferentiated rock/ice mixture, differentiated with ice above rock, and differentiated with an ocean. For the undifferentiated case without an ocean, the Pluto-Charon binary does not evolve to its current state unless its internal temperature Ti > 200K , which would likely lead to strong tidal heating, melting, and differentiation. Without an ocean, Pluto's interior temperature must be higher than 240 K for Charon to evolve on a time scale less than the age of the Solar System. Further tidal heating would likely create an ocean. If New Horizons finds evidence of ancient tidally-driven tectonic activity on either body, the most likely explanation is that Pluto had an internal ocean during Charon's orbital evolution.

  7. Structural and Electrochemical Impacts of Oxygen Doped and Surfactant Coated Activated Carbon Electrodes in Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Collins, John; Gourdin, Gerald; Qu, Deyang; Foster, Michelle

    2013-03-01

    Passive charge and discharge dynamics are necessary for advancing Li-ion batteries. Surfactant adsorption on activated carbon has been shown to promote advancements in the discharge capacity, time and cycle-ability of electrochemical systems--specifically by enhancing diffusion pathways for ion insertion/de-insertion and suppressing pore blockage from precipitates known to form during charge/discharge states. Enhancement of surfactant chemisorption on activated carbon is achieved through oxygen doping of the carbon surface. In addition, doping alters the degree of Faradaic processes occurring in solution, resulting in prolonged reduction at the carbon surface. The work presented describes how surface oxygen groups on a granulated activated carbon have been manipulated using nitric acid in a controlled, stepwise fashion. A nonionic surfactant was applied to oxidized and non-oxidized samples at various concentrations. The composition and structure of the activated carbon surface was characterized using DRIFTS, Raman Spectroscopy, SEM and Porosimetry. The charge/discharge Li insertion capacities along with correlating surface microstructure changes were analyzed for all treated electrodes at progressive oxidation stages.

  8. Theoretical study of the phototoxicity of naproxen and the active form of nabumetone.

    PubMed

    Musa, Klefah A K; Eriksson, Leif A

    2008-10-30

    Density functional theory using the hybrid functional B3LYP has been employed in order to study the mechanisms of photoinduced decomposition of the closely related nonsteroidal anti-inflammatory drugs naproxen (NP) and 6-methoxy-2-naphthylacetic acid (MNAA; the active form of nabumetone). The photochemical properties and computed energies of various species obtained in this study show that both drugs dominate in their deprotonated forms at physiological pH. The deprotonated acids are unable to decarboxylate from their excited singlets; instead, they decarboxylate from their first excited triplet states with high efficiency, overcoming energy barriers less than 3 and 1 kcal/mol for MNAA and NP, respectively. The ultraviolet and visible spectra of the neutral, deprotonated, and decarboxylated moieties of MNAA and NP are more-or-less similar but with higher probabilites (oscillator strength) for the latter. This fact, as well as the higher reactivity of NP, is explained in terms of the electron-donating effect of the additional methyl group present in NP. Singlet oxygen, superoxide radical anion, and corresponding peroxyl radical species are expected to be formed in different steps throughout the proposed photodegradation pathways of both drugs, which give rise to their effects on biomolecules, for example, lipid peroxidation.

  9. Role of activation in alveolar macrophage-mediated suppression of the plaque-forming cell response.

    PubMed Central

    Mbawuike, I N; Herscowitz, H B

    1988-01-01

    Alveolar macrophages (AM) are highly suppressive of the in vitro plaque-forming cell (PFC) response of spleen cells obtained from mice primed with sheep erythrocytes. Comparison of macrophage populations obtained from disparate anatomical sites revealed that although in both cases there was a cell-concentration-dependent suppression of the PFC response, resident AM or AM activated as a result of intravenous injection of Mycobacterium bovis BCG were equally suppressive at the doses examined. Although there was a similar dose-dependent suppression with peritoneal macrophages, BCG-activated cells were more suppressive of the PFC response than were resident cells. In contrast, splenic macrophages at comparable concentrations were not at all suppressive. Resident AM exhibited significantly lower levels of 5'-nucleotidase activity than did resident peritoneal macrophages. Macrophage-mediated suppression of the in vitro PFC response could not be attributed to the release of toxic oxygen metabolites (H2O2, O2- ,and .OH) or prostaglandins, since the addition of catalase, superoxide dismutase, 2-mercaptoethanol, or indomethacin did not completely reverse suppression. These results suggest that the lung microenvironment may maintain AM in an activated state which contributes to their potential immunoregulatory functions. PMID:2830191

  10. Tuning the activity of Pt(111) for oxygen electroreduction by subsurface alloying.

    PubMed

    Stephens, Ifan E L; Bondarenko, Alexander S; Perez-Alonso, Francisco J; Calle-Vallejo, Federico; Bech, Lone; Johansson, Tobias P; Jepsen, Anders K; Frydendal, Rasmus; Knudsen, Brian P; Rossmeisl, Jan; Chorkendorff, Ib

    2011-04-13

    To enable the development of low temperature fuel cells, significant improvements are required to the efficiency of the Pt electrocatalysts at the cathode, where oxygen reduction takes place. Herein, we study the effect of subsurface solute metals on the reactivity of Pt, using a Cu/Pt(111) near-surface alloy. Our investigations incorporate electrochemical measurements, ultrahigh vacuum experiments, and density functional theory. Changes to the OH binding energy, ΔE(OH), were monitored in situ and adjusted continuously through the subsurface Cu coverage. The incorporation of submonolayer quantities of Cu into Pt(111) resulted in an 8-fold improvement in oxygen reduction activity. The most optimal catalyst for oxygen reduction has an ΔE(OH) ≈ 0.1 eV weaker than that of pure Pt, validating earlier theoretical predictions. PMID:21417329

  11. Activities of oxygen in liquid copper and silver from electrochemical measurements

    NASA Astrophysics Data System (ADS)

    Otsuka, Shinya; Kozuka, Zensaku

    1981-09-01

    Modified coulometric titrations on the galvanic cell: O in liquid Cu or Ag / ZrO2( + CaO) / Air, Pt, were performed to determine precisely the oxygen activities in liquid copper and silver in the range of relatively low oxygen concentration. The present experimental results were remarkably reproducible in comparison with the published data. The standard Gibbs energies of solution of oxygen in liquid copper and liquid silver for 1/2 O2(l atm) → O(l at. pct) were determined respectively to be ΔG° (in Cu) = -18040 -0.03 T(K) (± 120) cal · g-atom-1 = -75500 -0.12 T(K)(± 500) J · g-atom-1, ΔG°(inAg)= -3860+ 1.56 T(K) (±90) cal · g-atom-1 = -16140 + 6.52 T(K)(±380) J · g-atom-1 where the reference state for dissolved oxygen was an infinitely dilute solution. The present value of the partial entropy of oxygen dissolved in liquid copper differs significantly from that suggested by many investigators. Further, the present equation for liquid copper has been found to be consistent with a correlation proposed previously by the present authors. The equation for liquid silver is in good agreement with the published ones.

  12. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water

    NASA Astrophysics Data System (ADS)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  13. Atrial natriuretic peptide regulates lipid mobilization and oxygen consumption in human adipocytes by activating AMPK

    SciTech Connect

    Souza, Sandra C.; Chau, Mary D.L.; Yang, Qing; Gauthier, Marie-Soleil; Clairmont, Kevin B.; Wu, Zhidan; Gromada, Jesper; Dole, William P.

    2011-07-08

    Highlights: {yields} Treatment of differentiated human adipocytes with atrial natriuretic peptide (ANP) increased lipolysis and oxygen consumption by activating AMP-activated protein kinase (AMPK). {yields} ANP stimulated lipid mobilization by selective activation of the alpha2 subunit of AMPK and increased energy utilization through activation of both the alpha1 and alpha2 subunits of AMPK. {yields} ANP enhanced adipocyte mitochondrial oxidative capacity as evidenced by induction of oxidative mitochondrial genes and increase in oxygen consumption. {yields} Exposure of human adipocytes to fatty acids and (TNF{alpha}) induced insulin resistance and decreased expression of mitochondrial genes which was restored to normal by ANP. -- Abstract: Atrial natriuretic peptide (ANP) has been shown to regulate lipid and carbohydrate metabolism providing a possible link between cardiovascular function and metabolism by mediating the switch from carbohydrate to lipid mobilization and oxidation. ANP exerts a potent lipolytic effect via cGMP-dependent protein kinase (cGK)-I mediated-stimulation of AMP-activated protein kinase (AMPK). Activation of the ANP/cGK signaling cascade also promotes muscle mitochondrial biogenesis and fat oxidation. Here we demonstrate that ANP regulates lipid metabolism and oxygen utilization in differentiated human adipocytes by activating the alpha2 subunit of AMPK. ANP treatment increased lipolysis by seven fold and oxygen consumption by two fold, both of which were attenuated by inhibition of AMPK activity. ANP-induced lipolysis was shown to be mediated by the alpha2 subunit of AMPK as introduction of dominant-negative alpha2 subunit of AMPK attenuated ANP effects on lipolysis. ANP-induced activation of AMPK enhanced mitochondrial oxidative capacity as evidenced by a two fold increase in oxygen consumption and induction of mitochondrial genes, including carnitine palmitoyltransferase 1A (CPT1a) by 1.4-fold, cytochrome C (CytC) by 1.3-fold, and

  14. Effect of different forms of acute stress in the generation of reactive oxygen species in albino Wistar rats.

    PubMed

    Smitha, K K; Mukkadan, J K

    2014-01-01

    Stress is common for all organisms either in the form of eustress (beneficial) or as distress (harmful). Stress is highly diverse in present world and its effects in organisms are well studied. This study is a comparative effect of stress in the generation of reactive oxygen species in albino Wistar rats, which are seldom reported. Here animals were grouped into four and the test animals of each group were administered with any one of the following stress, namely forced swimming induced stress (FS), and noise induced stress (NS), immobilization stress (IS) and overcrowding stress (OS). After stress administration, serum cortisol was estimated as a bio marker of stress in the albino rats, and the liver homogenate were used to estimate superoxide dismutase (SOD) by using rat Elisa kit in the spectrophotometer. The data were processed with unpaired 't' test. The cortisol levels were found to be increased in a highly significant level (P < 0.001) in all the groups as compared to the normal control. And the stress level was found to be maximum in the FS group in comparison with other groups. The mean cortisol level in different stress groups such as FS, NS, IS and OS were found to be 4.15, 3.7, 3.63, 3.62 μ gm/dl respectively. Among all the stressed groups, the SOD level in the FS group were found to be increased in a highly significant level (P < 0.001) in comparison with normal control group. The SOD level in FS group was (30.75 U/mgm. protein) followed by OS (28.96), noise (28.88) and IS (28.77).

  15. Hydrogen-transparent metal surfaces produced by use of molten salts with very low oxygen and water activities

    SciTech Connect

    Deublein, G.; Huggins, R.A. . Dept. of Materials Science and Engineering)

    1989-08-01

    One can employ simple thermodynamic principles to predict conditions under which metals will not form hydrogen-blocking surface oxide layers in electrolyte environments. These principles are used to show that very low oxygen and water activities can be produced in some halide-based molten salt systems by the incorporation of alkali hydrides. Under these conditions, some normally very reactive metals will not form oxide surface layers. As a result, rapid interfacial and surface/bulk equilibria with hydrogen can be attained. Experiments are presented that verify these principles in the titanium-hydrogen and vanadium-hydrogen systems by using electro chemical methods to measure the thermodynamic and kinetic aspects of the solution of hydrogen and the formation of metal hydrides. In addition, it is shown that interfacial equilibrium is obtained very rapidly upon iron and aluminum in such metals.

  16. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    PubMed

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts. PMID:25334050

  17. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    PubMed

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts.

  18. 76 FR 30738 - Agency Information Collection Activities: Form G-845 and Form G-845 Supplement, Revision of a...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-26

    ... the Federal Register on February 22, 2011, at 76 FR 9805, allowing for a 60-day public comment period... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form G-845 and Form G- 845 Supplement, Revision of a Currently Approved Information Collection; Comment Request...

  19. Oxygenation of Organoboronic Acids by a Nonheme Iron(II) Complex: Mimicking Boronic Acid Monooxygenase Activity.

    PubMed

    Chatterjee, Sayanti; Paine, Tapan Kanti

    2015-10-19

    Phenolic compounds are important intermediates in the bacterial biodegradation of aromatic compounds in the soil. An Arthrobacter sp. strain has been shown to exhibit boronic acid monooxygenase activity through the conversion of different substituted phenylboronic acids to the corresponding phenols using dioxygen. While a number of methods have been reported to cleave the C-B bonds of organoboronic acids, there is no report on biomimetic iron complex exhibiting this activity using dioxygen as the oxidant. In that direction, we have investigated the reactivity of a nucleophilic iron-oxygen oxidant, generated upon oxidative decarboxylation of an iron(II)-benzilate complex [(Tp(Ph2))Fe(II)(benzilate)] (Tp(Ph2) = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), toward organoboronic acids. The oxidant converts different aryl/alkylboronic acids to the corresponding oxygenated products with the incorporation of one oxygen atom from dioxygen. This method represents an efficient protocol for the oxygenation of boronic acids with dioxygen as the terminal oxidant.

  20. Oxygenation of Organoboronic Acids by a Nonheme Iron(II) Complex: Mimicking Boronic Acid Monooxygenase Activity.

    PubMed

    Chatterjee, Sayanti; Paine, Tapan Kanti

    2015-10-19

    Phenolic compounds are important intermediates in the bacterial biodegradation of aromatic compounds in the soil. An Arthrobacter sp. strain has been shown to exhibit boronic acid monooxygenase activity through the conversion of different substituted phenylboronic acids to the corresponding phenols using dioxygen. While a number of methods have been reported to cleave the C-B bonds of organoboronic acids, there is no report on biomimetic iron complex exhibiting this activity using dioxygen as the oxidant. In that direction, we have investigated the reactivity of a nucleophilic iron-oxygen oxidant, generated upon oxidative decarboxylation of an iron(II)-benzilate complex [(Tp(Ph2))Fe(II)(benzilate)] (Tp(Ph2) = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), toward organoboronic acids. The oxidant converts different aryl/alkylboronic acids to the corresponding oxygenated products with the incorporation of one oxygen atom from dioxygen. This method represents an efficient protocol for the oxygenation of boronic acids with dioxygen as the terminal oxidant. PMID:26430780

  1. A simple fluorescent probe for the determination of dissolved oxygen based on the catalytic activation of oxygen by iron(II) chelates.

    PubMed

    Luo, Wei; Abbas, M E; Zhu, Lihua; Zhou, Wenyi; Li, Kejing; Tang, Heqing; Liu, Shushen; Li, Weiying

    2009-04-27

    This work aims at establishing a simple fluorescent probe for the determination of dissolved oxygen. It is found that iron(II) ions activate oxygen to produce reactive species being capable of oxidizing non-fluorescent coumarin to fluorescent 7-hydroxycoumarin. However, this process is not effective because the yield of the reactive species is very low in the presence of simple iron(II) salts alone. The addition of organic ligands such as oxalate results in the formation of complexes between iron(II) ions, which leads to considerable increase in the yield of reactive species (such as hydroxyl radicals) and then increase in the fluorescence intensity of 7-hydroxycoumarin to a significant level. It has been observed that in the mixture solution of iron(II) ions, ligand, coumarin, and dissolved oxygen, there is an excellent linear response between the fluorescence and dissolved oxygen. Therefore, a new spectrofluorimetric method has been proposed for the determination of dissolved oxygen by using catalytic activation of O(2) by iron(II) chelates. Under optimized conditions, a linear correlation (r=0.995) has been observed between the fluorescence intensity of 7-hydroxycoumarin at 456 nm and the concentration of dissolved oxygen over the range of 0.96-9.22 mg L(-1). The limit of detection for dissolved oxygen at a signal-to-noise ratio of 3 has been estimated to be 0.35 mg L(-1). The proposed method has been applied to determine the concentration of dissolved oxygen in practical water samples with results as satisfactory as that obtained by the standard iodometric method.

  2. The Essay: Theory and Pedagogy for an Active Form.

    ERIC Educational Resources Information Center

    Heilker, Paul

    Calling for a radical reexamination of the traditional foundation of composition instruction--the thesis/support form, this book argues that the essay, with its informality, conversational tone, meditative mood, and integration of form and content, is better suited to developmental, epistemological, ideological, and feminist rhetorical…

  3. Auditory selective attention to speech modulates activity in the visual word form area.

    PubMed

    Yoncheva, Yuliya N; Zevin, Jason D; Maurer, Urs; McCandliss, Bruce D

    2010-03-01

    Selective attention to speech versus nonspeech signals in complex auditory input could produce top-down modulation of cortical regions previously linked to perception of spoken, and even visual, words. To isolate such top-down attentional effects, we contrasted 2 equally challenging active listening tasks, performed on the same complex auditory stimuli (words overlaid with a series of 3 tones). Instructions required selectively attending to either the speech signals (in service of rhyme judgment) or the melodic signals (tone-triplet matching). Selective attention to speech, relative to attention to melody, was associated with blood oxygenation level-dependent (BOLD) increases during functional magnetic resonance imaging (fMRI) in left inferior frontal gyrus, temporal regions, and the visual word form area (VWFA). Further investigation of the activity in visual regions revealed overall deactivation relative to baseline rest for both attention conditions. Topographic analysis demonstrated that while attending to melody drove deactivation equivalently across all fusiform regions of interest examined, attending to speech produced a regionally specific modulation: deactivation of all fusiform regions, except the VWFA. Results indicate that selective attention to speech can topographically tune extrastriate cortex, leading to increased activity in VWFA relative to surrounding regions, in line with the well-established connectivity between areas related to spoken and visual word perception in skilled readers.

  4. Oxygen isotope effects as probes of electron transfer mechanisms and structures of activated O2.

    PubMed

    Roth, Justine P

    2009-03-17

    Competitively determined oxygen ((18)O) isotope effects can be powerful probes of chemical and biological transformations involving molecular oxygen as well as superoxide and hydrogen peroxide. They play a complementary role to crystallography and spectroscopy in the study of activated oxygen intermediates by forging a link between electronic/vibrational structure and the bonding that occurs within ground and transition states along the reaction coordinate. Such analyses can be used to assess the plausibility of intermediates and their catalytic relevance in oxidative processes. This Account describes efforts to advance oxygen kinetic isotope effects ((18)O KIEs) and equilibrium isotope effects ((18)O EIEs) as mechanistic probes of reactive, oxygen-derived species. We focus primarily on transition metal mediated oxidations, outlining both advances over the past five years and current limitations of this approach. Computational methods are now being developed to probe transition states and the accompanying kinetic isotope effects. In particular, we describe the importance of using a full-frequency model to accurately predict the magnitudes as well as the temperature dependence of the isotope effects. Earlier studies have used a "cut-off model," which employs only a few isotopic vibrational modes, and such models tend to overestimate (18)O EIEs. Researchers in mechanistic biological inorganic chemistry would like to differentiate "inner-sphere" from "outer-sphere" reactivity of O(2), a designation that describes the extent of the bonding interaction between metal and oxygen in the transition state. Though this problem remains unsolved, we expect that this isotopic approach will help differentiate these processes. For example, comparisons of (18)O KIEs to (18)O EIEs provide benchmarks that allow us to calibrate computationally derived reaction coordinates. Once the physical origins of heavy atom isotope effects are better understood, researchers will be able to apply

  5. Reactive Oxygen Species Production by Potato Tuber Mitochondria Is Modulated by Mitochondrially Bound Hexokinase Activity1

    PubMed Central

    Camacho-Pereira, Juliana; Meyer, Laudiene Evangelista; Machado, Lilia Bender; Oliveira, Marcus Fernandes; Galina, Antonio

    2009-01-01

    Potato tuber (Solanum tuberosum) mitochondria (PTM) have a mitochondrially bound hexokinase (HK) activity that exhibits a pronounced sensitivity to ADP inhibition. Here we investigated the role of mitochondrial HK activity in PTM reactive oxygen species generation. Mitochondrial HK has a 10-fold higher affinity for glucose (Glc) than for fructose (KMGlc = 140 μm versus KMFrc = 1,375 μm). Activation of PTM respiration by succinate led to an increase in hydrogen peroxide (H2O2) release that was abrogated by mitochondrial HK activation. Mitochondrial HK activity caused a decrease in the mitochondrial membrane potential and an increase in oxygen consumption by PTM. Inhibition of Glc phosphorylation by mannoheptulose or GlcNAc induced a rapid increase in H2O2 release. The blockage of H2O2 release sustained by Glc was reverted by oligomycin and atractyloside, indicating that ADP recycles through the adenine nucleotide translocator and F0F1ATP synthase is operative during the mitochondrial HK reaction. Inhibition of mitochondrial HK activity by 60% to 70% caused an increase of 50% in the maximal rate of H2O2 release. Inhibition in H2O2 release by mitochondrial HK activity was comparable to, or even more potent, than that observed for StUCP (S. tuberosum uncoupling protein) activity. The inhibition of H2O2 release in PTM was two orders of magnitude more selective for the ADP produced from the mitochondrial HK reaction than for that derived from soluble yeast (Saccharomyces cerevisiae) HK. Modulation of H2O2 release and oxygen consumption by Glc and mitochondrial HK inhibitors in potato tuber slices shows that hexoses and mitochondrial HK may act as a potent preventive antioxidant mechanism in potato tubers. PMID:19109413

  6. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    NASA Astrophysics Data System (ADS)

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  7. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    DOE PAGES

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore » structures have the highest calculated activity to date.« less

  8. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    SciTech Connect

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  9. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    PubMed Central

    Holby, Edward F.; Taylor, Christopher D.

    2015-01-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date. PMID:25788358

  10. Selective nitrogen doping in graphene: Enhanced catalytic activity for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Huang, Sheng-Feng; Terakura, Kiyoyuki; Boero, Mauro; Oshima, Masaharu; Kakimoto, Masa-Aki; Miyata, Seizo

    2011-12-01

    The structural and electronic properties of N-doped zigzag graphene ribbons with various ratios of dihydrogenated to monohydrogenated edge carbons are investigated within the density functional theory framework. We find that the stability of graphitic N next to the edge, which is claimed to play important roles in the catalytic activity in our previous work, will be enhanced with increasing the concentration of dihydrogenated carbons. Furthermore, the dihydrogenated edge carbons turn out to be easily converted into monohydrogenated ones in the presence of oxygen molecules at room temperature. Based on our results, we propose a possible way to enhance the oxygen reduction catalytic activity of N-doped graphene by controlling the degrees of hydrogenation of edge carbons. The characteristic features in the x-ray absorption and emission spectra for each specific N site considered here will also be given.

  11. Adsorption of phenolics on activated carbon--impact of pore size and molecular oxygen.

    PubMed

    Lu, Qiuli; Sorial, George A

    2004-05-01

    The impact of pore size of activated carbon fibers (ACFs) on adsorption capacity and on the potential for oligomerization of phenolic compounds on the surface of ACFs in the presence of molecular oxygen has been investigated in this study. Compared with granular activated carbon (GAC), ACFs have unique pore size distributions, suitable to be used to elucidate the effect of pore structure on adsorption. Adsorption isotherm data were collected for o-cresol and 2-ethylphenol on four ACFs (ACC-10, ACC-15, ACC-20, and ACC-25) with different micropore volumes and BET surface area and on one type of GAC bituminous base. These isotherms were collected under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions. No significant impact of the presence of molecular oxygen on adsorption capacity was noted for ACC-10. ACC-10 has an average pore width of 19.2 A and total pore volume of 0.43 cm3g(-1). On the other hand, for the remaining ACFs, which have larger average pore width and larger pore volume, significant increase in the adsorptive capacity had been observed when molecular oxygen was present. The GAC gave the greatest difference between anoxic and oxic conditions when compared to all the ACFs studied. Binary adsorption of o-cresol and 2-ethylphenol on ACFs with the least pore size (ACC-10) also showed no significant differences between oxic and anoxic environment. The binary system under both anoxic and oxic conditions was well predicted by the ideal adsorbed solution theory (IAST).

  12. Structure and Form. Elementary Science Activity Series, Volume 2.

    ERIC Educational Resources Information Center

    Blackwell, Frank F.

    This book is number 2 of a series of elementary science books that presents a wealth of ideas for science activities for the elementary school teacher. Each activity includes a standard set of information designed to help teachers determine the activity's appropriateness for their students, plan its implementation, and help children focus on a…

  13. Reactive oxygen and nitrogen species in defense/stress responses activated by chitosan in sycamore cultured cells.

    PubMed

    Malerba, Massimo; Cerana, Raffaella

    2015-01-29

    Chitosan (CHT) is a non-toxic and inexpensive compound obtained by deacetylation of chitin, the main component of the exoskeleton of arthropods as well as of the cell walls of many fungi. In agriculture CHT is used to control numerous diseases on various horticultural commodities but, although different mechanisms have been proposed, the exact mode of action of CHT is still unknown. In sycamore (Acer pseudoplatanus L.) cultured cells, CHT induces a set of defense/stress responses that includes production of H2O2 and nitric oxide (NO). We investigated the possible signaling role of these reactive molecules in some CHT-induced responses by means of inhibitors of production and/or scavengers. The results show that both reactive nitrogen and oxygen species are not only a mere symptom of stress conditions but are involved in the responses induced by CHT in sycamore cells. In particular, NO appears to be involved in a cell death form induced by CHT that shows apoptotic features like DNA fragmentation, increase in caspase-3-like activity and release of cytochrome c from the mitochondrion. On the contrary, reactive oxygen species (ROS) appear involved in a cell death form induced by CHT that does not show these apoptotic features but presents increase in lipid peroxidation.

  14. Reactive oxygen and nitrogen species in defense/stress responses activated by chitosan in sycamore cultured cells.

    PubMed

    Malerba, Massimo; Cerana, Raffaella

    2015-01-01

    Chitosan (CHT) is a non-toxic and inexpensive compound obtained by deacetylation of chitin, the main component of the exoskeleton of arthropods as well as of the cell walls of many fungi. In agriculture CHT is used to control numerous diseases on various horticultural commodities but, although different mechanisms have been proposed, the exact mode of action of CHT is still unknown. In sycamore (Acer pseudoplatanus L.) cultured cells, CHT induces a set of defense/stress responses that includes production of H2O2 and nitric oxide (NO). We investigated the possible signaling role of these reactive molecules in some CHT-induced responses by means of inhibitors of production and/or scavengers. The results show that both reactive nitrogen and oxygen species are not only a mere symptom of stress conditions but are involved in the responses induced by CHT in sycamore cells. In particular, NO appears to be involved in a cell death form induced by CHT that shows apoptotic features like DNA fragmentation, increase in caspase-3-like activity and release of cytochrome c from the mitochondrion. On the contrary, reactive oxygen species (ROS) appear involved in a cell death form induced by CHT that does not show these apoptotic features but presents increase in lipid peroxidation. PMID:25642757

  15. A General Method for Multimetallic Platinum Alloy Nanowires as Highly Active and Stable Oxygen Reduction Catalysts.

    PubMed

    Bu, Lingzheng; Ding, Jiabao; Guo, Shaojun; Zhang, Xu; Su, Dong; Zhu, Xing; Yao, Jianlin; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2015-11-25

    An unconventional class of high-performance Pt alloy multimetallic nanowires (NWs) is produced by a general method. The obtained PtNi NWs exhibit amazingly specific and mass oxygen reduction reaction (ORR) activities with improvement factors of 51.1 and 34.6 over commercial Pt/C catalysts, respectively, and are also stable in ORR conditions, making them among the most efficient electrocatalysts for ORR.

  16. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

    NASA Astrophysics Data System (ADS)

    von Sperber, C.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

    2015-07-01

    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking

  17. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

    NASA Astrophysics Data System (ADS)

    Sperber, C. v.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

    2015-03-01

    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields plant available inorganic phosphate (Pi) and less phosphorylated inositol derivates as products. The hydrolysis of organic P-compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as substrate were prepared. During the hydrolysis of IP6 by phytase, four Pi are released, and one oxygen atom from water is incorporated into each Pi. This incorporation of oxygen from water into Pi is subject to an apparent inverse isotopic fractionation (ϵ ∼ 6 to 10‰), which is similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ∼ 7‰) where less than three Pi are released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ∼ -12‰), again similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ɛ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking substrate-dependency of

  18. Increased levels of peroxisomal active oxygen-related enzymes in copper-tolerant pea plants

    SciTech Connect

    Palma, J.M.; Gomez, M.; Yanez, J.; Del Rio, L.A.

    1987-10-01

    The effect in vivo of high nutrient levels of copper (240 micromolar) on the activity of different metalloenzymes containing Cu, Mn, Fe, and Zn, distributed in chloroplasts, peroxisomes, and mitochondria, was studied in leaves of two varieties of Pisum sativum L. plants with different sensitivity to copper. The metalloenzymes studied were: cytochrome c oxidase, Mn-superoxide dismutase (Mn-SOD) and Cu,Zn-superoxide dismutase I (Cu,Zn-SOD I), for mitochondria; catalase and Mn-SOD, for peroxisomes; and isozyme Cu,Zn-SOD II for chloroplasts. The activity of mitochondrial SOD isozymes (Mn-SOD and Cu,Zn-SOD I) was very similar in Cu-tolerant and Cu-sensitive plants, whereas cytochrome c oxidase was lower in Cu-sensitive plants. Chloroplastid Cu,Zn-SOD activity was the same in the two plant varieties. In contrast, the peroxisomal Mn-SOD activity was considerably higher in Cu-tolerant than in Cu-sensitive plants, and the activity of catalase was also increased in peroxisomes of Cu-tolerant plants. The higher activities of these peroxisomal active oxygen-related enzymes in Cu-tolerant plants suggest the involvement of reactive oxygen intermediates (O/sub 2//sup -/, OH) in the mechanism of Cu lethality, and also imply a function for peroxisomal Mn-SOD in the molecular mechanisms of plant tolerance to Cu in Pisum sativum L.

  19. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    NASA Astrophysics Data System (ADS)

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  20. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    PubMed Central

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  1. Enhanced oxygen evolution activity of IrO2 and RuO2 (100) surfaces

    SciTech Connect

    Stoerzinger, Kelsey; Qiao, Liang; Biegalski, Michael D; Christen, Hans M; Shao-Horn, Yang

    2014-01-01

    The activities of the oxygen evolution reaction (OER) on IrO2 and RuO2 catalysts are among the highest known to date. However, the intrinsic OER activities of surfaces with defined crystallographic orientations are not well established experimentally. Here we report that the (100) surface of IrO2 and RuO2 is more active than the (110) surface that has been traditionally explored by density functional theory studies. The relation between the OER activity and density of coordinatively undersaturated metal sites exposed on each rutile crystallographic facet is discussed. The surface-orientation dependent activities can guide the design of high-surface-area catalysts with increased activity for electrolyzers, metal-air batteries, and photoelectrochemical water splitting applications.

  2. 76 FR 13699 - Reports, Forms and Recordkeeping Requirements Information Collection Activity Under OMB Review

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-14

    ..., companies chartering ships from MARAD, and companies having Title XI guarantee obligations. Form(s): MA-172... TRANSPORTATION Maritime Administration Reports, Forms and Recordkeeping Requirements Information Collection Activity Under OMB Review AGENCY: Maritime Administration, DOT. ACTION: Notice and request for...

  3. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction.

    PubMed

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-01-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm(-2)) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

  4. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-09-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

  5. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction.

    PubMed

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-01-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm(-2)) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst. PMID:25229121

  6. Adsorption of cadmium ions on oxygen surface sites in activated carbon

    SciTech Connect

    Jia, Y.F.; Thomas, K.M.

    2000-02-08

    Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon by oxidation using nitric acid. Fourier-transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), and selective neutralization were used to characterize the surface oxygen functional groups. The oxidized carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stabilities were varied progressively. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released protons to adsorbed cadmium ions on oxidized carbon was approximately 2, indicating cation exchange was involved in the process of adsorption. Na{sup +} exchange studies with the oxidized carbon gave a similar ratio. After heat treatment of the oxidized carbons to remove oxygen functional groups, the ratio of H{sup +} released to Cd{sup 2+} adsorbed and the adsorption capacity decreased significantly. Both reversible and irreversible processes were involved in cadmium ion adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups, whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion.

  7. Improvement of photocatalytic activity of silver nanoparticles by radio frequency oxygen plasma irradiation

    NASA Astrophysics Data System (ADS)

    Fang, Yingcui; Zhang, Bing; Hong, Liu; Yao, Damao; Xie, Zhiqiang; Jiang, Yang

    2015-07-01

    Photocatalytic activity (PA) of silver nanoparticles (AgNPs) induced by radio frequency (RF) oxygen plasma irradiation (OPI) is investigated in this paper. An improvement in PA by 365% and 181% has been achieved when 15 nm AgNPs irradiated by oxygen plasma for 2 s were used to degrade 10-5 M Rhodamine 6 G (R6G) under ultraviolet (UV) and visible lights, respectively. The PA caused by OPI is better than that induced by the localized surface plasma resonance (LSPR) of AgNPs. The mechanism for the improvement was explored by scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectra. The OPI-induced formation of AgO/AgNP and Ag2O/AgNP-heterogeneous photocatalysts and electrophilic oxygen are considered to be responsible for the PA improvement. This investigation deepens our understanding of oxygen-assisted photocatalysis of AgNPs and provides a practical approach using solar light for broad spectra photocatalysis with high efficiency.

  8. Adair-based hemoglobin equilibrium with oxygen, carbon dioxide and hydrogen ion activity.

    PubMed

    Mateják, Marek; Kulhánek, Tomáš; Matoušek, Stanislav

    2015-04-01

    As has been known for over a century, oxygen binding onto hemoglobin is influenced by the activity of hydrogen ions (H⁺), as well as the concentration of carbon dioxide (CO₂). As is also known, the binding of both CO₂and H⁺ on terminal valine-1 residues is competitive. One-parametric situations of these hemoglobin equilibria at specific levels of H⁺, O₂or CO₂are also well described. However, we think interpolating or extrapolating this knowledge into an 'empirical' function of three independent variables has not yet been completely satisfactory. We present a model that integrates three orthogonal views of hemoglobin oxygenation, titration, and carbamination at different temperatures. The model is based only on chemical principles, Adair's oxygenation steps and Van't Hoff equation of temperature dependences. Our model fits the measurements of the Haldane coefficient and CO₂hemoglobin saturation. It also fits the oxygen dissociation curve influenced by simultaneous changes in H⁺, CO₂and O₂, which makes it a strong candidate for integration into more complex models of blood acid-base with gas transport, where any combination of mentioned substances can appear. PMID:25594800

  9. Adair-based hemoglobin equilibrium with oxygen, carbon dioxide and hydrogen ion activity.

    PubMed

    Mateják, Marek; Kulhánek, Tomáš; Matoušek, Stanislav

    2015-04-01

    As has been known for over a century, oxygen binding onto hemoglobin is influenced by the activity of hydrogen ions (H⁺), as well as the concentration of carbon dioxide (CO₂). As is also known, the binding of both CO₂and H⁺ on terminal valine-1 residues is competitive. One-parametric situations of these hemoglobin equilibria at specific levels of H⁺, O₂or CO₂are also well described. However, we think interpolating or extrapolating this knowledge into an 'empirical' function of three independent variables has not yet been completely satisfactory. We present a model that integrates three orthogonal views of hemoglobin oxygenation, titration, and carbamination at different temperatures. The model is based only on chemical principles, Adair's oxygenation steps and Van't Hoff equation of temperature dependences. Our model fits the measurements of the Haldane coefficient and CO₂hemoglobin saturation. It also fits the oxygen dissociation curve influenced by simultaneous changes in H⁺, CO₂and O₂, which makes it a strong candidate for integration into more complex models of blood acid-base with gas transport, where any combination of mentioned substances can appear.

  10. Microbial activities and phosphorus cycling: An application of oxygen isotope ratios in phosphate

    NASA Astrophysics Data System (ADS)

    Stout, Lisa M.; Joshi, Sunendra R.; Kana, Todd M.; Jaisi, Deb P.

    2014-08-01

    Microorganisms carry out biochemical transformations of nutrients that make up their cells. Therefore, understanding how these nutrients are transformed or cycled in natural environments requires knowledge of microbial activity. Commonly used indicators for microbial activity typically include determining microbial respiration by O2/CO2 measurements, cell counts, and measurement of enzyme activities. However, coupled studies on nutrient cycling and microbial activity are not given enough emphasis. Here we apply phosphate oxygen isotope ratios (δ18OP) as a tool for measurement of microbial activity and compare the rate of isotope exchange with methods of measuring microbial activities that are more commonly applied in environmental studies including respiration, dehydrogenase activity, alkaline phosphatase activity, and cell counts. Our results show that different bacteria may have different strategies for P uptake, storage and release, their respiration and consequently expression of DHA and APase activities, but in general the trend of their enzyme activities are comparable. Phosphate δ18OP values correlated well with these other parameters used to measure microbial activity with the strongest linear relationships between δ18OP and CO2 evolution (r = -0.99). Even though the rate of isotope exchange for each microorganism used in this study is different, the rate per unit CO2 respiration showed one general trend, where δ18OP values move towards equilibrium while CO2 is generated. While this suggests that P cycling among microorganisms used in this study can be generalized, further research is needed to determine whether the microorganism-specific isotope exchange trend may occur in natural environments. In summary, phosphate oxygen isotope measurements may offer an alternative for use as a tracer to measure microbial activity in soils, sediments, and many other natural environments.

  11. Oxygen activation and intramolecular C-H bond activation by an amidate-bridged diiron(II) complex.

    PubMed

    Jones, Matthew B; Hardcastle, Kenneth I; Hagen, Karl S; MacBeth, Cora E

    2011-07-18

    A diiron(II) complex containing two μ-1,3-(κN:κO)-amidate linkages has been synthesized using the 2,2',2''-tris(isobutyrylamido)triphenylamine (H(3)L(iPr)) ligand. The resulting diiron complex, 1, reacts with dioxygen (or iodosylbenzene) to effect intramolecular C-H bond activation at the methine position of the ligand isopropyl group. The ligand-activated product, 2, has been isolated and characterized by a variety of methods including X-ray crystallography. Electrospray ionization mass spectroscopy of 2 prepared from(18)O(2) was used to confirm that the oxygen atom incorporated into the ligand framework is derived from molecular oxygen.

  12. A cytosolic activator of DNA replication is tyrosine phosphorylated in its active form.

    PubMed

    Fresa, K L; Autieri, M V; Coffman, F D; Georgoff, I; Cohen, S

    1993-04-01

    Cytosolic extracts from actively dividing lymphoid cells have been shown to induce DNA synthesis in isolated, quiescent nuclei. An initiating factor in such extracts (activator of DNA replication; ADR) is a > 90-kDa aprotinin-binding protein whose activity is inhibitable not only by aprotinin, but also by several other protease inhibitors as well. Although cytosol from non-proliferating lymphocytes is devoid of ADR activity, we have shown that these preparations can be induced to express ADR activity by brief exposure to a membrane-enriched fraction of spontaneously proliferating MOLT-4 cells via a kinase-dependent mechanism. In the present study, we examine the role of tyrosine kinases in this process. Three inhibitors of tyrosine kinases (genistein, kaempferol, and quercetin) can inhibit the in vitro generation of ADR activity. In vitro generation of ADR activity is associated with the de novo phosphorylation of several proteins, many of which are detectable using anti-phosphotyrosine monoclonal antibodies. ADR itself may be tyrosine phosphorylated in active form as immunoprecipitation using such monoclonal antibodies leads to the depletion of its activity. Moreover, immunoprecipitation results in the removal of several de novo tyrosine-phosphorylated proteins, including species at approximately 122, 105, 93, 86, 79, and 65 kDa. A subset of de novo-phosphorylated proteins, migrating at approximately 105, 93, and 70 kDa, also bound to aprotinin, suggesting that at least one of these proteins may represent ADR itself. PMID:7683270

  13. Enhancing effect of oxygen radical scavengers on murine macrophage anticryptococcal activity through production of nitric oxide

    PubMed Central

    TOHYAMA, M.; KAWAKAMI, K.; FUTENMA, M.; SAITO, A.

    1996-01-01

    We examined the roles of reactive nitrogen intermediates (RNI) and reactive oxygen intermediates (ROI) in interferon-gamma (IFN-γ)-induced cryptococcostatic activity of murine peritoneal macrophages using NG-monomethyl-L-arginine (L-NMMA), a competitive inhibitor of RNI synthesis, and superoxide dismutase (SOD) and catalase, oxygen radical scavengers. IFN-γ-activated macrophages produced nitric oxide (NO) in a dose-dependent manner, as measured by increased nitrite concentration in the culture supernatant. IFN-γ also enhanced the suppressive effect on cryptococcal growth in a similar dose-dependent manner. The induction of killing activity and NO production by an optimal dose of IFN-γ (100 U/ml) was virtually suppressed by 500 μM L-NMMA. These results confirmed the importance of the RNI-mediated effector mechanism in anticryptococcal activity of macrophages. SOD and catalase significantly enhanced the cryptococcostatic activity of macrophages induced by a suboptimal dose of IFN-γ (20 U/ml). The augmenting effect of these reagents was mediated by NO, since they potentiated the production of NO by macrophages and their effects were totally blocked by L-NMMA. Our results indicate that the IFN-γ-induced anticryptococcal activity of macrophages is dependent mostly on RNI, and suggest that the ROI system down-regulates the effector mechanism for cryptococcostasis by suppressing the RNI system. PMID:8608643

  14. STYPu fuel form activities, March 1-September 30, 1985

    SciTech Connect

    Not Available

    1986-01-01

    The SRP portion of this report summarizes production STYPuO2 fuel forms for use in radioisotopic thermoelectric generators (RTG's) in the Plutonium Fuel Form (PuFF) Facility at the Savannah River Plant. The PuFF Facility began producing iridium-encapsulated, 62.5-watt STYPuO2 right circular cylinders for GPHS (General Purpose Heat Source) RTG's in June 1980; this program was completed in December 1983. The PuFF Facility has been placed in a production readiness mode of operation pending funding of additional heat source programs.

  15. Function of reactive oxygen species during animal development: passive or active?

    PubMed

    Covarrubias, Luis; Hernández-García, David; Schnabel, Denhí; Salas-Vidal, Enrique; Castro-Obregón, Susana

    2008-08-01

    Oxidative stress is considered causal of aging and pathological cell death, however, very little is known about its function in the natural processes that support the formation of an organism. It is generally thought that cells must continuously protect themselves from the possible damage caused by reactive oxygen species (ROS) (passive ROS function). However, presently, ROS are recognized as physiologically relevant molecules that mediate cell responses to a variety of stimuli, and the activities of several molecules, some developmentally relevant, are directly or indirectly regulated by oxidative stress (active ROS function). Here we review recent data that are suggestive of specific ROS functions during development of animals, particularly mammals.

  16. Reactive oxygen species and antioxidant enzymes activity of Anabaena sp. PCC 7120 (Cyanobacterium) under simulated microgravity

    NASA Astrophysics Data System (ADS)

    Li, Gen-bao; Liu, Yong-ding; Wang, Gao-hong; Song, Li-rong

    2004-12-01

    It was found that reactive oxygen species in Anabaena cells increased under simulated microgravity provided by clinostat. Activities of intracellular antioxidant enzymes, such as superoxide dismutase, catalase were higher than those in the controlled samples during the 7 days' experiment. However, the contents of gluathione, an intracellular antioxidant, decreased in comparison with the controlled samples. The results suggested that microgravity provided by clinostat might break the oxidative/antioxidative balance. It indicated a protective mechanism in algal cells, that the total antioxidant system activity increased, which might play an important role for algal cells to adapt the environmental stress of microgravity.

  17. Active-medium inhomogeneities and optical quality of radiation of supersonic chemical oxygen-iodine lasers

    SciTech Connect

    Boreysho, A S; Druzhinin, S L; Lobachev, V V; Savin, A V; Strakhov, S Yu; Trilis, A V

    2007-09-30

    Optical inhomogeneities of the active medium of a supersonic chemical oxygen-iodine laser (COIL) and their effect on the radiation parameters are studied in the case when an unstable resonator is used. Classification of optical inhomogeneities and the main factors affecting the quality of COIL radiation are considered. The results of numerical simulation of a three-dimensional gas-dynamic active medium and an unstable optical resonator in the diffraction approximation are presented. The constraints in the fabrication of large-scale COILs associated with a deterioration of the optical quality of radiation are determined. (lasers)

  18. Pt5Gd as a highly active and stable catalyst for oxygen electroreduction.

    PubMed

    Escudero-Escribano, María; Verdaguer-Casadevall, Arnau; Malacrida, Paolo; Grønbjerg, Ulrik; Knudsen, Brian P; Jepsen, Anders K; Rossmeisl, Jan; Stephens, Ifan E L; Chorkendorff, Ib

    2012-10-10

    The activity and stability of Pt(5)Gd for the oxygen reduction reaction (ORR) have been studied, using a combination of electrochemical measurements, angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and density functional theory calculations. Sputter-cleaned, polycrystalline Pt(5)Gd shows a 5-fold increase in ORR activity, relative to pure Pt at 0.9 V, approaching the most active in the literature for catalysts prepared in this way. AR-XPS profiles after electrochemical measurements in 0.1 M HClO(4) show the formation of a thick Pt overlayer on the bulk Pt(5)Gd, and the enhanced ORR activity can be explained by means of compressive strain effects. Furthermore, these novel bimetallic electrocatalysts are highly stable, which, in combination with their enhanced activity, makes them very promising for the development of new cathode catalysts for fuel cells. PMID:22998588

  19. Evidence that reactive oxygen species do not mediate NF-κB activation

    PubMed Central

    Hayakawa, Makio; Miyashita, Hiroshi; Sakamoto, Isao; Kitagawa, Masatoshi; Tanaka, Hirofumi; Yasuda, Hideyo; Karin, Michael; Kikugawa, Kiyomi

    2003-01-01

    It has been postulated that reactive oxygen species (ROS) may act as second messengers leading to nuclear factor (NF)-κB activation. This hypothesis is mainly based on the findings that N-acetyl-l-cysteine (NAC) and pyrrolidine dithiocarbamate (PDTC), compounds recognized as potential antioxidants, can inhibit NF-κB activation in a wide variety of cell types. Here we reveal that both NAC and PDTC inhibit NF-κB activation independently of antioxidative function. NAC selectively blocks tumor necrosis factor (TNF)-induced signaling by lowering the affinity of receptor to TNF. PDTC inhibits the IκB–ubiquitin ligase activity in the cell-free system where extracellular stimuli-regulated ROS production does not occur. Furthermore, we present evidence that endogenous ROS produced through Rac/NADPH oxidase do not mediate NF-κB signaling, but instead lower the magnitude of its activation. PMID:12839997

  20. Coupling of total hemoglobin concentration, oxygenation, and neural activity in rat somatosensory cortex.

    PubMed

    Devor, Anna; Dunn, Andrew K; Andermann, Mark L; Ulbert, Istvan; Boas, David A; Dale, Anders M

    2003-07-17

    Recent advances in brain imaging techniques, including functional magnetic resonance imaging (fMRI), offer great promise for noninvasive mapping of brain function. However, the indirect nature of the imaging signals to the underlying neural activity limits the interpretation of the resulting maps. The present report represents the first systematic study with sufficient statistical power to quantitatively characterize the relationship between changes in blood oxygen content and the neural spiking and synaptic activity. Using two-dimensional optical measurements of hemodynamic signals, simultaneous recordings of neural activity, and an event-related stimulus paradigm, we demonstrate that (1) there is a strongly nonlinear relationship between electrophysiological measures of neuronal activity and the hemodynamic response, (2) the hemodynamic response continues to grow beyond the saturation of electrical activity, and (3) the initial increase in deoxyhemoglobin that precedes an increase in blood volume is counterbalanced by an equal initial decrease in oxyhemoglobin. PMID:12873390

  1. Transcript levels of antioxidative genes and oxygen radical scavenging enzyme activities in chilled zucchini squash in response to superatmospheric oxygen

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The transcript levels of antioxidative genes including Mn-superoxide dismutase (Mn-SOD), Cu/Zn SOD, ascorbate peroxidise (APX), and catalase (CAT) do not vary significantly during storage at 5 °C with high oxygen treatment in freshly harvested zucchini squash (Cucurbita pepo L. cv. Elite). However, ...

  2. The fate of hydrogen peroxide as an oxygen source for bioremediation activities within saturated aquifer systems.

    PubMed

    Zappi, M; White, K; Hwang, H M; Bajpai, R; Qasim, M

    2000-10-01

    In situ bioremediation is an innovative technique for the remediation of contaminated aquifers that involves the use of microorganisms to remediate soils and groundwaters polluted by hazardous substances. During its application, this process may require the addition of nutrients and/or electron acceptors to stimulate appropriate biological activity. Hydrogen peroxide has been commonly used as an oxygen source because of the limited concentrations of oxygen that can be transferred into the groundwater using above-ground aeration followed by reinjection of the oxygenated groundwater into the aquifer or subsurface air sparging of the aquifer. Because of several potential interactions of H2O2 with various aquifer material constituents, its decomposition may be too rapid, making effective introduction of the H2O2 into targeted treatment zones extremely difficult and costly. Therefore, a bench-scale study was conducted to determine the fate of H2O2 within subsurface aquifer environments. The purpose of this investigation was to identify those aquifer constituents, both biotic and abiotic, that are most active in controlling the fate of H2O2. The decomposition rates of H2O2 were determined using both equilibrated water samples and soil slurries. Results showed H2O2 decomposition to be effected by several commonly found inorganic soil components; however, biologically mediated catalytic reactions were determined to be the most substantial.

  3. Composition-controlled PtCo alloy nanocubes with tuned electrocatalytic activity for oxygen reduction.

    PubMed

    Choi, Sang-Il; Lee, Su-Un; Kim, Woo Youn; Choi, Ran; Hong, Kwangwoo; Nam, Ki Min; Han, Sang Woo; Park, Joon T

    2012-11-01

    Modification of the electronic structure and lattice contraction of Pt alloy nanocatalysts through control over their morphology and composition has been a crucial issue for improving their electrocatalytic oxygen reduction reaction (ORR) activity. In the present work, we synthesized PtCo alloy nanocubes with controlled compositions (Pt(x)Co NCs, x = 2, 3, 5, 7, and 9) by regulating the ratio of surfactants and the amount of Co precursor to elucidate the effect of the composition of nanocatalysts on their ORR activity. Pt(x)Co NCs had a Pt-skin structure after electrochemical treatment. The electrocatalysis experiments revealed a strong correlation between ORR activity and Co composition. Pt₃Co NCs exhibited the best ORR performance among the various Pt(x)Co NCs. From density functional theory calculations, a typical volcano-type relationship was established between ORR activity and oxygen binding energy (E(OB)) on NC surfaces, which showed that Pt₃Co NCs had the optimal E(OB) to achieve the maximum ORR activity. X-ray photoelectron spectroscopy and X-ray diffraction measurements demonstrated that the electronic structure and lattice contraction of the Pt(x)Co NCs could be tuned by controlling the composition of NCs, which are highly correlated with the trends of E(OB) change.

  4. Design Insights for Tuning the Electrocatalytic Activity of Perovskite Oxides for the Oxygen Evolution Reaction

    SciTech Connect

    Malkhandi, S; Trinh, P; Manohar, AK; Manivannan, A; Balasubramanian, M; Prakash, GKS; Narayanan, SR

    2015-04-16

    Rechargeable metal-air batteries and water electrolyzers based on aqueous alkaline electrolytes hold the potential to be sustainable solutions to address the challenge of storing large amounts of electrical energy generated from solar and wind resources. For these batteries and electrolyzers to be economically viable, it is essential to have efficient, durable, and inexpensive electrocatalysts for the oxygen evolution reaction. In this article, we describe new insights for predicting and tuning the activity of inexpensive transition metal oxides for designing efficient and inexpensive electrocatalysts. We have focused on understanding the factors determining the electrocatalytic activity for oxygen evolution in a strong alkaline medium. To this end, we have conducted a systematic investigation of nanophase calcium-doped lanthanum cobalt manganese oxide, an example of a mixed metal oxide that can be tuned for its electrocatalytic activity by varying the transition metal composition. Using X-ray absorption spectroscopy (XANES), X-ray photoelectron spectroscopy (XPS), electrochemical polarization experiments, and analysis of mechanisms, we have identified the key determinants of electrocatalytic activity. We have found that the Tafel slopes are determined by the oxidation states and the bond energy of the surface intermediates of Mn-OH and Co-OH bonds while the catalytic activity increased with the average d-electron occupancy of the sigma* orbital of the M-OH bond. We anticipate that such understanding will be very useful in predicting the behavior of other transition metal oxide catalysts.

  5. Enhancing Electrocatalytic Oxygen Reduction on Nitrogen-Doped Graphene by Active Sites Implantation

    PubMed Central

    Feng, Leiyu; Yang, Lanqin; Huang, Zujing; Luo, Jingyang; Li, Mu; Wang, Dongbo; Chen, Yinguang

    2013-01-01

    The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology. PMID:24264379

  6. Enhancing Electrocatalytic Oxygen Reduction on Nitrogen-Doped Graphene by Active Sites Implantation

    NASA Astrophysics Data System (ADS)

    Feng, Leiyu; Yang, Lanqin; Huang, Zujing; Luo, Jingyang; Li, Mu; Wang, Dongbo; Chen, Yinguang

    2013-11-01

    The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology.

  7. Developing mononuclear copper-active-oxygen complexes relevant to reactive intermediates of biological oxidation reactions.

    PubMed

    Itoh, Shinobu

    2015-07-21

    Active-oxygen species generated on a copper complex play vital roles in several biological and chemical oxidation reactions. Recent attention has been focused on the reactive intermediates generated at the mononuclear copper active sites of copper monooxygenases such as dopamine β-monooxygenase (DβM), tyramine β-monooxygenase (TβM), peptidylglycine-α-hydroxylating monooxygenase (PHM), and polysaccharide monooxygenases (PMO). In a simple model system, reaction of O2 and a reduced copper(I) complex affords a mononuclear copper(II)-superoxide complex or a copper(III)-peroxide complex, and subsequent H(•) or e(-)/H(+) transfer, which gives a copper(II)-hydroperoxide complex. A more reactive species such as a copper(II)-oxyl radical type species could be generated via O-O bond cleavage of the peroxide complex. However, little had been explored about the chemical properties and reactivity of the mononuclear copper-active-oxygen complexes due to the lack of appropriate model compounds. Thus, a great deal of effort has recently been made to develop efficient ligands that can stabilize such reactive active-oxygen complexes in synthetic modeling studies. In this Account, I describe our recent achievements of the development of a mononuclear copper(II)-(end-on)superoxide complex using a simple tridentate ligand consisting of an eight-membered cyclic diamine with a pyridylethyl donor group. The superoxide complex exhibits a similar structure (four-coordinate tetrahedral geometry) and reactivity (aliphatic hydroxylation) to those of a proposed reactive intermediate of copper monooxygenases. Systematic studies based on the crystal structures of copper(I) and copper(II) complexes of the related tridentate supporting ligands have indicated that the rigid eight-membered cyclic diamine framework is crucial for controlling the geometry and the redox potential, which are prerequisites for the generation of such a unique mononuclear copper(II)-(end-on)superoxide complex

  8. Tuning the surface oxygen concentration of {111} surrounded ceria nanocrystals for enhanced photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Younis, Adnan; Chu, Dewei; Kaneti, Yusuf Valentino; Li, Sean

    2015-12-01

    For oxide semiconductors, the morphology, particle size and oxygen vacancies are usually considered as key influential parameters for photocatalytic degradation of organic pollutants/dyes. It is widely accepted that cation doping not only modifies their phase and microstructures but also introduces variations in oxygen vacancy concentration. Herein, we report the fabrication of sub-10 nm sized pure and indium doped CeO2 nanocrystals (NCs) via a facile, green hydrothermal method for the investigation of photocatalytic activities. X-ray diffraction and transmission electron microscopy were employed to examine the crystal phase and morphology of the as-prepared nanocrystals. Raman and X-ray photoelectron spectroscopy techniques were implemented to investigate the presence and variations in oxygen vacancy concentration in un-doped and indium doped CeO2 nanocrystals. The photocatalytic activity results revealed that 10 at% doping is the optimal indium doping level to demonstrate superior dye removal efficiency (~40%) over un-doped and doped CeO2 NCs. Moreover, the 10% In-doped CeO2 nanocrystals expressed excellent cycling stability and superior photocatalytic performance toward other dye pollutants. Finally, on the basis of our findings, a possible photocatalytic mechanism in which indium doping can generate more surface oxygen vacancies in the ceria lattice which delay the electron-hole recombination rates, thus increasing the lifetime of electron-hole separation for enhanced photocatalytic performances was proposed.For oxide semiconductors, the morphology, particle size and oxygen vacancies are usually considered as key influential parameters for photocatalytic degradation of organic pollutants/dyes. It is widely accepted that cation doping not only modifies their phase and microstructures but also introduces variations in oxygen vacancy concentration. Herein, we report the fabrication of sub-10 nm sized pure and indium doped CeO2 nanocrystals (NCs) via a facile

  9. Oxygen deficient ZnO1-x nanosheets with high visible light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Guo, Hong-Li; Zhu, Qing; Wu, Xi-Lin; Jiang, Yi-Fan; Xie, Xiao; Xu, An-Wu

    2015-04-01

    Zinc oxide is one of the most important wide-band-gap (3.2 eV) materials with versatile properties, however, it can not be excited by visible light. In this work, we have developed an exquisite and simple way to prepare oxygen-deficient ZnO1-x nanosheets with a gray-colored appearance and excellent visible light photocatalytic activity. Detailed analysis based on UV-Vis absorption spectra, X-band electron paramagnetic resonance (EPR) spectra, and photoluminescence (PL) spectra confirms the existence of oxygen vacancies in ZnO1-x. The incorporation of oxygen defects could effectively extend the light absorption of ZnO1-x into the visible-light region due to the fact that the energy of the localized state is located in the forbidden gap. Thus, our obtained ZnO1-x shows a higher photodegradation of methyl orange (MO) compared to defect-free ZnO under visible light illumination. Additionally, the high content of &z.rad;OH radicals with a strong photo-oxidation capability over the ZnO1-x nanosheets significantly contributes to the improvement in the photocatalytic performance. Our oxygen deficient ZnO1-x sample shows a very high photocatalytic activity for the degradation of MO even after 5 cycles without any obvious decline. The results demonstrate that defect engineering is a powerful tool to enhance the optoelectronic and photocatalytic performances of nanomaterials.Zinc oxide is one of the most important wide-band-gap (3.2 eV) materials with versatile properties, however, it can not be excited by visible light. In this work, we have developed an exquisite and simple way to prepare oxygen-deficient ZnO1-x nanosheets with a gray-colored appearance and excellent visible light photocatalytic activity. Detailed analysis based on UV-Vis absorption spectra, X-band electron paramagnetic resonance (EPR) spectra, and photoluminescence (PL) spectra confirms the existence of oxygen vacancies in ZnO1-x. The incorporation of oxygen defects could effectively extend the light

  10. High performance electrodes in vanadium redox flow batteries through oxygen-enriched thermal activation

    NASA Astrophysics Data System (ADS)

    Pezeshki, Alan M.; Clement, Jason T.; Veith, Gabriel M.; Zawodzinski, Thomas A.; Mench, Matthew M.

    2015-10-01

    The roundtrip electrochemical energy efficiency is improved from 63% to 76% at a current density of 200 mA cm-2 in an all-vanadium redox flow battery (VRFB) by utilizing modified carbon paper electrodes in the high-performance no-gap design. Heat treatment of the carbon paper electrodes in a 42% oxygen/58% nitrogen atmosphere increases the electrochemically wetted surface area from 0.24 to 51.22 m2 g-1, resulting in a 100-140 mV decrease in activation overpotential at operationally relevant current densities. An enriched oxygen environment decreases the amount of treatment time required to achieve high surface area. The increased efficiency and greater depth of discharge doubles the total usable energy stored in a fixed amount of electrolyte during operation at 200 mA cm-2.

  11. Reactive oxygen species in signalling the transcriptional activation of WIPK expression in tobacco.

    PubMed

    Xu, Juan; Yang, Kwang-Yeol; Yoo, Seung Jin; Liu, Yidong; Ren, Dongtao; Zhang, Shuqun

    2014-07-01

    Plant mitogen-activated protein kinases represented by tobacco WIPK (wounding-induced protein kinase) and its orthologs in other species are unique in their regulation at transcriptional level in response to stress and pathogen infection. We previously demonstrated that transcriptional activation of WIPK is essential for induced WIPK activity, and activation of salicylic acid-induced protein kinase (SIPK) by the constitutively active NtMEK2(DD) is sufficient to induce WIPK gene expression. Here, we report that the effect of SIPK on WIPK gene expression is mediated by reactive oxygen species (ROS). Using a combination of pharmacological and gain-of-function transgenic approaches, we studied the relationship among SIPK activation, WIPK gene activation in response to fungal cryptogein, light-dependent ROS generation in chloroplasts, and ROS generated via NADPH oxidase. In the conditional gain-of-function GVG-NtMEK2(DD) transgenic tobacco, induction of WIPK expression is dependent on the ROS generation in chloroplasts. Consistently, methyl viologen, an inducer of ROS generation in chloroplasts, highly activated WIPK expression. In addition to chloroplast-originated ROS, H(2)O(2) generated from the cell-surface NADPH oxidase could also activate WIPK gene expression, and inhibition of cryptogein-induced ROS generation also abolished WIPK gene activation. Our data demonstrate that WIPK gene activation is mediated by ROS, which provides a mechanism by which ROS influence cellular signalling processes in plant stress/defence response.

  12. EFFECT OF MOLECULAR OXYGEN ON THE ACTIVATED CARBON ADSORPTION OF NATURAL ORGANIC MATTER IN OHIO RIVER WATER

    EPA Science Inventory

    Recently published data show that the adsorptive capacity of granular activated carbon for phenois increases significantly in the presence of molecular oxygen (Vidic, Suidan,Traegner and Nakhla, 1990). in this study, the effect of molecular oxygen on the adsorptive capacity of a...

  13. Submaximal oxygen uptake kinetics, functional mobility, and physical activity in older adults with heart failure and reduced ejection fraction

    PubMed Central

    Hummel, Scott L; Herald, John; Alpert, Craig; Gretebeck, Kimberlee A; Champoux, Wendy S; Dengel, Donald R; Vaitkevicius, Peter V; Alexander, Neil B

    2016-01-01

    Background Submaximal oxygen uptake measures are more feasible and may better predict clinical cardiac outcomes than maximal tests in older adults with heart failure (HF). We examined relationships between maximal oxygen uptake, submaximal oxygen kinetics, functional mobility, and physical activity in older adults with HF and reduced ejection fraction. Methods Older adults with HF and reduced ejection fraction (n = 25, age 75 ± 7 years) were compared to 25 healthy age- and gender-matched controls. Assessments included a maximal treadmill test for peak oxygen uptake (VO2peak), oxygen uptake kinetics at onset of and on recovery from a submaximal treadmill test, functional mobility testing [Get Up and Go (GUG), Comfortable Gait Speed (CGS), Unipedal Stance (US)], and self-reported physical activity (PA). Results Compared to controls, HF had worse performance on GUG, CGS, and US, greater delays in submaximal oxygen uptake kinetics, and lower PA. In controls, VO2peak was more strongly associated with functional mobility and PA than submaximal oxygen uptake kinetics. In HF patients, submaximal oxygen uptake kinetics were similarly associated with GUG and CGS as VO2peak, but weakly associated with PA. Conclusions Based on their mobility performance, older HF patients with reduced ejection fraction are at risk for adverse functional outcomes. In this population, submaximal oxygen uptake measures may be equivalent to VO2 peak in predicting functional mobility, and in addition to being more feasible, may provide better insight into how aerobic function relates to mobility in older adults with HF. PMID:27594875

  14. Submaximal oxygen uptake kinetics, functional mobility, and physical activity in older adults with heart failure and reduced ejection fraction

    PubMed Central

    Hummel, Scott L; Herald, John; Alpert, Craig; Gretebeck, Kimberlee A; Champoux, Wendy S; Dengel, Donald R; Vaitkevicius, Peter V; Alexander, Neil B

    2016-01-01

    Background Submaximal oxygen uptake measures are more feasible and may better predict clinical cardiac outcomes than maximal tests in older adults with heart failure (HF). We examined relationships between maximal oxygen uptake, submaximal oxygen kinetics, functional mobility, and physical activity in older adults with HF and reduced ejection fraction. Methods Older adults with HF and reduced ejection fraction (n = 25, age 75 ± 7 years) were compared to 25 healthy age- and gender-matched controls. Assessments included a maximal treadmill test for peak oxygen uptake (VO2peak), oxygen uptake kinetics at onset of and on recovery from a submaximal treadmill test, functional mobility testing [Get Up and Go (GUG), Comfortable Gait Speed (CGS), Unipedal Stance (US)], and self-reported physical activity (PA). Results Compared to controls, HF had worse performance on GUG, CGS, and US, greater delays in submaximal oxygen uptake kinetics, and lower PA. In controls, VO2peak was more strongly associated with functional mobility and PA than submaximal oxygen uptake kinetics. In HF patients, submaximal oxygen uptake kinetics were similarly associated with GUG and CGS as VO2peak, but weakly associated with PA. Conclusions Based on their mobility performance, older HF patients with reduced ejection fraction are at risk for adverse functional outcomes. In this population, submaximal oxygen uptake measures may be equivalent to VO2 peak in predicting functional mobility, and in addition to being more feasible, may provide better insight into how aerobic function relates to mobility in older adults with HF.

  15. Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

    SciTech Connect

    Lim, B.; Tao, J.; Jiang, M.; Camargo, P.H.C.; Cho, E.C.; Lu, X.; Zhu, Y.; Xia, Y.

    2009-06-05

    Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K{sub 2}PtCl{sub 4} with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

  16. Structural Basis for Oxygen Activation at a Heterodinuclear Manganese/Iron Cofactor.

    PubMed

    Griese, Julia J; Kositzki, Ramona; Schrapers, Peer; Branca, Rui M M; Nordström, Anders; Lehtiö, Janne; Haumann, Michael; Högbom, Martin

    2015-10-16

    Two recently discovered groups of prokaryotic di-metal carboxylate proteins harbor a heterodinuclear Mn/Fe cofactor. These are the class Ic ribonucleotide reductase R2 proteins and a group of oxidases that are found predominantly in pathogens and extremophiles, called R2-like ligand-binding oxidases (R2lox). We have recently shown that the Mn/Fe cofactor of R2lox self-assembles from Mn(II) and Fe(II) in vitro and catalyzes formation of a tyrosine-valine ether cross-link in the protein scaffold (Griese, J. J., Roos, K., Cox, N., Shafaat, H. S., Branca, R. M., Lehtiö, J., Gräslund, A., Lubitz, W., Siegbahn, P. E., and Högbom, M. (2013) Proc. Natl. Acad. Sci. U.S.A. 110, 17189-17194). Here, we present a detailed structural analysis of R2lox in the nonactivated, reduced, and oxidized resting Mn/Fe- and Fe/Fe-bound states, as well as the nonactivated Mn/Mn-bound state. X-ray crystallography and x-ray absorption spectroscopy demonstrate that the active site ligand configuration of R2lox is essentially the same regardless of cofactor composition. Both the Mn/Fe and the diiron cofactor activate oxygen and catalyze formation of the ether cross-link, whereas the dimanganese cluster does not. The structures delineate likely routes for gated oxygen and substrate access to the active site that are controlled by the redox state of the cofactor. These results suggest that oxygen activation proceeds via similar mechanisms at the Mn/Fe and Fe/Fe center and that R2lox proteins might utilize either cofactor in vivo based on metal availability.

  17. Breakpoints in ventilation, cerebral and muscle oxygenation, and muscle activity during an incremental cycling exercise

    PubMed Central

    Racinais, Sebastien; Buchheit, Martin; Girard, Olivier

    2014-01-01

    The aim of this study was to locate the breakpoints of cerebral and muscle oxygenation and muscle electrical activity during a ramp exercise in reference to the first and second ventilatory thresholds. Twenty-five cyclists completed a maximal ramp test on an electromagnetically braked cycle-ergometer with a rate of increment of 25 W/min. Expired gazes (breath-by-breath), prefrontal cortex and vastus lateralis (VL) oxygenation [Near-infrared spectroscopy (NIRS)] together with electromyographic (EMG) Root Mean Square (RMS) activity for the VL, rectus femoris (RF), and biceps femoris (BF) muscles were continuously assessed. There was a non-linear increase in both cerebral deoxyhemoglobin (at 56 ± 13% of the exercise) and oxyhemoglobin (56 ± 8% of exercise) concomitantly to the first ventilatory threshold (57 ± 6% of exercise, p > 0.86, Cohen's d < 0.1). Cerebral deoxyhemoglobin further increased (87 ± 10% of exercise) while oxyhemoglobin reached a plateau/decreased (86 ± 8% of exercise) after the second ventilatory threshold (81 ± 6% of exercise, p < 0.05, d > 0.8). We identified one threshold only for muscle parameters with a non-linear decrease in muscle oxyhemoglobin (78 ± 9% of exercise), attenuation in muscle deoxyhemoglobin (80 ± 8% of exercise), and increase in EMG activity of VL (89 ± 5% of exercise), RF (82 ± 14% of exercise), and BF (85 ± 9% of exercise). The thresholds in BF and VL EMG activity occurred after the second ventilatory threshold (p < 0.05, d > 0.6). Our results suggest that the metabolic and ventilatory events characterizing this latter cardiopulmonary threshold may affect both cerebral and muscle oxygenation levels, and in turn, muscle recruitment responses. PMID:24782786

  18. Structural Basis for Oxygen Activation at a Heterodinuclear Manganese/Iron Cofactor*

    PubMed Central

    Griese, Julia J.; Kositzki, Ramona; Schrapers, Peer; Branca, Rui M. M.; Nordström, Anders; Lehtiö, Janne; Haumann, Michael; Högbom, Martin

    2015-01-01

    Two recently discovered groups of prokaryotic di-metal carboxylate proteins harbor a heterodinuclear Mn/Fe cofactor. These are the class Ic ribonucleotide reductase R2 proteins and a group of oxidases that are found predominantly in pathogens and extremophiles, called R2-like ligand-binding oxidases (R2lox). We have recently shown that the Mn/Fe cofactor of R2lox self-assembles from MnII and FeII in vitro and catalyzes formation of a tyrosine-valine ether cross-link in the protein scaffold (Griese, J. J., Roos, K., Cox, N., Shafaat, H. S., Branca, R. M., Lehtiö, J., Gräslund, A., Lubitz, W., Siegbahn, P. E., and Högbom, M. (2013) Proc. Natl. Acad. Sci. U.S.A. 110, 17189–17194). Here, we present a detailed structural analysis of R2lox in the nonactivated, reduced, and oxidized resting Mn/Fe- and Fe/Fe-bound states, as well as the nonactivated Mn/Mn-bound state. X-ray crystallography and x-ray absorption spectroscopy demonstrate that the active site ligand configuration of R2lox is essentially the same regardless of cofactor composition. Both the Mn/Fe and the diiron cofactor activate oxygen and catalyze formation of the ether cross-link, whereas the dimanganese cluster does not. The structures delineate likely routes for gated oxygen and substrate access to the active site that are controlled by the redox state of the cofactor. These results suggest that oxygen activation proceeds via similar mechanisms at the Mn/Fe and Fe/Fe center and that R2lox proteins might utilize either cofactor in vivo based on metal availability. PMID:26324712

  19. Chromophore structure of the physiologically active form (Pfr) of phytochrome

    PubMed Central

    Rüdiger, W.; Thümmler, F.; Cmiel, E.; Schneider, S.

    1983-01-01

    Chromopeptides were prepared by proteolytic digestion of phytochrome (far-red absorbing form, Pfr) and of phycocyanin. The phycocyanobilin peptide, the chromophore of which is Z,Z,Z-configurated, was modified to the Z,Z,E isomeric chromophore. It has been demonstrated earlier that the Pfr chromopeptide and the Z,Z,E-configurated phycocyanin chromopeptide behave similarly with regard to spectral and chromatographic properties and reactivity. We present evidence here, obtained by high-resolution 1H NMR spectroscopy, that both the modified phycocyanobilin chromophore and the phytochrome chromophore obtained directly from Pfr are 15E-configurated. PMID:16593380

  20. Reconstructing ecosystem functions of the active microbial community of the Baltic Sea oxygen depleted sediments

    PubMed Central

    Franzetti, Andrea; Lundin, Daniel; Sjöling, Sara

    2016-01-01

    Baltic Sea deep water and sediments hold one of the largest anthropogenically induced hypoxic areas in the world. High nutrient input and low water exchange result in eutrophication and oxygen depletion below the halocline. As a consequence at Landsort Deep, the deepest point of the Baltic Sea, anoxia in the sediments has been a persistent condition over the past decades. Given that microbial communities are drivers of essential ecosystem functions we investigated the microbial community metabolisms and functions of oxygen depleted Landsort Deep sediments by metatranscriptomics. Results show substantial expression of genes involved in protein metabolism demonstrating that the Landsort Deep sediment microbial community is active. Identified expressed gene suites of metabolic pathways with importance for carbon transformation including fermentation, dissimilatory sulphate reduction and methanogenesis were identified. The presence of transcripts for these metabolic processes suggests a potential for heterotrophic-autotrophic community synergism and indicates active mineralisation of the organic matter deposited at the sediment as a consequence of the eutrophication process. Furthermore, cyanobacteria, probably deposited from the water column, are transcriptionally active in the anoxic sediment at this depth. Results also reveal high abundance of transcripts encoding integron integrases. These results provide insight into the activity of the microbial community of the anoxic sediment at the deepest point of the Baltic Sea and its possible role in ecosystem functioning. PMID:26823996

  1. Reactive Oxygen Species in the Paraventricular Nucleus of the Hypothalamus Alter Sympathetic Activity During Metabolic Syndrome.

    PubMed

    Cruz, Josiane C; Flôr, Atalia F L; França-Silva, Maria S; Balarini, Camille M; Braga, Valdir A

    2015-01-01

    The paraventricular nucleus of the hypothalamus (PVN) contains heterogeneous populations of neurons involved in autonomic and neuroendocrine regulation. The PVN plays an important role in the sympathoexcitatory response to increasing circulating levels of angiotensin II (Ang-II), which activates AT1 receptors in the circumventricular organs (OCVs), mainly in the subfornical organ (SFO). Circulating Ang-II induces a de novo synthesis of Ang-II in SFO neurons projecting to pre-autonomic PVN neurons. Activation of AT1 receptors induces intracellular increases in reactive oxygen species (ROS), leading to increases in sympathetic nerve activity (SNA). Chronic sympathetic nerve activation promotes a series of metabolic disorders that characterizes the metabolic syndrome (MetS): dyslipidemia, hyperinsulinemia, glucose intolerance, hyperleptinemia and elevated plasma hormone levels, such as noradrenaline, glucocorticoids, leptin, insulin, and Ang-II. This review will discuss the contribution of our laboratory and others regarding the sympathoexcitation caused by peripheral Ang-II-induced reactive oxygen species along the subfornical organ and paraventricular nucleus of the hypothalamus. We hypothesize that this mechanism could be involved in metabolic disorders underlying MetS. PMID:26779026

  2. Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution

    PubMed Central

    Bergmann, Arno; Martinez-Moreno, Elias; Teschner, Detre; Chernev, Petko; Gliech, Manuel; de Araújo, Jorge Ferreira; Reier, Tobias; Dau, Holger; Strasser, Peter

    2015-01-01

    Water splitting catalysed by earth-abundant materials is pivotal for global-scale production of non-fossil fuels, yet our understanding of the active catalyst structure and reactivity is still insufficient. Here we report on the structurally reversible evolution of crystalline Co3O4 electrocatalysts during oxygen evolution reaction identified using advanced in situ X-ray techniques. At electrode potentials facilitating oxygen evolution, a sub-nanometre shell of the Co3O4 is transformed into an X-ray amorphous CoOx(OH)y which comprises di-μ-oxo-bridged Co3+/4+ ions. Unlike irreversible amorphizations, here, the formation of the catalytically-active layer is reversed by re-crystallization upon return to non-catalytic electrode conditions. The Co3O4 material thus combines the stability advantages of a controlled, stable crystalline material with high catalytic activity, thanks to the structural flexibility of its active amorphous oxides. We propose that crystalline oxides may be tailored for generating reactive amorphous surface layers at catalytic potentials, just to return to their stable crystalline state under rest conditions. PMID:26456525

  3. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  4. Reconstructing ecosystem functions of the active microbial community of the Baltic Sea oxygen depleted sediments.

    PubMed

    Thureborn, Petter; Franzetti, Andrea; Lundin, Daniel; Sjöling, Sara

    2016-01-01

    Baltic Sea deep water and sediments hold one of the largest anthropogenically induced hypoxic areas in the world. High nutrient input and low water exchange result in eutrophication and oxygen depletion below the halocline. As a consequence at Landsort Deep, the deepest point of the Baltic Sea, anoxia in the sediments has been a persistent condition over the past decades. Given that microbial communities are drivers of essential ecosystem functions we investigated the microbial community metabolisms and functions of oxygen depleted Landsort Deep sediments by metatranscriptomics. Results show substantial expression of genes involved in protein metabolism demonstrating that the Landsort Deep sediment microbial community is active. Identified expressed gene suites of metabolic pathways with importance for carbon transformation including fermentation, dissimilatory sulphate reduction and methanogenesis were identified. The presence of transcripts for these metabolic processes suggests a potential for heterotrophic-autotrophic community synergism and indicates active mineralisation of the organic matter deposited at the sediment as a consequence of the eutrophication process. Furthermore, cyanobacteria, probably deposited from the water column, are transcriptionally active in the anoxic sediment at this depth. Results also reveal high abundance of transcripts encoding integron integrases. These results provide insight into the activity of the microbial community of the anoxic sediment at the deepest point of the Baltic Sea and its possible role in ecosystem functioning. PMID:26823996

  5. Activation of Akt protects alveoli from neonatal oxygen-induced lung injury.

    PubMed

    Alphonse, Rajesh S; Vadivel, Arul; Coltan, Lavinia; Eaton, Farah; Barr, Amy J; Dyck, Jason R B; Thébaud, Bernard

    2011-02-01

    Bronchopulmonary dysplasia (BPD) is the main complication of extreme prematurity, resulting in part from mechanical ventilation and oxygen therapy. Currently, no specific treatment exists for BPD. BPD is characterized by an arrest in alveolar development and increased apoptosis of alveolar epithelial cells (AECs). Type 2 AECs are putative distal lung progenitor cells, capable of regenerating alveolar homeostasis after injury. We hypothesized that the protection of AEC2 death via the activation of the prosurvival Akt pathway prevents arrested alveolar development in experimental BPD. We show that the pharmacologic inhibition of the prosurvival factor Akt pathway with wortmannin during the critical period of alveolar development impairs alveolar development in newborn rats, resulting in larger and fewer alveoli, reminiscent of BPD. Conversely, in an experimental model of BPD induced by oxygen exposure of newborn rats, alveolar simplification is associated with a decreased activation of lung Akt. In vitro studies with rat lung epithelial (RLE) cells cultured in hyperoxia (95% O(2)) showed decreased apoptosis and improved cell survival after the forced expression of active Akt by adenovirus-mediated gene transfer. In vivo, adenovirus-mediated Akt gene transfer preserves alveolar architecture in the newborn rat model of hyperoxia-induced BPD. We conclude that inhibition of the prosurvival factor Akt disrupts normal lung development, whereas the expression of active Akt in experimental BPD preserves alveolar development. We speculate that the modulation of apoptosis may have therapeutic potential in lung diseases characterized by alveolar damage. PMID:20348209

  6. Forming a Learning Culture to Promote Fracture Prevention Activities

    ERIC Educational Resources Information Center

    Hjalmarson, Helene V.; Strandmark, Margaretha

    2012-01-01

    Purpose: The purpose of this paper is to explore interprofessional experiences of incorporating fracture prevention activities in clinical practice inspired by an empowerment approach. Design/methodology/approach: Data collection consisted primarily of focus groups interviews, systematized and analyzed by the grounded theory method. The study took…

  7. Thrombomodulin Binding Selects the Catalytically Active Form of Thrombin.

    PubMed

    Handley, Lindsey D; Treuheit, Nicholas A; Venkatesh, Varun J; Komives, Elizabeth A

    2015-11-01

    Human α-thrombin is a serine protease with dual functions. Thrombin acts as a procoagulant, cleaving fibrinogen to make the fibrin clot, but when bound to thrombomodulin (TM), it acts as an anticoagulant, cleaving protein C. A minimal TM fragment consisting of the fourth, fifth, and most of the sixth EGF-like domain (TM456m) that has been prepared has much improved solubility, thrombin binding capacity, and anticoagulant activity versus those of previous TM456 constructs. In this work, we compare backbone amide exchange of human α-thrombin in three states: apo, D-Phe-Pro-Arg-chloromethylketone (PPACK)-bound, and TM456m-bound. Beyond causing a decreased level of amide exchange at their binding sites, TM and PPACK both cause a decreased level of amide exchange in other regions including the γ-loop and the adjacent N-terminus of the heavy chain. The decreased level of amide exchange in the N-terminus of the heavy chain is consistent with the historic model of activation of serine proteases, which involves insertion of this region into the β-barrel promoting the correct conformation of the catalytic residues. Contrary to crystal structures of thrombin, hydrogen-deuterium exchange mass spectrometry results suggest that the conformation of apo-thrombin does not yet have the N-terminus of the heavy chain properly inserted for optimal catalytic activity, and that binding of TM allosterically promotes the catalytically active conformation. PMID:26468766

  8. Cellular Metabolic Activity and the Oxygen and Hydrogen Stable Isotope Composition of Intracellular Water and Metabolites

    NASA Astrophysics Data System (ADS)

    Kreuzer-Martin, H. W.; Hegg, E. L.

    2008-12-01

    Intracellular water is an important pool of oxygen and hydrogen atoms for biosynthesis. Intracellular water is usually assumed to be isotopically identical to extracellular water, but an unexpected experimental result caused us to question this assumption. Heme O isolated from Escherichia coli cells grown in 95% H218O contained only a fraction of the theoretical value of labeled oxygen at a position where the O atom was known to be derived from water. In fact, fewer than half of the oxygen atoms were labeled. In an effort to explain this surprising result, we developed a method to determine the isotope ratios of intracellular water in cultured cells. The results of our experiments showed that during active growth, up to 70% of the oxygen atoms and 50% of the hydrogen atoms in the intracellular water of E. coli are generated during metabolism and can be isotopically distinct from extracellular water. The fraction of isotopically distinct atoms was substantially less in stationary phase and chilled cells, consistent with our hypothesis that less metabolically-generated water would be present in cells with lower metabolic activity. Our results were consistent with and explained the result of the heme O labeling experiment. Only about 40% of the O atoms on the heme O molecule were labeled because, presumably, only about 40% of the water inside the cells was 18O water that had diffused in from the culture medium. The rest of the intracellular water contained 16O atoms derived from either nutrients or atmospheric oxygen. To test whether we could also detect metabolically-derived hydrogen atoms in cellular constituents, we isolated fatty acids from log-phase and stationary phase E. coli and determined the H isotope ratios of individual fatty acids. The results of these experiments showed that environmental water contributed more H atoms to fatty acids isolated in stationary phase than to the same fatty acids isolated from log-phase cells. Stable isotope analyses of

  9. Characterizing Warm Molecular Hydrogen in Active Star-Forming Systems

    NASA Astrophysics Data System (ADS)

    Rangwala, Naseem

    2014-10-01

    Herschel observations of nearby star-forming galaxies have determined that the warm component of the molecular gas traced by the high-J CO lines dominates the luminosity (~90% of the total CO luminosity) and hence the energetics of the molecular ISM. At the temperatures (T = 300 - 2000 K) and densities (n_H < 1E6 per cubic cm) typically found in our survey, H2 emission is the dominant gas coolant, much more important than CO. A fundamental assumption of all analyses of CO emission has been that CO emission traces H2 over the entire range of physical conditions in the observed sources. However, a direct observational comparison of spatial distributions and kinematics of CO and H2 has never been made for the warm molecular gas. We propose to observe the warm H2, in S(1) and S(2) transitions, with the SOFIA-EXES instrument in a diverse sample of star-forming systems: NGC 253 (starburst nucleus), NGC 6240 (luminous infrared galaxy), NGC 1068 (Seyfert-2), and SgrB2(M)/(N) (Galactic hot cores). The primary goal is to compare these measurements with the warm CO (J = 6-5 transition) observed with the Atacama Large Millimeter Array (ALMA) to investigate differences in the kinematics and spatial distributions (for the extended targets) of the two molecules and thereby confirm whether CO is a reliable tracer of H2 in the warm gas.

  10. 76 FR 31972 - Agency Information Collection Activities: Form I-508 and Form I-508F, Extension of a Currently...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-02

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-508 and... and Immigration Services (USCIS), will be submitting the following information collection request for... Immigration Services. (4) Affected public who will be asked or required to respond, as well as a...

  11. Singlet molecular oxygen-quenching activity of carotenoids: relevance to protection of the skin from photoaging

    PubMed Central

    Terao, Junji; Minami, Yuko; Bando, Noriko

    2011-01-01

    Carotenoids are known to be potent quenchers of singlet molecular oxygen [O2 (1Δg)]. Solar light-induced photooxidative stress causes skin photoaging by accelerating the generation of reactive oxygen species via photodynamic actions in which O2 (1Δg) can be generated by energy transfer from excited sensitizers. Thus, dietary carotenoids seem to participate in the prevention of photooxidative stress by accumulating as antioxidants in the skin. An in vivo study using hairless mice clarified that a O2 (1Δg) oxygenation-specific peroxidation product of cholesterol, cholesterol 5α-hydroperoxide, accumulates in skin lipids due to ultraviolet-A exposure. Matrix metalloproteinase-9, a metalloproteinase family enzyme responsible for the formation of wrinkles and sagging, was enhanced in the skin of ultraviolet-A -irradiated hairless mice. The activation of metalloproteinase-9 and the accumulation of 5α-hydroperoxide, as well as formation of wrinkles and sagging, were lowered in mice fed a β-carotene diet. These results strongly suggest that dietary β-carotene prevents the expression of metalloproteinase-9 (at least in part), by inhibiting the photodynamic action involving the formation of 5α-hydroperoxide in the skin. Intake of β-Carotene therefore appears to be helpful in slowing down ultraviolet-A -induced photoaging in human skin by acting as a O2 (1Δg) quencher. PMID:21297913

  12. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    NASA Astrophysics Data System (ADS)

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-08-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s -0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol-1s-1 was observed for the polydopamine-coated material-over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells.

  13. Investigation of a sterilization system using active oxygen species generated by ultraviolet irradiation.

    PubMed

    Yoshino, Kiyoshi; Matsumoto, Hiroyuki; Iwasaki, Tatsuyuki; Kinoshita, Shinobu; Noda, Kazutoshi; Oya, Kei; Iwamori, Satoru

    2015-01-01

    We have been investigating an advanced sterilization system that employs active oxygen species (AOS). We designed the sterilization equipment, including an evacuation system, which generates AOS from pure oxygen gas using ultraviolet irradiation, in order to study the conditions necessary for sterilization in the system's chamber. Using Geobachillus stearothermophilus spores (10(6) CFU) in a sterile bag as a biological indicator (BI) in the chamber of the AOS sterilization apparatus, we examined the viability of the BI as a function of exposure time, assessing the role of the decompression level in the sterilization performance. We found that the survival curves showed exponential reduction, and that the decompression level did not exert a significant influence on the survival curve. Subsequently, we investigated the sterilization effect as influenced by the spatial and environmental temperature variation throughout the chamber, and found that the sterilization effect varied with position, due to the varying environmental temperature in the respective areas. We confirmed that temperature is one of the most important factors influencing sterilization in the chamber, and estimated the temperature effect on the distribution of atomic oxygen concentration, using the quartz crystal microbalance (QCM) method with fluorocarbon thin film prepared by radio frequency sputtering.

  14. UV-B-Induced PR-1 Accumulation Is Mediated by Active Oxygen Species.

    PubMed

    Green, R.; Fluhr, R.

    1995-02-01

    Depletion of the stratospheric ozone layer may result in an increase in the levels of potentially harmful UV-B radiation reaching the surface of the earth. We have found that UV-B is a potent inducer of the plant pathogenesis-related protein PR-1 in tobacco leaves. UV-B fluences required for PR-1 accumulation are similar to those of other UV-B-induced responses. The UV-B-induced PR-1 accumulation was confined precisely to the irradiated area of the leaf but displayed no leaf tissue specificity. A study of some of the possible components of the signal transduction pathway between UV-B and PR-1 induction showed that photosynthetic processes are not essential, and photoreversible DNA damage is not involved. Antioxidants and cycloheximide were able to block the induction of PR-1 by UV-B, and treatment of leaves with a generator of reactive oxygen resulted in the accumulation of PR-1 protein. These results demonstrate an absolute requirement for active oxygen species and protein synthesis in this UV-B signal transduction pathway. In contrast, we also show that other elicitors, notably salicylic acid, are able to elicit PR-1 via nonreactive oxygen species-requiring pathways.

  15. Investigation of a sterilization system using active oxygen species generated by ultraviolet irradiation.

    PubMed

    Yoshino, Kiyoshi; Matsumoto, Hiroyuki; Iwasaki, Tatsuyuki; Kinoshita, Shinobu; Noda, Kazutoshi; Oya, Kei; Iwamori, Satoru

    2015-01-01

    We have been investigating an advanced sterilization system that employs active oxygen species (AOS). We designed the sterilization equipment, including an evacuation system, which generates AOS from pure oxygen gas using ultraviolet irradiation, in order to study the conditions necessary for sterilization in the system's chamber. Using Geobachillus stearothermophilus spores (10(6) CFU) in a sterile bag as a biological indicator (BI) in the chamber of the AOS sterilization apparatus, we examined the viability of the BI as a function of exposure time, assessing the role of the decompression level in the sterilization performance. We found that the survival curves showed exponential reduction, and that the decompression level did not exert a significant influence on the survival curve. Subsequently, we investigated the sterilization effect as influenced by the spatial and environmental temperature variation throughout the chamber, and found that the sterilization effect varied with position, due to the varying environmental temperature in the respective areas. We confirmed that temperature is one of the most important factors influencing sterilization in the chamber, and estimated the temperature effect on the distribution of atomic oxygen concentration, using the quartz crystal microbalance (QCM) method with fluorocarbon thin film prepared by radio frequency sputtering. PMID:25817808

  16. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    PubMed Central

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s −0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol−1s−1 was observed for the polydopamine-coated material–over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  17. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction.

    PubMed

    Parnell, Charlette M; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A; Mudalige, Thilak K; Biris, Alexandru S; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material's -0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 10(6) mol(-1)s(-1) was observed for the polydopamine-coated material-over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  18. Hypolyminetic Oxygen Depletion And Dynamics of P Binding Forms: Insights From Modeling Sediment Early Diagenesis Coupled With Automatic Parameter Estimation

    NASA Astrophysics Data System (ADS)

    Shafei, Babak; Schmid, Martin; Müller, Beat; Chwalek, Thomas

    2014-05-01

    Sediment diagenesis can significantly impact on lake water quality through depleting hypolimnion oxygen and acting as a sink or source of nutrients and contaminants. In this study, we apply MATsedLAB, a sediment diagenesis module developed in MATLAB [1, 2] to quantify benthic oxygen consumption and biogeochemical cycling of phosphate (P) in lacustrine sediments of Lake Baldegg, located in central Switzerland. MATsedLAB provides an access to the advanced computational and visualization capabilities of the interactive programming environment of MATLAB. It allows for a flexible definition of non steady-state boundary conditions at the sediment-water interface (SWI), the model parameters as well as transport and biogeochemical reactions. The model has been extended to facilitate the model-independent parameter estimation and uncertainty analysis using the software package, PEST. Lake Baldegg represents an interesting case where sediment-water interactions control P loading in an eutrophic lake. It is of 5.2 km2 surface area and has been artificially aerated since 1982. Between 1960 and 1980, low oxygen concentrations and meromictic condition were established as a result of high productivity. Here, we use the cores for the measurements of anions and cations which were collected in April and June 2012 respectively from the deepest location (66 m), by Torres et al. (2013) to calibrate the developed model [3]. Depth profiles of thirty three species were simulated by including thirty mixed kinetic-equilibrium biogeochemical processes as well as imposing the fluxes of organic and inorganic matters along with solute concentrations at the SWI as dynamic boundary conditions. The diffusive transport in the boundary layer (DBL) above the SWI was included as the supply of O2 to the sediment surface can be diffusion-limited, and applying a constant O2 concentration at the sediment surface may overestimate O2 consumption. Benthic oxygen consumption was calculated as a function of

  19. Multiple forms of endopeptidase activity from jojoba seeds.

    PubMed

    Wolf, M J; Storey, R D

    1990-01-01

    The cotyledons of 27 day post-germination jojoba seedlings (Simmondsia chinensis) contained five distinct endopeptidase activities separable by DEAE Bio-Gel and CM-cellulose ion exchange chromatography. The endopeptidases were purified 108- to 266-fold and their individuality was confirmed by activity-specific assays in native acrylamide gels along with differences in their Mr and catalytic properties. The five endopeptidases, which showed activity on model substrates and protein, were named EP Ia, EP Ib, EP II, EP III and EP IV. EP Ia was a serine proteinase with a pH optimum of ca 8 and Mr of 58,000. EP Ib, II and III were discrete cysteine proteinases showing pH optima of ca 6.8, 6.0 and 5.4 and Mr of 41,000, 47,000 and 35,000 respectively. EP IV was an aspartic acid proteinase with a ca pH optimum of 3.5 and Mr of 33,000.

  20. Evaluation of the persistence of micropollutants through pure-oxygen activated sludge nitrification and denitrification

    USGS Publications Warehouse

    Levine, A.D.; Meyer, M.T.; Kish, G.

    2006-01-01

    The persistence of pharmaceuticals, hormones, and household and industrial chemicals through a pure-oxygen activated sludge, nitrification, denitrification wastewater treatment facility was evaluated. Of the 125 micropollutants that were tested in this study, 55 compounds were detected in the untreated wastewater, and 27 compounds were detected in the disinfected effluent. The persistent compounds included surfactants, fire-retardant chemicals, pesticides, fragrance compounds, hormones, and one pharmaceutical. Physical-chemical properties of micropollutants that affected partitioning onto wastewater solids included vapor pressure and octanol-water partition coefficients.

  1. Testing and Oxygen Assessment Results for a Next Generation Extravehicular Activity Portable Life Support System Fan

    NASA Technical Reports Server (NTRS)

    Paul, Heather L.; Jennings, Mallory A.; Rivera, Fatonia L.; Martin, Devin

    2011-01-01

    NASA is designing a next generation Extravehicular Activity (EVA) Portable Life Support System (PLSS) for use in future surface exploration endeavors. To meet the new requirements for ventilation flow at nominal and buddy modes, a fan has been developed and tested. This paper summarizes the results of the performance and life cycle testing efforts conducted at the NASA Johnson Space Center. Additionally, oxygen compatibility assessment results from an evaluation conducted at White Sands Test Facility (WSTF) are provided, and lessons learned and future recommendations are outlined.

  2. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination

    NASA Astrophysics Data System (ADS)

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

  3. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination.

    PubMed

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-10

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

  4. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination.

    PubMed

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-01-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation. PMID:26059552

  5. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination

    PubMed Central

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-01-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon–nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation. PMID:26059552

  6. Antioxidant Activity of Oxygen Evolving Enhancer Protein 1 Purified from Capsosiphon fulvescens.

    PubMed

    Kim, Eun-Young; Choi, Youn Hee; Lee, Jung Im; Kim, In-Hye; Nam, Taek-Jeong

    2015-06-01

    This study was conducted to determine the antioxidant activity of a protein purified from Capsosiphon fulvescens. The purification steps included sodium acetate (pH 6) extraction and diethylaminoethyl-cellulose, reversed phase Shodex C4P-50 column chromatography. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis indicated that the molecular weight of the purified protein was 33 kDa. The N-terminus and partial peptide amino acid sequence of this protein was identical to the sequence of oxygen evolving enhancer (OEE) 1 protein. The antioxidant activity of the OEE 1 was determined in vitro using a scavenging test with 4 types of reactive oxygen species (ROS), including the 2,2-diphenyl-1-picrylhydrazyl radical, hydroxyl radical, superoxide anion, and hydrogen peroxide (H2 O2 ). OEE 1 had higher H2 O2 scavenging activity, which proved to be the result of enzymatic antioxidants rather than nonenzymatic antioxidants. In addition, OEE 1 showed less H2 O2 -mediated ROS formation in HepG2 cells. In conclusion, this study demonstrates that OEE 1 purified from C. fulvescens is an excellent antioxidant. PMID:25944160

  7. Electrochemical activation of commercial polyacrylonitrile-based carbon fiber for the oxygen reduction reaction.

    PubMed

    Xu, Haibo; Xia, Guangsen; Liu, Haining; Xia, Shuwei; Lu, Yonghong

    2015-03-28

    Nitrogen (N)-doped carbon and its non-noble metal composite replacing platinum-based oxygen reduction reaction (ORR) electrocatalysts still have some fundamental problems that remain. Here the micron-sized commercial polyacrylonitrile-based carbon fiber (PAN-CF) electrode was modified using an electrochemical method, converting its inherent pyridinic-N into 2-pyridone (or 2-hydroxyl pyridine) functional group existing in three-dimensional active layers with remarkable ORR catalytic activity and stability. The carbon atom adjacent to the nitrogen and oxygen atoms is prone to act as an active site to efficiently catalyze a two-electron ORR process. However, after coordinating pyridone to the Cu(2+) ion, together with the electrochemical reaction, the chemical redox between Cu(+) and ORR intermediates synergistically tends towards a four-electron pathway in alkaline solution. In different medium, the complexation and dissociation can induce the charge transfer and reconstruction among proton, metal ion and pyridone functionalities, eventually leading to the changes of ORR performance. PMID:25712410

  8. Active Curved Polymers Form Vortex Patterns on Membranes

    NASA Astrophysics Data System (ADS)

    Denk, Jonas; Huber, Lorenz; Reithmann, Emanuel; Frey, Erwin

    2016-04-01

    Recent in vitro experiments with FtsZ polymers show self-organization into different dynamic patterns, including structures reminiscent of the bacterial Z ring. We model FtsZ polymers as active particles moving along chiral, circular paths by Brownian dynamics simulations and a Boltzmann approach. Our two conceptually different methods point to a generic phase behavior. At intermediate particle densities, we find self-organization into vortex structures including closed rings. Moreover, we show that the dynamics at the onset of pattern formation is described by a generalized complex Ginzburg-Landau equation.

  9. Active Curved Polymers Form Vortex Patterns on Membranes.

    PubMed

    Denk, Jonas; Huber, Lorenz; Reithmann, Emanuel; Frey, Erwin

    2016-04-29

    Recent in vitro experiments with FtsZ polymers show self-organization into different dynamic patterns, including structures reminiscent of the bacterial Z ring. We model FtsZ polymers as active particles moving along chiral, circular paths by Brownian dynamics simulations and a Boltzmann approach. Our two conceptually different methods point to a generic phase behavior. At intermediate particle densities, we find self-organization into vortex structures including closed rings. Moreover, we show that the dynamics at the onset of pattern formation is described by a generalized complex Ginzburg-Landau equation. PMID:27176542

  10. Active Curved Polymers Form Vortex Patterns on Membranes.

    PubMed

    Denk, Jonas; Huber, Lorenz; Reithmann, Emanuel; Frey, Erwin

    2016-04-29

    Recent in vitro experiments with FtsZ polymers show self-organization into different dynamic patterns, including structures reminiscent of the bacterial Z ring. We model FtsZ polymers as active particles moving along chiral, circular paths by Brownian dynamics simulations and a Boltzmann approach. Our two conceptually different methods point to a generic phase behavior. At intermediate particle densities, we find self-organization into vortex structures including closed rings. Moreover, we show that the dynamics at the onset of pattern formation is described by a generalized complex Ginzburg-Landau equation.

  11. Catalytic activity of metal oxides in hydrogen sulfide oxidation by oxygen and sulfur dioxide

    SciTech Connect

    Marshneva, V.I.; Mokrinskii, V.V.

    1989-02-01

    Separate investigations have been made of the catalytic activities of a wide range of oxides by groups I-VIII metals in the Claus reaction and oxidation of H/sub 2/S by oxygen. Only 9 of 21 oxides used in the Claus reaction exhibit stable activity. The remaining oxides are deactivated, mainly by absorbing H/sub 2/S and being converted into sulfides. There are similar tendencies in the changes of sulfur formation specific velocities in both processes in the series of stable oxides V/sub 2/O/sub 5/, TiO/sub 2/, Mn/sub 2/O/sub 3/, Al/sub 2/O/sub 3/, MgO, Cr/sub 2/O/sub 3/. Vanadium pentoxide is the most active catalyst in the total and partial oxidations of H/sub 2/S and the Claus reaction.

  12. Elucidating the activity of stepped Pt single crystals for oxygen reduction.

    PubMed

    Bandarenka, Aliaksandr S; Hansen, Heine A; Rossmeisl, Jan; Stephens, Ifan E L

    2014-07-21

    The unexpectedly high measured activity of Pt[n(111) × (111)] and Pt[n(111) × (100)] stepped single crystal surfaces towards the oxygen reduction reaction (ORR) is explained utilizing the hydroxyl binding energy as the activity descriptor. Using this descriptor (estimated using experimental data obtained by different groups), a well-defined Sabatier-type volcano is observed for the activities measured for the Pt[n(111) × (111)] and Pt[n(111) × (100)] stepped single crystals, in remarkable agreement with earlier theoretical studies. We propose that the observed destabilisation of *OH species at these surfaces is due to the decreased solvation of the adsorbed hydroxyl intermediates on adjacent terrace sites. PMID:24643715

  13. Reactive oxygen species production and antioxidant enzyme activity during epididymal sperm maturation in Corynorhinus mexicanus bats.

    PubMed

    Arenas-Ríos, Edith; Rosado García, Adolfo; Cortés-Barberena, Edith; Königsberg, Mina; Arteaga-Silva, Marcela; Rodríguez-Tobón, Ahiezer; Fuentes-Mascorro, Gisela; León-Galván, Miguel Angel

    2016-03-01

    Prolonged sperm storage in the epididymis of Corynorhinus mexicanus bats after testicular regression has been associated with epididymal sperm maturation in the caudal region, although the precise factors linked with this phenomenon are unknown. The aim of this work is to determine the role of reactive oxygen species (ROS) and changes in antioxidant enzymatic activity occurring in the spermatozoa and epididymal fluid over time, in sperm maturation and storage in the caput, corpus and cauda of the bat epididymis. Our data showed that an increment in ROS production coincided with an increase in superoxide dismutase (SOD) activity in epididymal fluid and with a decrease in glutathione peroxidase (GPX) activity in the spermatozoa in at different time points and epididymal regions. The increase in ROS production was not associated with oxidative damage measured by lipid peroxidation. The results of the current study suggest the existence of a shift in the redox balance, which might be associated with sperm maturation and storage.

  14. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    SciTech Connect

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  15. Oxygen reduction activity of N-doped carbon-based films prepared by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Hakoda, Teruyuki; Yamamoto, Shunya; Kawaguchi, Kazuhiro; Yamaki, Tetsuya; Kobayashi, Tomohiro; Yoshikawa, Masahito

    2010-12-01

    Carbon-based films with nitrogen species on their surface were prepared on a glassy carbon (GC) substrate for application as a non-platinum cathode catalyst for polymer electrolyte fuel cells. Cobalt and carbon were deposited in the presence of N 2 gas using a pulsed laser deposition method and then the metal Co was removed by HCl-washing treatment. Oxygen reduction reaction (ORR) activity was electrochemically determined using a rotating disk electrode system in which the film samples on the GC substrate were replaceable. The ORR activity increased with the temperature of the GC substrate during deposition. A carbon-based film prepared at 600 °C in the presence of N 2 at 66.7 Pa showed the highest ORR activity among the tested samples (0.66 V vs. NHE). This film was composed of amorphous carbons doped with pyridine type nitrogen atoms on its surface.

  16. Active Oxygen Metabolites and Thromboxane in Phorbol Myristate Acetate Toxicity to the Isolated, Perfused Rat Lung.

    NASA Astrophysics Data System (ADS)

    Carpenter, Laurie Jean

    When administered intravenously or intratracheally to rats, rabbits and sheep, phorbol myristate acetate (PMA) produces changes in lung morphology and function are similar to those seen in humans with the adult respiratory distress syndrome (ARDS). Therefore, it is thought that information about the mechanism of ARDS development can be gained from experiments using PMA-treated animals. Currently, the mechanisms by which PMA causes pneumotoxicity are unknown. Results from other studies in rabbits and in isolated, perfused rabbit lungs suggest that PMA-induced lung injury is mediated by active oxygen species from neutrophils (PMN), whereas studies in sheep and rats suggest that PMN are not required for the toxic response. The role of PMN, active oxygen metabolites and thromboxane (TxA_2) in PMA-induced injury to isolated, perfused rat lungs (IPLs) was examined in this thesis. To determine whether PMN were required for PMA to produce toxicity to the IPL, lungs were perfused for 30 min with buffer containing various concentrations of PMA (in the presence or absence of PMN). When concentrations >=q57 ng/ml were added to medium devoid of added PMN, perfusion pressure and lung weight increased. When a concentration of PMA (14-28 ng/ml) that did not by itself cause lungs to accumulate fluid was added to the perfusion medium containing PMN (1 x 10 ^8), perfusion pressure increased, and lungs accumulated fluid. These results indicate that high concentrations of PMA produce lung injury which is independent of PMN, whereas injury induced by lower concentrations is PMN-dependent. To examine whether active oxygen species were involved in mediating lung injury induced by PMA and PMN, lungs were coperfused with the oxygen radical scavengers SOD and/or catalase. Coperfusion with either or both of these enzymes totally protected lungs against injury caused by PMN and PMA. These results suggest that active oxygen species (the hydroxyl radical in particular), mediate lung injury in

  17. Activation of the JAK-STAT pathway by reactive oxygen species.

    PubMed

    Simon, A R; Rai, U; Fanburg, B L; Cochran, B H

    1998-12-01

    Reactive oxygen species (ROS) play an important role in the pathogenesis of many human diseases, including the acute respiratory distress syndrome, Parkinson's disease, pulmonary fibrosis, and Alzheimer's disease. In mammalian cells, several genes known to be induced during the immediate early response to growth factors, including the protooncogenes c-fos and c-myc, have also been shown to be induced by ROS. We show that members of the STAT family of transcription factors, including STAT1 and STAT3, are activated in fibroblasts and A-431 carcinoma cells in response to H2O2. This activation occurs within 5 min, can be inhibited by antioxidants, and does not require protein synthesis. STAT activation in these cell lines is oxidant specific and does not occur in response to superoxide- or nitric oxide-generating stimuli. Buthionine sulfoximine, which depletes intracellular glutathione, also activates the STAT pathway. Moreover, H2O2 stimulates the activity of the known STAT kinases JAK2 and TYK2. Activation of STATs by platelet-derived growth factor (PDGF) is significantly inhibited by N-acetyl-L-cysteine and diphenylene iodonium, indicating that ROS production contributes to STAT activation in response to PDGF. These findings indicate that the JAK-STAT pathway responds to intracellular ROS and that PDGF uses ROS as a second messenger to regulate STAT activation.

  18. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  19. 77 FR 15787 - Agency Information Collection Activities: Form I-131, Revision of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-16

    ... the Form/Collection: Application for Travel Document. (3) Agency Form Number, if any, and the... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-131... Collection Under Review: Form I- 131, Application for Travel Document. The Department of Homeland Security,...

  20. 76 FR 81517 - Agency Information Collection Activities: Form I-131, Revision of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-28

    ... the Form/Collection: Application for Travel Document. (3) Agency form number, if any, and the... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-131... Collection Under Review: Form I- 131, Application for Travel Document. The Department of Homeland Security,...

  1. 76 FR 10385 - Agency Information Collection Activities: Various Contract Related Forms That Will be Included in...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-24

    ... SECURITY Agency Information Collection Activities: Various Contract Related Forms That Will be Included in the Homeland Security Acquisition Regulation, DHS FORM 0700-01, DHS FORM 0700-02, DHS FORM 0700-03...: The Department of Homeland Security, Office of Chief Procurement Officer, Acquisition Policy...

  2. 75 FR 21013 - Agency Information Collection Activities: Form N-644; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-22

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-644... Collection Under Review; Form N- 644, Application for Posthumous Citizenship; OMB Control No. 1615-0059. The..., USCIS will be evaluating whether to revise the Form N-644. Should USCIS decide to revise Form N-644...

  3. 76 FR 21913 - Agency Information Collection Activities: Form N-644; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-19

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-644... Collection Under Review: Form N- 644, Application for Posthumous Citizenship; OMB Control No. 1615-0059. The..., USCIS will be evaluating whether to revise the Form N-644. Should USCIS decide to revise Form N-644...

  4. Combinatorial high-throughput screening for highly active Pd-Ir-Ce based ternary catalysts in electrochemical oxygen reduction reaction.

    PubMed

    Park, Sung Hyeon; Choi, Chang Hyuck; Koh, Jae Kang; Pak, Chanho; Jin, Seon-ah; Woo, Seong Ihl

    2013-11-11

    A combinatorial library having 66 different ternary compositions of Pd-Ir-Ce was prepared via the impregnation method to find the optimum ternary composition with the highest performance toward oxygen reduction reaction (ORR) in acid media. Its performance in ORR activity of the combinatorial array was evaluated through two different combinatorial high-throughput screening methods to gain validity: (1) multielectrode half-cell method and (2) optical screening method. From the combinatorial results, the spot at 79:12:9 for Pd-Ir-Ce (at. %) in the array showed the highest ORR activity. The electrochemical characterizations of the single catalyst demonstrates that the optimized Pd79Ir12Ce9/C catalyst shows 1.5 times the ORR activity compared to that of Pd/C catalyst at 0.85 V (vs. RHE). In the Pd-Ir-Ce based catalysts, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results reveal that Ir and Ce are present in the form of IrO2 and CeO2, respectively, and the electron configuration of Pd is effectively modified through the decoration with IrO2 and CeO2. From the results, we suggest that the electro-modification of Pd through strong metal-metal oxide interaction with IrO2-CeO2 was a reason for the enhanced ORR activity.

  5. Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal–Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems

    PubMed Central

    2015-01-01

    Detailed understanding of the nature of the active centers in non-precious-metal-based electrocatalyst, and their role in oxygen reduction reaction (ORR) mechanistic pathways will have a profound effect on successful commercialization of emission-free energy devices such as fuel cells. Recently, using pyrolyzed model structures of iron porphyrins, we have demonstrated that a covalent integration of the Fe–Nx sites into π-conjugated carbon basal plane modifies electron donating/withdrawing capability of the carbonaceous ligand, consequently improving ORR activity. Here, we employ a combination of in situ X-ray spectroscopy and electrochemical methods to identify the various structural and functional forms of the active centers in non-heme Fe/N/C catalysts. Both methods corroboratively confirm the single site 2e– × 2e– mechanism in alkaline media on the primary Fe2+–N4 centers and the dual-site 2e– × 2e– mechanism in acid media with the significant role of the surface bound coexisting Fe/FexOy nanoparticles (NPs) as the secondary active sites. PMID:24817921

  6. Heat of Hydration of Low Activity Cementitious Waste Forms

    SciTech Connect

    Nasol, D.

    2015-07-23

    During the curing of secondary waste grout, the hydraulic materials in the dry mix react exothermally with the water in the secondary low-activity waste (LAW). The heat released, called the heat of hydration, can be measured using a TAM Air Isothermal Calorimeter. By holding temperature constant in the instrument, the heat of hydration during the curing process can be determined. This will provide information that can be used in the design of a waste solidification facility. At the Savannah River National Laboratory (SRNL), the heat of hydration and other physical properties are being collected on grout prepared using three simulants of liquid secondary waste generated at the Hanford Site. From this study it was found that both the simulant and dry mix each had an effect on the heat of hydration. It was also concluded that the higher the cement content in the dry materials mix, the greater the heat of hydration during the curing of grout.

  7. Maximal Oxygen Intake and Maximal Work Performance of Active College Women.

    ERIC Educational Resources Information Center

    Higgs, Susanne L.

    Maximal oxygen intake and associated physiological variables were measured during strenuous exercise on women subjects (N=20 physical education majors). Following assessment of maximal oxygen intake, all subjects underwent a performance test at the work level which had elicited their maximal oxygen intake. Mean maximal oxygen intake was 41.32…

  8. Identification of biotransformation products of citalopram formed in activated sludge.

    PubMed

    Beretsou, Vasiliki G; Psoma, Aikaterini K; Gago-Ferrero, Pablo; Aalizadeh, Reza; Fenner, Kathrin; Thomaidis, Nikolaos S

    2016-10-15

    Citalopram (CTR) is a worldwide highly consumed antidepressant which has demonstrated incomplete removal by conventional wastewater treatment. Despite its global ubiquitous presence in different environmental compartments, little is known about its behaviour and transformation processes during wastewater treatment. The present study aims to expand the knowledge on fate and transformation of CTR during the biological treatment process. For this purpose, batch reactors were set up to assess biotic, abiotic and sorption losses of this compound. One of the main objectives of the study was the identification of the formed transformation products (TPs) by applying suspect and non-target strategies based on liquid chromatography quadrupole-time-of-flight mass spectrometry (LC-QTOF-MS). The complementary use of reversed phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) for the identification of polar TPs, and the application of in-house developed quantitative structure-retention relationship (QSRR) prediction models, in addition to the comprehensive evaluation of the obtained MS/MS spectra, provided valuable information to support identification. In total, fourteen TPs were detected and thirteen of them were tentatively identified. Four compounds were confirmed (N-desmethylCTR, CTR amide, CTR carboxylic acid and 3-oxo-CTR) through the purchase of the corresponding reference standard. Probable structures based on diagnostic evidence were proposed for the additional nine TPs. Eleven TPs are reported for the first time. A transformation pathway for the biotransformation of CTR was proposed. The presence of the identified TPs was assessed in real wastewater samples through retrospective analysis, resulting in the detection of five compounds. Finally, the potential ecotoxicological risk posed by CTR and its TPs to different trophic levels of aquatic organisms was evaluated by means of risk quotients. PMID:27459150

  9. Measuring the activities of higher organisms in activated sludge by means of mechanical shearing pretreatment and oxygen uptake rate.

    PubMed

    Hao, Xiaodi; Wang, Qilin; Cao, Yali; van Loosdrecht, Mark C M

    2010-07-01

    A pretreatment method was developed to assess the activities of higher organisms. The method is based on mechanical shearing to damage the large cells of the protozoan and metazoan community in activated sludge. The procedure was confirmed through experimentation to be effective in determining the activities of higher organisms by comparing oxygen uptake rates (OURs) before and after the higher organisms were eradicated. Shearing led to disintegration of flocs, which could be effectively reconstituted by centrifugation. The reconstitution of the sludge flocs was essential since otherwise the activity of the floc mass would be too high due to lack of diffusion limitation. Mechanical shearing had no influence on the morphology, quantity and specific activity of yeasts, and it was inferred that bacteria smaller than yeasts in size would also not be influenced by the applied shearing procedure. Moreover, the effect of filamentous organisms on the measured activities of higher organisms was experimentally demonstrated and analyzed, and determined to be so weak that it could be ignored. Based on these tests, five typical activated sludge processes were selected to measure the contribution of higher organisms to the original OUR. The measured activities of higher organisms ranged from 9.4 to 25.0% of the original OURs.

  10. The oxygen fugacity at which graphite or diamond forms from carbonate-bearing melts in eclogitic rocks

    NASA Astrophysics Data System (ADS)

    Stagno, V.; Frost, D. J.; McCammon, C. A.; Mohseni, H.; Fei, Y.

    2015-02-01

    The oxygen fugacity ( fO2) at which carbonate-bearing melts are reduced to either graphite or diamond in synthetic eclogite compositions has been measured in multi-anvil experiments performed at pressures between 3 and 7 GPa and temperatures between 800 and 1,300 °C using iron-iridium and iron-platinum alloys as sliding redox sensors. The determined oxygen fugacities buffered by the coexistence of elemental carbon and carbonate-bearing melt are approximately 1 log unit below thermodynamic calculations for a similar redox buffering equilibrium involving only solid phases. The measured oxygen fugacities normalized to the fayalite-magnetite-quartz oxygen buffer decrease with temperature from ~-0.8 to ~-1.7 log units at 3 GPa, most likely as a result of increasing dilution of the carbonate liquid with silicate. The normalized fO2 values also decrease with pressure and show a similar decrease with temperature at 6 GPa from ~-1.5 log units at 1,100 °C to ~-2.4 log units at 1,300 °C. In contrast to previous arguments, the stability field of the carbonate-bearing melt extends to lower oxygen fugacity in eclogite rocks than in peridotite rocks, which implies a wider range of conditions over which carbon remains mobile in natural eclogites. The raised prevalence of diamonds in eclogites compared to peridotites may, therefore, reflect more effective scavenging of carbon by melts in these rocks. The ferric iron contents of monomineralic layers of clinopyroxene and garnet contained in the same experiments were also measured using Mössbauer spectroscopy. A preliminary model was derived for determining the fO2 of eclogitic rocks from the compositions of garnet and clinopyroxene, including the Fe3+/ΣFe ratio of garnet, using the equilibrium, The model, which reproduces the independently determined fO2 of the experimental data to within 0.5 log units, can be used to estimate the fO2 of ultrahigh-pressure metamorphic eclogites and cratonic eclogitic xenoliths. Although there

  11. Oxygen safety

    MedlinePlus

    COPD - oxygen safety; Chronic obstructive pulmonary disease - oxygen safety; Chronic obstructive airways disease - oxygen safety; Emphysema - oxygen safety; Heart failure - oxygen-safety; Palliative care - oxygen safety; ...

  12. Oxygen dependence of two-photon activation of zinc and copper phthalocyanine tetrasulfonate in Jurkat cells.

    PubMed

    Mir, Youssef; van Lier, Johan E; Paquette, Benoit; Houde, Daniel

    2008-01-01

    Photodynamic therapy (PDT), the use of light-activated drugs, is a promising treatment of cancer as well as several nonmalignant conditions. However, the efficacy of one-photon (1-gamma) PDT is limited by hypoxia, which can prevent the production of the cytotoxic singlet oxygen ((1)O(2)) species, leading to tumor resistance to PDT. To solve this problem, we propose an irradiation protocol based on a simultaneous, two-photon (2-gamma) excitation of the photosensitizer (Ps). Excitation of the Ps triplet state leads to an upper excited triplet state T(n) with distinct photochemical properties, which could inflict biologic damage independent of the presence of molecular oxygen. To determine the potential of a 2-gamma excitation process, Jurkat cells were incubated with zinc or copper phthalocyanine tetrasulfonate (ZnPcS(4) or CuPcS(4)). ZnPcS(4) is a potent (1)O(2) generator in 1-gamma PDT, while CuPcS(4) is inactive under these conditions. Jurkat cells incubated with either ZnPcS(4) or CuPcS(4) were exposed to a 670 nm continuous laser (1-gamma PDT), 532 nm pulsed-laser light (2-gamma PDT), or a combination of 532 and 670 nm (2-gamma PDT). The efficacy of ZnPcS(4) to photoinactivate the Jurkat cells decreased as the concentration of oxygen decreased for both the 1-gamma and 2-gamma protocols. In the case of CuPcS(4), cell phototoxicity was measured only following 2-gamma irradiation, and its efficacy also decreased at a lower oxygen concentration. Our results suggest that for CuPcS(4) the T(n) excited state can be populated after 2-gamma irradiation at 532 nm or the combination of 532 and 670 nm light. Dependency of phototoxicity upon aerobic conditions for both 1-gamma and 2-gamma PDT suggests that reactive oxygen species play an important role in 1-gamma and 2-gamma PDT.

  13. Transgenic tobacco expressing a foreign calmodulin gene shows an enhanced production of active oxygen species.

    PubMed Central

    Harding, S A; Oh, S H; Roberts, D M

    1997-01-01

    A strategy for elucidating specific molecular targets of calcium and calmodulin in plant defense responses has been developed. We have used a dominant-acting calmodulin mutant (VU-3, Lys to Arg115) to investigate the oxidative burst and nicotinamide co-enzyme fluxes after various stimuli (cellulase, harpin, incompatible bacteria, osmotic and mechanical) that elicit plant defense responses in transgenic tobacco cell cultures. VU-3 calmodulin differs from endogenous plant calmodulin in that it cannot be methylated post-translationally, and as a result it hyperactivates calmodulin-dependent NAD kinase. Cells expressing VU-3 calmodulin exhibited a stronger active oxygen burst that occurred more rapidly than in normal control cells challenged with the same stimuli. Increases in NADPH level were also greater in VU-3 cells and coincided both in timing and magnitude with development of the active oxygen species (AOS) burst. These data show that calmodulin is a target of calcium fluxes in response to elicitor or environmental stress, and provide the first evidence that plant NAD kinase may be a downstream target which potentiates AOS production by altering NAD(H)/NADP(H) homeostasis. PMID:9135130

  14. Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

    PubMed Central

    Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

    2013-01-01

    The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

  15. Semi-synthesis of oxygenated dolabellane diterpenes with highly in vitro anti-HIV-1 activity.

    PubMed

    Pardo-Vargas, Alonso; Ramos, Freddy A; Cirne-Santos, Claudio Cesar; Stephens, Paulo Roberto; Paixão, Izabel Christina Palmer; Teixeira, Valeria Laneuville; Castellanos, Leonardo

    2014-09-15

    Research on dolabellane diterpenes of brown algae Dictyota spp. has shown that these diterpenoids have strong anti-HIV-1 activity, but there are not data about antiviral activity of dolabellane diterpenes isolated from octocorals, which are antipodes of those isolated from the brown algae. Dolabellanes 13-keto-1(R),11(S)-dolabella-3(E),7(E),12(18)-triene (1) and β-Araneosene (2) were isolated from the Caribbean octocoral Eunicea laciniata, and both showed low anti-HIV-1 activity and low toxicity. Since it was shown that oxygenated dolabellanes from algae have better anti-HIV-1 activity, in this work some derivatives of the main dolabellane of E. laciniata1 were obtained by epoxidation (3), epoxide opening (4), and allylic oxidation (5). The derivatives showed significant improvement in the anti-HIV-1potency (100-fold), being compounds 3 and 5 the most active ones. Their high antiviral activities, along with their low cytotoxicity, make them promissory antiviral compounds; and it is worth noting that the absolute configuration at the ring junction in the dolabellane skeleton does not seem to be determinant in the antiviral potency of these diterpeneoids. PMID:25176328

  16. Semi-synthesis of oxygenated dolabellane diterpenes with highly in vitro anti-HIV-1 activity.

    PubMed

    Pardo-Vargas, Alonso; Ramos, Freddy A; Cirne-Santos, Claudio Cesar; Stephens, Paulo Roberto; Paixão, Izabel Christina Palmer; Teixeira, Valeria Laneuville; Castellanos, Leonardo

    2014-09-15

    Research on dolabellane diterpenes of brown algae Dictyota spp. has shown that these diterpenoids have strong anti-HIV-1 activity, but there are not data about antiviral activity of dolabellane diterpenes isolated from octocorals, which are antipodes of those isolated from the brown algae. Dolabellanes 13-keto-1(R),11(S)-dolabella-3(E),7(E),12(18)-triene (1) and β-Araneosene (2) were isolated from the Caribbean octocoral Eunicea laciniata, and both showed low anti-HIV-1 activity and low toxicity. Since it was shown that oxygenated dolabellanes from algae have better anti-HIV-1 activity, in this work some derivatives of the main dolabellane of E. laciniata1 were obtained by epoxidation (3), epoxide opening (4), and allylic oxidation (5). The derivatives showed significant improvement in the anti-HIV-1potency (100-fold), being compounds 3 and 5 the most active ones. Their high antiviral activities, along with their low cytotoxicity, make them promissory antiviral compounds; and it is worth noting that the absolute configuration at the ring junction in the dolabellane skeleton does not seem to be determinant in the antiviral potency of these diterpeneoids.

  17. Electron transport chain inhibitors induce microglia activation through enhancing mitochondrial reactive oxygen species production.

    PubMed

    Ye, Junli; Jiang, Zhongxin; Chen, Xuehong; Liu, Mengyang; Li, Jing; Liu, Na

    2016-01-15

    Reactive oxygen species (ROS) are believed to be mediators of excessive microglial activation, yet the resources and mechanism are not fully understood. Here we stimulated murine microglial BV-2 cells and primary microglial cells with different inhibitors of electron transport chain (ETC), rotenone, thenoyltrifluoroacetone (TTFA), antimycin A, and NaN3 to induce mitochondrial ROS production and we observed the role of mitochondrial ROS in microglial activation. Our results showed that ETC inhibitors resulted in significant changes in cell viability, microglial morphology, cell cycle arrest and mitochondrial ROS production in a dose-dependent manner in both primary cultural microglia and BV-2 cell lines. Moreover, ETC inhibitors, especially rotenone and antimycin A stimulated secretion of interleukin 1β (IL-1β), interleukin 6 (IL-6), interleukin 12 (IL-12) and tumor necrosis factor α (TNF-α) by microglia with marked activation of mitogen-activated proteinkinases (MAPKs) and nuclear factor κB (NF-κB), which could be blocked by specific inhibitors of MAPK and NF-κB and mitochondrial antioxidants, Mito-TEMPO. Taken together, our results demonstrated that inhibition of mitochondrial respiratory chain in microglia led to production of mitochondrial ROS and therefore may activate MAPK/NF-кB dependent inflammatory cytokines release in microglia, which indicated that mitochondrial-derived ROS were contributed to microglial activation.

  18. Segregated Pt on Pd nanotubes for enhanced oxygen reduction activity in alkaline electrolyte.

    PubMed

    St John, Samuel; Atkinson, Robert W; Dyck, Ondrej; Sun, Cheng-Jun; Zawodzinski, Thomas A; Papandrew, Alexander B

    2015-12-01

    Nanoscaled Pt domains were integrated with Pd nanotubes via vapor deposition to yield a highly active electrocatalyst for the oxygen reduction reaction (ORR) in alkaline media. The surface-area-normalized ORR activity of these bi-metallic Pt-on-Pd nanotubes (PtPdNTs) was nearly 6× the corresponding carbon-supported Pt nanoparticle (Pt/C) activity at 0.9 V vs. RHE (1.5 vs. 0.24 mA cmmetal(-2), respectively). Furthermore, the high specific activity of the PtPdNTs was achieved without sacrificing mass-normalized activity, which is more than twice that of Pt/C (0.333 A mgPtPdNT(-1)vs. 0.141 A mgPt/C(-1)) and also greater than that of Pd/C (0.221 A mgPd/C(-1)). We attribute the enhancements in specific and mass activity to modifications of the segregated Pt electronic structure and to nanoscale porosity, respectively. PMID:26553367

  19. Enhanced electrocatalytic activity of nitrogen-doped olympicene/graphene hybrids for the oxygen reduction reaction.

    PubMed

    Hou, Xiuli; Zhang, Peng; Li, Shuang; Liu, Wei

    2016-08-17

    Developing inexpensive and non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) is among the major goals in fuel cells. Herein, by using density-functional theory calculations, we show that N-doped olympicene/graphene hybrids exhibit unexpectedly high ORR catalytic activity-even comparable to that of the Pt(111) surface. Both graphitic-type and pyridine-type N-doped olympicene/graphene hybrids are highly active for the ORR and have good CO tolerance. The formation of the second H2O molecule is the rate-determining step for the ORR with the graphitic-type hybrid, whereas on the pyridine-type hybrid, it is the formation of OOH. Note that N-doped olympicene/graphene hybrid materials combine the high reactivity of olympicene and the high electrical conductivity of graphene, which allows them to be potentially used as low-cost and non-precious-metal ORR catalysts.

  20. Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

    PubMed

    Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

    2015-03-11

    Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode.

  1. Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

    PubMed

    Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

    2014-03-01

    Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances.

  2. NOx reduction Activity over Phosphate-supported Platinum Catalysts with Hydrogen under Oxygen-rich Condition

    NASA Astrophysics Data System (ADS)

    Itoh, M.; Takehara, M.; Saito, M.; Machida, K.

    2011-10-01

    The phosphate supported Pt catalysts (Pt/AlPO4, Pt/CePO4, Pt/CeP2O7, Pt/SnP2O7, Pt/TiP2O7, Pt/Zn3(PO4)2) were prepared by a conventional impregnation method to evaluate their selective catalytic reduction activity of NOx under excess oxygen condition. Among them, good NOx reduction activity was obtained on the Pt/AlPO4 catalyst. Specific adsorption species during the NOx reduction were checked by a diffuse reflectance infrared Fourier transform spectrum (DRIFTs) measurement to examine the reaction mechanism. Also NH3 temperature programmed desorption measurements were performed for all catalysts and their catalytic properties were discussed from the viewpoints of solid acidity.

  3. Auxin-induced reactive oxygen species production requires the activation of phosphatidylinositol 3-kinase.

    PubMed

    Joo, Jung Hee; Yoo, Ho Jung; Hwang, Inhwan; Lee, June Seung; Nam, Kyoung Hee; Bae, Yun Soo

    2005-02-14

    We recently reported that production of reactive oxygen species (ROS) is essential for auxin-induced gravitropic signaling. Here, we investigated the role of phosphatidylinositol 3-kinase and its product, PtdIns(3)P, in auxin-mediated ROS production and the root gravitropic response. Pretreatment with LY294002, an inhibitor of PtdIns 3-kinase activity, blocked auxin-mediated ROS generation, and reduced the sensitivity of root tissue to gravistimulation. The amount of PtdIns(3)P increased in response to auxin, and this effect was abolished by pretreatment with LY294002. In addition, sequestration of PtdIns(3)P by transient expression of the endosome binding domain in protoplasts abrogated IAA-induced ROS accumulation. These results indicate that activation of PtdIns 3-kinase and its product PtdIns(3)P are required for auxin-induced production of ROS and root gravitropism. PMID:15710420

  4. Rationalizing the Hydrogen and Oxygen Evolution Reaction Activity of Two-Dimensional Hydrogenated Silicene and Germanene.

    PubMed

    Rupp, Caroline J; Chakraborty, Sudip; Anversa, Jonas; Baierle, Rogério J; Ahuja, Rajeev

    2016-01-20

    We have undertaken first-principles electronic structure calculations to show that the chemical functionalization of two-dimensional hydrogenated silicene (silicane) and germanene (germanane) can become a powerful tool to increase the photocatalytic water-splitting activity. Spin-polarized density functional theory within the GGA-PBE and HSE06 types of exchange correlation functionals has been used to obtain the structural, electronic, and optical properties of silicane and germanane functionalized with a series of nonmetals (N, P, and S), alkali metals (Li, Na, and K) and alkaline-earth metals (Mg and Ca). The surface-adsorbate interaction between the functionalized systems with H2 and O2 molecules that leads to envisaged hydrogen and oxygen evolution reaction activity has been determined.

  5. Understanding Iron-based catalysts with efficient Oxygen reduction activity from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Hafiz, Hasnain; Barbiellini, B.; Jia, Q.; Tylus, U.; Strickland, K.; Bansil, A.; Mukerjee, S.

    2015-03-01

    Catalysts based on Fe/N/C clusters can support the oxygen-reduction reaction (ORR) without the use of expensive metals such as platinum. These systems can also prevent some poisonous species to block the active sites from the reactant. We have performed spin-polarized calculations on various Fe/N/C fragments using the Vienna Ab initio Simulation Package (VASP) code. Some results are compared to similar calculations obtained with the Gaussian code. We investigate the partial density of states (PDOS) of the 3d orbitals near the Fermi level and calculate the binding energies of several ligands. Correlations of the binding energies with the 3d electronic PDOS's are used to propose electronic descriptors of the ORR associated with the 3d states of Fe. We also suggest a structural model for the most active site with a ferrous ion (Fe2+) in the high spin state or the so-called Doublet 3 (D3).

  6. Enhanced Oxygen Reduction Activity In Acid By Tin-Oxide Supported Au Nanoparticle Catalysts

    SciTech Connect

    Baker,W.; Pietron, J.; Teliska, M.; Bouwman, P.; Ramaker, D.; Swider-Lyons, K.

    2006-01-01

    Gold nanoparticles supported on hydrous tin-oxide (Au-SnO{sub x}) are active for the four-electron oxygen reduction reaction in an acid electrolyte. The unique electrocatalytic of the Au-SnO is confirmed by the low amount of peroxide detected with rotating ring-disk electrode voltammetry and Koutecky-Levich analysis. In comparison, 10 wt % Au supported on Vulcan carbon and SnO{sub x} catalysts both produce significant peroxide in the acid electrolyte, indicating only a two-electron reduction reaction. Characterization of the Au-SnO{sub x} catalyst reveals a high-surface area, amorphous support with 1.7 nm gold metal particles. The high catalytic activity of the Au-SnO is attributed to metal support interactions. The results demonstrate a possible path to non-Pt catalysts for proton exchange membrane fuel cell cathodes.

  7. The MOSDEF Survey: Detection of [O III]λ4363 and the Direct-method Oxygen Abundance of a Star-forming Galaxy at z = 3.08

    NASA Astrophysics Data System (ADS)

    Sanders, Ryan L.; Shapley, Alice E.; Kriek, Mariska; Reddy, Naveen A.; Freeman, William R.; Coil, Alison L.; Siana, Brian; Mobasher, Bahram; Shivaei, Irene; Price, Sedona H.; de Groot, Laura

    2016-07-01

    We present measurements of the electron-temperature-based oxygen abundance for a highly star-forming galaxy at z = 3.08, COSMOS-1908. This is the highest redshift at which [O iii]λ4363 has been detected and the first time that this line has been measured at z\\gt 2. We estimate an oxygen abundance of 12+{log}({{O}}/{{H}})={8.00}-0.14+0.13. This galaxy is a low-mass ({10}9.3 {M}ȯ ), highly star-forming (˜50 {M}ȯ yr‑1) system that hosts a young stellar population (˜160 Myr). We investigate the physical conditions of the ionized gas in COSMOS-1908 and find that this galaxy has a high ionization parameter, little nebular reddening (E{(B-V)}{{gas}}\\lt 0.14), and a high electron density ({n}e˜ 500 cm‑3). We compare the ratios of strong oxygen, neon, and hydrogen lines to the direct-method oxygen abundance for COSMOS-1908 and additional star-forming galaxies at z=0-1.8 with [O iii]λ4363 measurements and show that galaxies at z˜ 1{--}3 follow the same strong-line correlations as galaxies in the local universe. This agreement suggests that the relationship between ionization parameter and O/H is similar for z˜ 0 and high-redshift galaxies. These results imply that metallicity calibrations based on lines of oxygen, neon, and hydrogen do not strongly evolve with redshift and can reliably estimate abundances out to z˜ 3, paving the way for robust measurements of the evolution of the mass–metallicity relation to high redshift. Based on data obtained at the W.M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and NASA, and was made possible by the generous financial support of the W.M. Keck Foundation.

  8. The MOSDEF Survey: Detection of [O III]λ4363 and the Direct-method Oxygen Abundance of a Star-forming Galaxy at z = 3.08

    NASA Astrophysics Data System (ADS)

    Sanders, Ryan L.; Shapley, Alice E.; Kriek, Mariska; Reddy, Naveen A.; Freeman, William R.; Coil, Alison L.; Siana, Brian; Mobasher, Bahram; Shivaei, Irene; Price, Sedona H.; de Groot, Laura

    2016-07-01

    We present measurements of the electron-temperature-based oxygen abundance for a highly star-forming galaxy at z = 3.08, COSMOS-1908. This is the highest redshift at which [O iii]λ4363 has been detected and the first time that this line has been measured at z\\gt 2. We estimate an oxygen abundance of 12+{log}({{O}}/{{H}})={8.00}-0.14+0.13. This galaxy is a low-mass ({10}9.3 {M}⊙ ), highly star-forming (˜50 {M}⊙ yr-1) system that hosts a young stellar population (˜160 Myr). We investigate the physical conditions of the ionized gas in COSMOS-1908 and find that this galaxy has a high ionization parameter, little nebular reddening (E{(B-V)}{{gas}}\\lt 0.14), and a high electron density ({n}e˜ 500 cm-3). We compare the ratios of strong oxygen, neon, and hydrogen lines to the direct-method oxygen abundance for COSMOS-1908 and additional star-forming galaxies at z=0-1.8 with [O iii]λ4363 measurements and show that galaxies at z˜ 1{--}3 follow the same strong-line correlations as galaxies in the local universe. This agreement suggests that the relationship between ionization parameter and O/H is similar for z˜ 0 and high-redshift galaxies. These results imply that metallicity calibrations based on lines of oxygen, neon, and hydrogen do not strongly evolve with redshift and can reliably estimate abundances out to z˜ 3, paving the way for robust measurements of the evolution of the mass-metallicity relation to high redshift. Based on data obtained at the W.M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California, and NASA, and was made possible by the generous financial support of the W.M. Keck Foundation.

  9. K(+) channel activity and redox status are differentially required for JNK activation by UV and reactive oxygen species.

    PubMed

    Gao, Jie; Wu, Dan; Guo, Taylor B; Ruan, Qin; Li, Tie; Lu, Zhenyu; Xu, Ming; Dai, Wei; Lu, Luo

    2004-07-15

    Upon exposure to ultraviolet (UV) radiation, osmotic changes or the presence of reactive oxygen species (ROS) c-Jun N-terminal kinases (JNKs) are rapidly activated. Extensive studies have elucidated molecular components that mediate the activation of JNKs. However, it remains unclear whether activation of JNKs by various stress signals involves different pathways. Here we show that K(+) channel activity is involved in mediating apoptosis induced by UV but not by H(2)O(2) in myelocytic leukemic ML-1 cells. Specifically, JNKs were rapidly phosphorylated upon treatment of ML-1 cells with UV and H(2)O(2). UV-induced, but not H(2)O(2)-induced, JNK-1 phosphorylation was inhibited by pretreatment with 4-aminopyridine (4-AP), a K(+) channel blocker. 4-AP also blocked UV-induced increase in JNK activity as well as p38 phosphorylation. Immunofluorescent microscopy revealed that phosphorylated JNKs were concentrated at centrosomes in ML-1 cells and that these proteins underwent rapid subcellular translocation upon UV treatment. Consistently, the subcellular translocation of JNKs induced by UV was largely blocked by 4-AP. Furthermore, UV-induced JNK activation was blocked by NEM, a sulfhydryl alkylating agent also affecting K(+) current. Both UV- and H(2)O(2)-induced JNK activities were inhibited by glutathione, suggesting that the redox status does play an important role in the activation of JNKs. Taken together, our findings suggest that JNK activation by UV and H(2)O(2) is mediated by distinct yet overlapping pathways and that K(+) channel activity and redox status are differentially required for UV- and H(2)O(2)-induced activation of JNKs.

  10. Reactive Oxygen Species and Nuclear Factor Erythroid 2-Related Factor 2 Activation in Diabetic Nephropathy: A Hidden Target

    PubMed Central

    Abdo, Shaaban; Zhang, Shao-Ling; Chan, John S.D.

    2015-01-01

    Hyperglycemia, oxidative stress and renin-angiotensin system (RAS) dysfunction have been implicated in diabetic nephropathy (DN) progression, but the underlying molecular mechanisms are far from being fully understood. In addition to the systemic RAS, the existence of a local intrarenal RAS in renal proximal tubular cells has been recognized. Angiotensinogen is the sole precursor of all angiotensins (Ang). Intrarenal reactive oxygen species (ROS) generation, Ang II level and RAS gene expression are up-regulated in diabetes, indicating that intrarenal ROS and RAS activation play an important role in DN. The nuclear factor erythroid 2-related factor 2 (Nrf2)-Kelch-like ECH-associated protein 1 (Keap1) pathway is one of the major protective processes that occurs in response to intracellular oxidative stress. Nrf2 stimulates an array of antioxidant enzymes that convert excessive ROS to less reactive or less damaging forms. Recent studies have, however, revealed that Nrf2 activation might have other undesirable effects in diabetic animals and in diabetic patients with chronic kidney disease. This mini-review summarizes current knowledge of the relationship between ROS, Nrf2 and intra renal RAS activation in DN progression as well as possible novel target(s) for DN treatment. PMID:26213634

  11. Activation of NF-kappa B by reactive oxygen intermediates in the nervous system.

    PubMed

    Kaltschmidt, B; Sparna, T; Kaltschmidt, C

    1999-01-01

    Nuclear factor kappa B (NF-kappa B) is a transcription factor crucially involved in glial and neuronal function. NF-kappa B is ubiquitously distributed within the nervous system, and its inducible activity can be discerned from constitutive activity. Prototypic inducible NF-kappa B in the nervous system is composed of the DNA-binding subunits p50 and p65 complexed with an inhibitory I kappa B-alpha molecule. A number of signals from the cell surface can lead to rapid activation of NK-kappa B, thus releasing the inhibition by I kappa B. This activates translocation of NF-kappa B to the nucleus, where it binds to kappa B motifs of target genes and activates transcription. Previous findings have identified reactive oxygen intermediates (ROI) as a common denominator of NF-kappa B activating signals. More specifically, hydrogen peroxide (H2O2) might be used as second messenger in the NF-kappa B system, despite its cytotoxicity. Analysis of pathways leading to NF-kappa B activation in the nervous system has identified a number of ROI-dependent pathways such as cytokine- and neurotrophin-mediated activation, glutamatergic signal transduction, and various diseases with crucial ROI involvement (e.g., Alzheimer's disease, Parkinson's disease, experimental autoimmune encephalomyelitis, multiple sclerosis, amyotrophic lateral sclerosis, and injury). A number of NF-kappa B-specific target genes contribute to the production of ROI or are involved in detoxification of ROIs. In this review, possible mechanisms and regulatory pathways of ROI-mediated NF-kappa B activation are discussed.

  12. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGES

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; et al

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  13. Complement activation by in vivo neonatal and in vitro extracorporeal membrane oxygenation.

    PubMed Central

    Graulich, Johannes; Sonntag, Joseph; Marcinkowski, Monika; Bauer, Karl; Kössel, Hans; Bührer, Christoph; Obladen, Michael; Versmold, Hans T

    2002-01-01

    Complment activation during extracorporeal membrane oxygenation (ECMO) in newborns can be caused by both the underlying disease processes and by blood contact with the ECMO circuit. We investigated the relative importance of these mechanisms by measuring C3a, C5a and sC5b-9 before, during and after neonatal ECMO in six consecutive newborn patients using enzyme-linked immunoassay. In addition complement activation during in vitro ECMO with repeated flow of the same blood volume was measured using blood from healthy adult donors. C3a increased significantly in vivo after 1 h (from 1035+/-193 to 1865+/-419 microg/l) and in vitro ECMO (from 314+/-75 to 1962+/-1062 microg/l). C5a increased during ECMO without significant differences between in vivo and in vitro activation. In neonatal patients, sC5b-9 rose faster than in vitro, but the rapid increase was also significant for in vitro experiments (in vivo: from 328+/-63 to 1623+/-387 microg/l after 2 h; and in vitro: from 78+/-32 to 453+/-179 microg/l after 8 h). After this initial peak at 1-2 h, complement activation decreased gradually until 2-3 days after the initiation of ECMO. We conclude that in newborns the rapid activation of the complement system after the start of ECMO is predominantly caused by contact with artificial surfaces rather than the patient's underlying disease. PMID:12061426

  14. Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH.

    PubMed

    Han, Binghong; Risch, Marcel; Lee, Yueh-Lin; Ling, Chen; Jia, Hongfei; Shao-Horn, Yang

    2015-09-21

    Perovskite oxides (ABO3) have been studied extensively to promote the kinetics of the oxygen evolution reaction (OER) in alkaline electrolytes. However, developing highly active catalysts for OER at near-neutral pH is desirable for many photoelectrochemical/electrochemical devices. In this paper, we systematically studied the activity and stability of well-known perovskite oxides for OER at pH 7. Previous activity descriptors established for perovskite oxides at pH 13, such as having an eg occupancy close to unity or having an O p-band center close to Fermi level, were shown to scale with OER activity at pH 7. Stability was a greater challenge at pH 7 than at pH 13, where two different modes of instability were identified from combined transmission electron microscopy and density functional theory analyses. Perovskites with O p-band close to Fermi level showed leaching of A-site atoms and surface amorphization under all overpotentials examined at pH 7, while those with O p-band far from Fermi level were stable under low OER current/potential but became unstable at high current/potential accompanied by leaching of B-site atoms. Therefore, efforts are needed to enhance the activity and stability of perovskites against A-site or B-site loss if used at neutral pH. PMID:26271910

  15. Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH.

    PubMed

    Han, Binghong; Risch, Marcel; Lee, Yueh-Lin; Ling, Chen; Jia, Hongfei; Shao-Horn, Yang

    2015-09-21

    Perovskite oxides (ABO3) have been studied extensively to promote the kinetics of the oxygen evolution reaction (OER) in alkaline electrolytes. However, developing highly active catalysts for OER at near-neutral pH is desirable for many photoelectrochemical/electrochemical devices. In this paper, we systematically studied the activity and stability of well-known perovskite oxides for OER at pH 7. Previous activity descriptors established for perovskite oxides at pH 13, such as having an eg occupancy close to unity or having an O p-band center close to Fermi level, were shown to scale with OER activity at pH 7. Stability was a greater challenge at pH 7 than at pH 13, where two different modes of instability were identified from combined transmission electron microscopy and density functional theory analyses. Perovskites with O p-band close to Fermi level showed leaching of A-site atoms and surface amorphization under all overpotentials examined at pH 7, while those with O p-band far from Fermi level were stable under low OER current/potential but became unstable at high current/potential accompanied by leaching of B-site atoms. Therefore, efforts are needed to enhance the activity and stability of perovskites against A-site or B-site loss if used at neutral pH.

  16. Activity and stability of the oxygen evolution reaction on electrodeposited Ru and its thermal oxides

    NASA Astrophysics Data System (ADS)

    Kim, Jin Yeong; Choi, Jihui; Kim, Ho Young; Hwang, Eunkyoung; Kim, Hyoung-Juhn; Ahn, Sang Hyun; Kim, Soo-Kil

    2015-12-01

    The activity and stability of Ru metal and its thermal oxide films for the oxygen evolution reaction (OER) were investigated. The metallic Ru films were prepared by electrodeposition on a Ti substrate and then thermally oxidized at various temperatures under atmospheric conditions. During long-term operation of the OER with cyclic voltammetry (CV) in H2SO4 electrolyte, changes in the properties of the Ru and its thermal oxides were monitored in terms of their morphology, crystal structure, and electronic structure. In the initial stages of the OER, all of the Ru thermal oxide films underwent an activation process that was related to the continuous removal of low-activity Ru oxides from the surface. With further cycling, the OER activity decreased. The rate of decrease was different for each Ru film and was related to the annealing temperatures. Monitoring of material properties indicates that the amount of stable anhydrous RuO2 is important for OER stability because it prevents both the severe dissolution of metallic Ru beneath the oxide surface and the formation of a less active hydrous RuO2 at the surface.

  17. Different activation of ERK1/2 and p38 with hyperbaric oxygen in dorsal root ganglion.

    PubMed

    Li, Kai-Cheng; Bao, Xiao-Chen; Fang, Yi-Qun; Ma, Jun; Meng, Miao; Chen, Hai-Ting; Li, Chi

    2011-01-01

    Prolonged hyperbaric oxygen exposure causes pulmonary and nervous system toxicity, although hyperbaric oxygen treatment has been used to treat a broad spectrum of ailments. In the current study, animals have been exposed to 100% oxygen at a pressure of 2.3 atmospheres absolute (ATA) for two, six and 10 hours or 0.23 MPa normoxic hyperbaric nitrogen (N2-O2 mixture, oxygen partial pressure = 21 kPa) for 10 hours. Then we investigated whether ERK1/2 and p38 had been activated in the dorsal root ganglion (DRG) by hyperbaric conditions. Using Western blot analysis, we found that the phosphorylation levels of ERK1/2 (phospho-ERK1/2) increased significantly (p < 0.05, n = 3 for each group) in the six-hour treatment of 100% oxygen at a pressure of 2.3 ATA. The phosphorylation levels of p38 (phospho-p38) increased significantly (p < 0.05, n = 3 for each group) in the 10-hour treatment of 100% oxygen at a pressure of 2.3 ATA--which was consistent with time course changes of an apoptosis marker, cleavage caspase-3--while the phospho-p38 decreased in the 10 hours of N2-O2 mixture. These results demonstrate that the ERK1/2 and p38 have been differently activated in the DRG by prolonged hyperbaric oxygen exposure.

  18. A method to determine photosynthetic activity from oxygen microsensor data in biofilms subjected to evaporation.

    PubMed

    Li, Tong; Podola, Björn; de Beer, Dirk; Melkonian, Michael

    2015-10-01

    Phototrophic biofilms are widely distributed in nature and their ecological importance is well recognized. More recently, there has been a growing interest in using artificial phototrophic biofilms in innovative photobioreactors for production of microalgal biomass in biotechnological applications. To study physiological processes within these biofilms, microsensors have been applied in several studies. Here, the 'light-dark shift method' relies on measurement of photosynthetic activity in terms of light-induced oxygen production. However, when applied to non-submerged biofilms that can be found in numerous locations in nature, as well as in some types of photobioreactors, limitations of this approach are obvious due to rapid removal of gaseous species at the biofilm surface. Here, we introduce a mathematical correction to recover the distribution of the actual photosynthetic activity along the depth gradient in the biofilm, based on a numerical solution of the inversed diffusion equation of oxygen. This method considers changes in mass transport during the measurement period as can found on biofilms possessing a thin flow/mass transfer boundary layer (e. g., non-submerged biofilms). Using both simulated and real microsensor data, the proposed method was shown to be much more accurate than the classical method, which leads to underestimations of rates near the biofilm surface. All test profiles could be recovered with a high fit. According to our simulated microsensor measurements, a depth resolution of ≤20 μm is recommended near the surface. We conclude that our method strongly improves the quality of data acquired from light-dark measurements of photosynthetic activity in biofilms.

  19. Tumour-promoting activity of polycyclic aromatic hydrocarbons and their oxygenated or nitrated derivatives.

    PubMed

    Misaki, Kentaro; Takamura-Enya, Takeji; Ogawa, Hideoki; Takamori, Kenji; Yanagida, Mitsuaki

    2016-03-01

    Various types of polycyclic aromatic compounds (PACs) in diesel exhaust particles are thought to contribute to carcinogenesis in mammals. Although the carcinogenicity, mutagenicity and tumour-initiating activity of these compounds have been evaluated, their tumour-promoting activity is unclear. In the present study, to determine the tumour-inducing activity of PACs, including previously known mutagenic compounds in atmospheric environments, a transformation assay for promoting activity mediated by the release of contact inhibition was conducted for six polycyclic aromatic hydrocarbons (PAHs), seven oxygenated PAHs (oxy-PAHs) and seven nitrated PAHs (nitro-PAHs) using mouse embryonic fibroblast cells transfected with the v-Ha-ras gene (Bhas 42 cells). Of these, two PAHs [benzo[k]fluoranthene (B[k]FA) and benzo[b]fluoranthene (B[b]FA)], one oxy-PAH [6H-benzo[cd]pyren-6-one (BPO)] and two nitro-PAHs (3-nitro-7H-benz[de]anthracen-7-one and 6-nitrochrysene) were found to exhibit particularly powerful tumour-promoting activity (≥10 foci following exposure to <100nM). In addition, clear mRNA expression of CYP1A1, which is associated with aryl hydrocarbon receptor (AhR)-mediated activation, was observed following the exposure of cells to two PAHs (B[k]FA and B[b]FA) and three oxy-PAHs (1,2-naphthoquinone, 11H-benzo[b]fluoren-11-one and BPO). Further, an HO-1 antioxidant response activation was observed following exposure to B[k]FA, B[b]FA and BPO, suggesting that the induction of tumour-promoting activity in these compounds is correlated with the dysfunction of signal transduction via AhR-mediated responses and/or oxidative stress responses.

  20. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene.

    PubMed

    Hao, Yufeng; Wang, Lei; Liu, Yuanyue; Chen, Hua; Wang, Xiaohan; Tan, Cheng; Nie, Shu; Suk, Ji Won; Jiang, Tengfei; Liang, Tengfei; Xiao, Junfeng; Ye, Wenjing; Dean, Cory R; Yakobson, Boris I; McCarty, Kevin F; Kim, Philip; Hone, James; Colombo, Luigi; Ruoff, Rodney S

    2016-05-01

    Bernal (AB)-stacked bilayer graphene (BLG) is a semiconductor whose bandgap can be tuned by a transverse electric field, making it a unique material for a number of electronic and photonic devices. A scalable approach to synthesize high-quality BLG is therefore critical, which requires minimal crystalline defects in both graphene layers and maximal area of Bernal stacking, which is necessary for bandgap tunability. Here we demonstrate that in an oxygen-activated chemical vapour deposition (CVD) process, half-millimetre size, Bernal-stacked BLG single crystals can be synthesized on Cu. Besides the traditional 'surface-limited' growth mechanism for SLG (1st layer), we discovered new microscopic steps governing the growth of the 2nd graphene layer below the 1st layer as the diffusion of carbon atoms through the Cu bulk after complete dehydrogenation of hydrocarbon molecules on the Cu surface, which does not occur in the absence of oxygen. Moreover, we found that the efficient diffusion of the carbon atoms present at the interface between Cu and the 1st graphene layer further facilitates growth of large domains of the 2nd layer. The CVD BLG has superior electrical quality, with a device on/off ratio greater than 10(4), and a tunable bandgap up to ∼100 meV at a displacement field of 0.9 V nm(-1). PMID:26828845

  1. Changes in cerebral blood oxygenation induced by active standing test in children with POTS and NMS.

    PubMed

    Endo, Ayumi; Fujita, Yukihiko; Fuchigami, Tatsuo; Takahashi, Shori; Mugishima, Hideo; Skatani, Kaoru

    2014-01-01

    Orthostatic dysregulation (OD) has been classified into subtypes by heart rate and blood pressure; however, the hemodynamics of brains have not yet been revealed. Therefore, we investigated changes in cerebral blood flow and oxygenation during an active standing test to clarify the pathophysiology of two subtypes: postural tachycardia syndrome (POTS) and neurally mediated syncope (NMS). We studied 31 children (15 boys, 16 girls; mean age, 14.0 ± 1.7 years) who presented with OD at the Department of Pediatrics and Child Health, Nihon University School of Medicine between 2009 and 2011. OD was diagnosed using the Japanese clinical guidelines for juvenile orthostatic dysregulation. After a 10-min resting period in the supine position, patients were asked to quickly stand up and keep upright for 10 min. Cerebral blood flow and cerebral oxygenation were measured using transcranial Doppler sonography and near-infrared spectroscopy. POTS showed a significant decrease of oxy-Hb and resistance index (RI), suggesting transient ischemia with maintainable cerebral autoregulation. NMS showed a decrease of oxy-Hb and an increase of RI, suggesting ischemia and impairment of autoregulation.

  2. Abundance ratios of oxygen, neon, and magnesium in solar active regions and flares: The FIP effect

    NASA Technical Reports Server (NTRS)

    Widing, K. G.; Feldman, U.

    1995-01-01

    Relative abundances of oxygen, neon, and magnesium have been derived for a sample of nine solar active regions, flares, and an erupting prominance by combining plots of the ion differential emission measures. The observations were photographed in the 300-600 A range by the Naval Research Laboratory (NRL) spectroheliograph on Skylab. Methods for deriving the Mg/Ne abundance ratio-which measures the separation between the low- first ionization potential (FIP) and high-FIP abundnace plateaus-have been described in previous papers. In this paper we describe the spectroscopic methods for deriving the O/Ne abundance ratio, which gives the ratio between two high-FIP elements. The plot of the O/Ne ratio versus the Mg/Ne ratio in the sample of nine Skylab events is shown. The variation in the Mg/Ne ratio by a factor of 6 is associated with a much smaller range in the O/Ne ratio. This is broadly consistent with the presence of the standard FIP pattern of abundances in the outer atmosphere of the Sun. However, a real change in the relative abundances of oxygen and neon by a factor of 1.5 cannot be excluded.

  3. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene.

    PubMed

    Hao, Yufeng; Wang, Lei; Liu, Yuanyue; Chen, Hua; Wang, Xiaohan; Tan, Cheng; Nie, Shu; Suk, Ji Won; Jiang, Tengfei; Liang, Tengfei; Xiao, Junfeng; Ye, Wenjing; Dean, Cory R; Yakobson, Boris I; McCarty, Kevin F; Kim, Philip; Hone, James; Colombo, Luigi; Ruoff, Rodney S

    2016-05-01

    Bernal (AB)-stacked bilayer graphene (BLG) is a semiconductor whose bandgap can be tuned by a transverse electric field, making it a unique material for a number of electronic and photonic devices. A scalable approach to synthesize high-quality BLG is therefore critical, which requires minimal crystalline defects in both graphene layers and maximal area of Bernal stacking, which is necessary for bandgap tunability. Here we demonstrate that in an oxygen-activated chemical vapour deposition (CVD) process, half-millimetre size, Bernal-stacked BLG single crystals can be synthesized on Cu. Besides the traditional 'surface-limited' growth mechanism for SLG (1st layer), we discovered new microscopic steps governing the growth of the 2nd graphene layer below the 1st layer as the diffusion of carbon atoms through the Cu bulk after complete dehydrogenation of hydrocarbon molecules on the Cu surface, which does not occur in the absence of oxygen. Moreover, we found that the efficient diffusion of the carbon atoms present at the interface between Cu and the 1st graphene layer further facilitates growth of large domains of the 2nd layer. The CVD BLG has superior electrical quality, with a device on/off ratio greater than 10(4), and a tunable bandgap up to ∼100 meV at a displacement field of 0.9 V nm(-1).

  4. [Active oxygen species of Co-V-O catalysts in propane oxidative dehydrogenation analyzed by FTIR and XPS spectra].

    PubMed

    Xu, Ai-Ju; Lin, Qin; Bao, Zhaorigetu; Jia, Mei-Lin; Liu, Lian-Yun

    2009-02-01

    A series of Co-V-O (meta-CoV2O6, pyro-Co2 V2 O7, and ortho-Co3 V2 O8) catalysts were prepared by microwave oxalate co-precipitation method and characterized by (XRD), TEM, BET, FTIR, XPS, H2-TPR and conductivity measurement. The catalytic characters of the catalysts for propane oxidative dehydrogenation were investigated. The FTIR spectra of catalysts were obtained in the range of 400-1 100 cm(-1) and their major bands were assigned. The peak separation fitting of O(1s) XPS spectra was carried out and the quantity of oxygen species was calculated. The results of XRD characterization showed that pure meta-CoV2O6, pyro-Co2 V2O7, and ortho-Co3 V2O8 with nice structure were obtained. The TEM images demonstrated that the catalysts showed uniform particle with the mean particle size of 20-30 nm. The diagram of the relationship between electrical conductivity and oxygen partial pressure of Co3V2O8 and Co2 V2O7 showed dsigma/dPo2 > 0, which implied that these were p-type semiconductor, and CoV2O6 reverse showed dsigma/dPo2 < 0, which implied n-type semiconductor. 48.12%, 47.82% and 35.24% of C3 H6 selectivities were obtained for p-type semiconductor Co3 V2O8, CO2 V2O7 and n-type CoV2O6 catalysts respectively at 10% C3H6 conversion, and the results showed that p-type semiconductor catalysts Co3 V2O8 and Co2 V2O7 showed higher activity than n-type catalyst CoV2O6. The results of FTIR, XPS, H2-TPR and conductivity measurement indicated that transferring between non-stoichiometric and lattice oxygen that easily happened in Co3 V2O8 and Co2 V2O7 catalysts might promote the oxidation-reduction reaction between different valence vanadium species, and promoted the oxygen vacancy formation. Furthermore, the forming of Co-O-V bridge bond that was easy to shift between Co and V increased the mobile oxygen species of O2-, O2(2-) and O- and made the redox reaction among different valence V be realized. It is concluded that high catalytic properties of p-type semiconductor Co3 V2O8 and

  5. Low Oxygen Tension Enhances Expression of Myogenic Genes When Human Myoblasts Are Activated from G0 Arrest

    PubMed Central

    Sellathurai, Jeeva; Nielsen, Joachim; Hejbøl, Eva Kildall; Jørgensen, Louise Helskov; Dhawan, Jyotsna; Nielsen, Michael Friberg Bruun; Schrøder, Henrik Daa

    2016-01-01

    Objectives Most cell culture studies have been performed at atmospheric oxygen tension of 21%, however the physiological oxygen tension is much lower and is a factor that may affect skeletal muscle myoblasts. In this study we have compared activation of G0 arrested myoblasts in 21% O2 and in 1% O2 in order to see how oxygen tension affects activation and proliferation of human myoblasts. Materials and Methods Human myoblasts were isolated from skeletal muscle tissue and G0 arrested in vitro followed by reactivation at 21% O2 and 1% O2. The effect was assesses by Real-time RT-PCR, immunocytochemistry and western blot. Results and Conclusions We found an increase in proliferation rate of myoblasts when activated at a low oxygen tension (1% O2) compared to 21% O2. In addition, the gene expression studies showed up regulation of the myogenesis related genes PAX3, PAX7, MYOD, MYOG (myogenin), MET, NCAM, DES (desmin), MEF2A, MEF2C and CDH15 (M-cadherin), however, the fraction of DES and MYOD positive cells was not increased by low oxygen tension, indicating that 1% O2 may not have a functional effect on the myogenic response. Furthermore, the expression of genes involved in the TGFβ, Notch and Wnt signaling pathways were also up regulated in low oxygen tension. The differences in gene expression were most pronounced at day one after activation from G0-arrest, thus the initial activation of myoblasts seemed most sensitive to changes in oxygen tension. Protein expression of HES1 and β-catenin indicated that notch signaling may be induced in 21% O2, while the canonical Wnt signaling may be induced in 1% O2 during activation and proliferation of myoblasts. PMID:27442119

  6. 76 FR 66944 - Agency Information Collection Activities: Form I-914; Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-28

    ... Information Collection Under Review: Form I- 914 and Supplements A and B, Application for T Nonimmigrant... required to respond, as well as a brief abstract: Primary: Individuals or households. Form I- 914 permits... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form...

  7. 76 FR 24908 - Agency Information Collection Activities: Form G-639; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-03

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  8. 76 FR 28444 - Agency Information Collection Activities: Form G-884, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-17

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form G-884... information collection under review: Form G- 884, Request for the Return of Original Documents; OMB Control No... July 18, 2011. During this 60-day period, USCIS will be evaluating whether to revise the Form...

  9. 75 FR 23785 - Agency Information Collection Activities: Form G-639; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-05-04

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form G-639... Collection Under Review; Form G- 639, Freedom of Information/Privacy Act Request; OMB Control No. 1615- 0102... this 60 day period, USCIS will be evaluating whether to revise the Form G-639. Should USCIS decide...

  10. 75 FR 5099 - Agency Information Collection Activities: Form N-648, Revision of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-01

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  11. 76 FR 38197 - Agency Information Collection Activities; Form N-600K, Revision of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-29

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  12. 76 FR 59710 - Agency Information Collection Activities: Form N-600; Revision of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-27

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  13. 75 FR 13776 - Agency Information Collection Activities: Form N-300; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-23

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-300... Collection Under Review; Form N- 300, Application to File Declaration of Intention; OMB Control No. 1615-0078... this 60-day period, USCIS will be evaluating whether to revise the Form N-300. Should USCIS decide...

  14. 75 FR 18871 - Agency Information Collection Activities: Form N-600K, Revision of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-13

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-600K... Information Collection under Review: Form N- 600K, Application for Citizenship and Issuance of Certificate...: Form N-600K, U.S. Citizenship and Immigration Services. (4) Affected public who will be asked...

  15. Composition and topology of activity cliff clusters formed by bioactive compounds.

    PubMed

    Stumpfe, Dagmar; Dimova, Dilyana; Bajorath, Jürgen

    2014-02-24

    The assessment of activity cliffs has thus far mostly focused on compound pairs, although the majority of activity cliffs are not formed in isolation but in a coordinated manner involving multiple active compounds and cliffs. However, the composition of coordinated activity cliff configurations and their topologies are unknown. Therefore, we have identified all activity cliff configurations formed by currently available bioactive compounds and analyzed them in network representations where activity cliff configurations occur as clusters. The composition, topology, frequency of occurrence, and target distribution of activity cliff clusters have been determined. A limited number of large cliff clusters with unique topologies were identified that were centers of activity cliff formation. These clusters originated from a small number of target sets. However, most clusters were of small to moderate size. Three basic topologies were sufficient to describe recurrent activity cliff cluster motifs/topologies. For example, frequently occurring clusters with star topology determined the scale-free character of the global activity cliff network and represented a characteristic activity cliff configuration. Large clusters with complex topology were often found to contain different combinations of basic topologies. Our study provides a first view of activity cliff configurations formed by currently available bioactive compounds and of the recurrent topologies of activity cliff clusters. Activity cliff clusters of defined topology can be selected, and from compounds forming the clusters, SAR information can be obtained. The SAR information of activity cliff clusters sharing a/one specific activity and topology can be compared.

  16. Cisplatin induces production of reactive oxygen species via NADPH oxidase activation in human prostate cancer cells.

    PubMed

    Itoh, Tomohiro; Terazawa, Riyako; Kojima, Keitaro; Nakane, Keita; Deguchi, Takashi; Ando, Masashi; Tsukamasa, Yasuyuki; Ito, Masafumi; Nozawa, Yoshinori

    2011-09-01

    This study aimed to examine the roles of reactive oxygen species (ROS) in cisplatin treatment of human prostate cancer cells; hormone-sensitive LNCaP and hormone-refractory PC3 and DU145 cells. Intracellular levels of ROS and H(2)O(2) were measured and visualized using specific fluorescent probes. NADPH oxidase (NOX) activity was detected by lucigenin chemiluminescence assay. Expression levels of NOX isoforms were determined by semi-quantitative RT-PCR. Cisplatin treatment increased the intracellular levels of ROS and H(2)O(2) in three prostate cancer cell lines. The increase was transient and robust in hormone-sensitive LNCaP cells compared with hormone-refractory PC3 and DU145 cells. Consistent with these findings, the NOX activity induced by cisplatin was higher in LNCaP cells than in PC3 and DU145 cells. Expression pattern of NOX isoforms varied among three cell lines and the NOX activity was independent of NOX expression. Taken together, we have shown that cisplatin induces production of ROS and H(2)O(2) via NOX activation in human prostate cancer cell lines, which is most prominent in hormone-sensitive LNCaP cells. PMID:21682664

  17. Copper compound induces autophagy and apoptosis of glioma cells by reactive oxygen species and jnk activation

    PubMed Central

    2012-01-01

    Background Glioblastoma multiforme (GBM) is the most aggressive of the primary brain tumors, with a grim prognosis despite intensive treatment. In the past decades, progress in research has not significantly increased overall survival rate. Methods The in vitro antineoplastic effect and mechanism of action of Casiopeina III-ia (Cas III-ia), a copper compound, on rat malignant glioma C6 cells was investigated. Results Cas III-ia significantly inhibited cell proliferation, inducing autophagy and apoptosis, which correlated with the formation of autophagic vacuoles, overexpression of LC3, Beclin 1, Atg 7, Bax and Bid proteins. A decrease was detected in the mitochondrial membrane potential and in the activity of caspase 3 and 8, together with the generation of intracellular reactive oxygen species (ROS) and increased activity of c-jun NH2-terminal kinase (JNK). The presence of 3-methyladenine (as selective autophagy inhibitor) increased the antineoplastic effect of Cas III-ia, while Z-VAD-FMK only showed partial protection from the antineoplastic effect induced by Cas III-ia, and ROS antioxidants (N-acetylcysteine) decreased apoptosis, autophagy and JNK activity. Moreover, the JNK –specific inhibitor SP600125 prevented Cas III-ia-induced cell death. Conclusions Our data suggest that Cas III-ia induces cell death by autophagy and apoptosis, in part due to the activation of ROS –dependent JNK signaling. These findings support further studies of Cas III-ia as candidate for treatment of human malignant glioma. PMID:22540380

  18. Nitrogen-Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction.

    PubMed

    Miura, Akira; Rosero-Navarro, Carolina; Masubuchi, Yuji; Higuchi, Mikio; Kikkawa, Shinichi; Tadanaga, Kiyoharu

    2016-07-01

    The catalytic activity of manganese oxynitrides in the oxygen reduction reaction (ORR) was investigated in alkaline solutions to clarify the effect of the incorporated nitrogen atoms on the ORR activity. These oxynitrides, with rock-salt-like structures with different nitrogen contents, were synthesized by reacting MnO, Mn2 O3 , or MnO2 with molten NaNH2 at 240-280 °C. The anion contents and the Mn valence states were determined by combustion analysis, powder X-ray diffraction, and X-ray absorption near-edge structure analysis. An increase in the nitrogen content of rock-salt-based manganese oxynitrides increases the valence of the manganese ions and reinforces the catalytic activity for the ORR in 1 m KOH solution. Nearly single-electron occupancy of the antibonding eg states and highly covalent Mn-N bonding thus enhance the ORR activity of nitrogen-rich manganese oxynitrides. PMID:27193352

  19. Acute larvicidal activity against mosquitoes and oxygen consumption inhibitory activity of dihydroguaiaretic acid derivatives.

    PubMed

    Nishiwaki, Hisashi; Tabara, Yoshimi; Kishida, Taro; Nishi, Kosuke; Shuto, Yoshihiro; Sugahara, Takuya; Yamauchi, Satoshi

    2015-03-11

    (-)-Dihydroguaiaretic acid (DGA) and its derivatives having 3-hydroxyphenyl (3-OH-DGA) and variously substituted phenyl groups instead of 3-hydroxy-4-methoxyphenyl groups were synthesized to measure their larvicidal activity against the mosquito Culex pipiens Linnaeus, 1758 (Diptera: Culicidae). Compared with DGA and 3-OH-DGA (LC50 (M), 3.52 × 10(-5) and 4.57 × 10(-5), respectively), (8R,8'R)-lignan-3-ol (3) and its 3-Me (10), 2-OH (12), 3-OH (13), and 2-OMe (15) derivatives showed low potency (ca. 6-8 × 10(-5) M). The 4-Me derivative (11) showed the lowest potency (12.1 × 10(-5) M), and the 2-F derivative (4) showed the highest (2.01 × 10(-5) M). All of the synthesized compounds induced an acute toxic symptom against mosquito larvae, with potency varying with the type and position of the substituents. The 4-F derivative (6), which killed larvae almost completely within 45 min, suppressed the O2 consumption of the mitochondrial fraction, demonstrating that this compound inhibited mitochondrial O2 consumption contributing to a respiratory inhibitory activity.

  20. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

  1. Activities of oxygen in liquid Cu-Sb and Cu-Ge alloys

    NASA Astrophysics Data System (ADS)

    Otsuka, Shinya; Matsumura, Yoshihiro; Kozuka, Zensaku

    1982-03-01

    In order to determine the activity coefficients of oxygen, γΩ in liquid Cu-Sb and Cu-Ge alloys at 1373 K as a function of alloy composition, the modified coulometric titrations, described previously, have been performed by using the galvanic cell: O in liquid Cu-Sb or Cu-Ge alloys/ZrO2 (+CaO)/Air, Pt. A pronounced point of inflection in the In γΩ vs alloy composition curve has been observed both for Cu-Sb and Cu-Ge alloys, as predicted by Jacob and Alcock’s quasichemical equation. The measured data itself, however, are significantly different from those predicted by their equation. The validity of Wagner’s solution model with one or two energy parameters has been also tested.

  2. Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters

    SciTech Connect

    Esswein, AJ; Surendranath, Y; Reece, SY; Nocera, DG

    2011-02-01

    A high surface area electrode is functionalized with cobalt-based oxygen evolving catalysts (Co-OEC = electrodeposited from pH 7 phosphate, Pi, pH 8.5 methylphosphonate, MePi, and pH 9.2 borate electrolyte, Bi). Co-OEC prepared from MePi and operated in Pi and Bi achieves a current density of 100 mA cm(-2) for water oxidation at 442 and 363 mV overpotential, respectively. The catalyst retains activity in near-neutral pH buffered electrolyte in natural waters such as those from the Charles River (Cambridge, MA) and seawater (Woods Hole, MA). The efficacy and ease of operation of anodes functionalized with Co-OEC at appreciable current density together with its ability to operate in near neutral pH buffered natural water sources bodes well for the translation of this catalyst to a viable renewable energy storage technology.

  3. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA were more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.

  4. Short Self-Assembling Peptides Are Able to Bind to Copper and Activate Oxygen.

    PubMed

    Makhlynets, Olga V; Gosavi, Pallavi M; Korendovych, Ivan V

    2016-07-25

    We have shown that de novo designed peptides self-assemble in the presence of copper to create supramolecular assemblies capable of carrying out the oxidation of dimethoxyphenol in the presence of dioxygen. Formation of the supramolecular assembly, which is akin to a protein fold, is critical for productive catalysis since peptides possessing the same functional groups but lacking the ability to self-assemble do not catalyze substrate oxidation. The ease with which we have discovered robust and productive oxygen activation catalysts suggests that these prion-like assemblies might have served as intermediates in the evolution of enzymatic function and opens the path for the development of new catalyst nanomaterials. PMID:27276534

  5. EFFECT OF MOLECULAR OXYGEN ON ADSORPTIVE CAPACITY AND EXTRACTION EFFICIENCY OF GRANULATED ACTIVATED CARBON FOR THREE ORTHO-SUBSTITUTED PHENOLS

    EPA Science Inventory

    Adsorptive capacity of activated carbon for several organic compounds was found to be strongly influenced by the presence of molecular oxygen. This influence is manifested by the polymerization of adsorbate on the surface of activated carbon. As a result, GAC exhibits much high...

  6. Regulation of IDO activity by oxygen supply: inhibitory effects on antimicrobial and immunoregulatory functions.

    PubMed

    Schmidt, Silvia K; Ebel, Sebastian; Keil, Eric; Woite, Claudia; Ernst, Joachim F; Benzin, Anika E; Rupp, Jan; Däubener, Walter

    2013-01-01

    Tryptophan is an essential amino acid for human beings as well as for some microorganisms. In human cells the interferon-γ (IFN-γ) inducible enzyme indoleamine 2,3-dioxygenase (IDO) reduces local tryptophan levels and is therefore able to mediate broad-spectrum effector functions: IDO activity restricts the growth of various clinically relevant pathogens such as bacteria, parasites and viruses. On the other hand, it has been observed that IDO has immunoregulatory functions as it efficiently controls the activation and survival of T-cells. Although these important effects have been analysed in much detail, they have been observed in vitro using cells cultured in the presence of 20% O₂ (normoxia). Such high oxygen concentrations are not present in vivo especially within infected and inflamed tissues. We therefore analysed IDO-mediated effects under lower oxygen concentrations in vitro and observed that the function of IDO is substantially impaired in tumour cells as well as in native cells. Hypoxia led to reduced IDO expression and as a result to reduced production of kynurenine, the downstream product of tryptophan degradation. Consequently, effector functions of IDO were abrogated under hypoxic conditions: in different human cell lines such as tumour cells (glioblastoma, HeLa) but also in native cells (human foreskin fibroblasts; HFF) IDO lost the capacity to inhibit the growth of bacteria (Staphylococcus aureus), parasites (Toxoplasma gondii) or viruses (herpes simplex virus type 1). Additionally, IDO could no longer efficiently control the proliferation of T-cells that have been co-cultured with IDO expressing HFF cells in vitro. In conclusion, the potent antimicrobial as well as immunoregulatory functions of IDO were substantially impaired under hypoxic conditions that pathophysiologically occurs in vivo.

  7. Labor Contractions Enhance Oxygenation and Behavioral Activity of Newborn Rat Pups

    NASA Technical Reports Server (NTRS)

    Mills, N. A.; Baer, L. A.; Ronca, A. E.; Balton, Bonnie (Technical Monitor)

    2002-01-01

    Labor contractions help instigate behavioral responses at birth (viz., breathing and suckling) that are vital for the newborn's adaptation to the extrauterine world (Ronca et al., 1996). In the present study, we analyzed the role of labor contractions in postpartum oxygenation and behavioral activity of newborn rat pups. Newborns were observed following either vaginal (V) or cesarean delivery. For cesarean delivery, day 21 pregnant dams' were administered a spinal transaction to eliminate lower body sensation, a laparotomy was performed and the uterus was maintained in a heated (37.5 C) bath. Four rat fetuses in one of the dams' paired uterine horn were compressed (C) to Simulate labor contractions (20 sec/min for 10 min) while four fetuses in the opposite horn were not compressed (NC). Fetuses were surgically removed from the uterus, stroked with a soft brush to mimic postnatal licking by the dam, the umbilical cord occluded. Pups were exposed to room temperature (22 C) for one hr, then nest temperature (33 C) for one hr. PO2, CO2, and O2, saturation were determined at 0, 30, 60, or 120 min post delivery using a blood gas analyzer. V and C delivered neonates showed comparable rates of PO2, CO2 and O2 saturation whereas NC neonates showed depressed levels at all time points (p<0.05). Respiratory rates of V, C and NC neonates increased significantly (p<0.05) over the first two postpartum hrs and did not differ across groups. Postpartum behavioral activity was significantly greater in V and C conditions and positively correlated with postnatal oxygenation. These findings provide further evidence for importance of labor contractions in early postpartum adaptation.

  8. Shoulder and forearm oxygenation and myoelectric activity in patients with work-related muscle pain and healthy subjects.

    PubMed

    Elcadi, Guilherme H; Forsman, Mikael; Aasa, Ulrika; Fahlstrom, Martin; Crenshaw, Albert G

    2013-05-01

    We tested hypotheses of (a) reduced oxygen usage, oxygen recovery, blood flow and oxygen consumption; and (b) increased muscle activity for patients diagnosed with work-related muscle pain (WRMP) in comparison to healthy controls. Oxygenation was measured with near infrared spectroscopy (NIRS), and muscle activity with EMG for the extensor carpi radialis (ECR) and trapezius descendens (TD) muscles. Eighteen patients with diffuse neck-shoulder-arm pain and 17 controls (matched in age and sex) were equipped with NIRS and EMG probes. After determining an individual's maximum voluntary contraction (MVC) force, short-term (20 s) isometric contractions for the ECR and TD of 10, 30, 50 and 70 % MVC generated ∆StO₂ and StO₂% recovery (Rslope) from NIRS, and RMS%max from EMG signals. In addition, upper arm venous (VO) and arterial (AO) occlusions generated slopes of total hemoglobin (HbTslope) and deoxyhemoglobin (HHbslope) for the resting ECR as surrogates of blood flow and oxygen consumption, respectively. Mixed model analyses, t tests, and Mann-Whitney test were used to assess differences between groups. There was no significant difference in MVC between groups for either muscle. Also, ∆StO₂%, Rslope for either muscle, and ECR-HbTslope were not different between groups, thus our hypotheses of reduced oxygen use, recovery, and blood flow for patients were not confirmed. However, patients had a significantly lower ECR-HHbslope confirming our hypothesis of reduced consumption. Further, there was no difference in RMS%max during contractions meaning that the hypothesis of increased activity for patients was not confirmed. When taking into account the number of NIRS variables studied, differences we found between our patient group and healthy controls (i.e., in forearm oxygen consumption and shoulder oxygen saturation level) may be considered modest. Overall our findings may have been impacted by the fact that our patients and controls were similar in muscle strength

  9. Effects of oxygen functional groups on the enhancement of the hydrogen spillover of Pd-doped activated carbon.

    PubMed

    Chung, Tsui-Yun; Tsao, Cheng-Si; Tseng, Hui-Ping; Chen, Chien-Hung; Yu, Ming-Sheng

    2015-03-01

    The hydrogen storage performance of Pd-doped oxidized activated carbon (Pd/AC-ox) with various oxygen contents or functional groups was investigated. The surface chemistry of the Pd/AC-ox sample was modified by treatment with hydrogen gas. Temperature-programmed desorption was performed to characterize the oxygen functional groups in each sample. In this study, low- and high-pressure hydrogen adsorption isotherm experiments were conducted using a static volumetric measurement at room temperature (RT) and pressures of up to 8 MPa. The results showed that increasing the oxygen content and functional groups on the surface of the Pd/AC-ox significantly improved the reversible RT hydrogen storage capacity due to the spillover effect. The hydrogen spillover enhancement factors at 0.12 MPa were greater than 100% for all samples. The hydrogen uptake of Pd/AC-ox1 at RT and 8 MPa with an oxygen content of 8.94 wt.% was 0.37 wt.%, which was 48% greater than that of Pd-free AC-ox (0.25 wt.%). In addition, the hydrogen uptake of Pd/AC-ox3 with lower oxygen contents demonstrates that the hydrogen spillover enhancement gradually disappears when the pressure is increased to more than 2 MPa (i.e., a transition from spillover to physisorption). The surface diffusion, or reversible adsorption, of the spiltover H atoms, which is enhanced by oxygen functional groups, was affected by a threshold amount of oxygen groups (such as hydroxyl groups). PMID:25490569

  10. Mesoscale Activity and Nitrogen-loss in the Oxygen Minimum Zone of the Eastern Tropical Pacific During ENSO Conditions

    NASA Astrophysics Data System (ADS)

    Montes, I.; Dewitte, B.; Gutknecht, E.; Paulmier, A.; Dadou, I.; Oschlies, A.; Garçon, V. C.

    2015-12-01

    The Eastern Tropical South Pacific encompasses one of the most extended Oxygen Minimum zones, which is mainly maintained by a combination of sluggish circulation and high biological productivity in the surface layer leading to elevate organic matter decomposition consuming dissolved oxygen. Low-oxygen areas are important not only for macroorganisms that cannot survive in oxygen-poor conditions, but also because of special biogeochemical processes occurring at low oxygen concentrations. In particular, a large fraction of oceanic nitrogen-loss occurs in these areas via anaerobic microbial processes. These include denitrification and axammox that both lead to a net loss of fixed nitrogen once oxygen concentrations have fallen below some threshold of a few umol/l. Recently it has been found that eddies may act as nitrogen-loss hotspots, possibly by shielding enclosed water parcels from lateral mixing with better ventilated oxygen-richer waters outside the eddies. Here we used a regional coupled biogeochemical model to investigate the relationship between eddies and the nitrogen-loss. We also investigate the mechanisms responsible for the generation of eddies and for possible modulations of eddy activity on interannual timescales, in particular during cold and warm phases of the El Nino Southern Oscillation.

  11. Leinamycin E1 acting as an anticancer prodrug activated by reactive oxygen species

    PubMed Central

    Huang, Sheng-Xiong; Yun, Bong-Sik; Ma, Ming; Basu, Hirak S.; Church, Dawn R.; Ingenhorst, Gudrun; Huang, Yong; Yang, Dong; Lohman, Jeremy R.; Tang, Gong-Li; Ju, Jianhua; Liu, Tao; Wilding, George; Shen, Ben

    2015-01-01

    Leinamycin (LNM) is a potent antitumor antibiotic produced by Streptomyces atroolivaceus S-140, featuring an unusual 1,3-dioxo-1,2-dithiolane moiety that is spiro-fused to a thiazole-containing 18-membered lactam ring. Upon reductive activation in the presence of cellular thiols, LNM exerts its antitumor activity by an episulfonium ion-mediated DNA alkylation. Previously, we have cloned the lnm gene cluster from S. atroolivaceus S-140 and characterized the biosynthetic machinery responsible for the 18-membered lactam backbone and the alkyl branch at C3 of LNM. We now report the isolation and characterization of leinamycin E1 (LNM E1) from S. atroolivacues SB3033, a ΔlnmE mutant strain of S. atroolivaceus S-140. Complementary to the reductive activation of LNM by cellular thiols, LNM E1 can be oxidatively activated by cellular reactive oxygen species (ROS) to generate a similar episulfonium ion intermediate, thereby alkylating DNA and leading to eventual cell death. The feasibility of exploiting LNM E1 as an anticancer prodrug activated by ROS was demonstrated in two prostate cancer cell lines, LNCaP and DU-145. Because many cancer cells are under higher cellular oxidative stress with increased levels of ROS than normal cells, these findings support the idea of exploiting ROS as a means to target cancer cells and highlight LNM E1 as a novel lead for the development of anticancer prodrugs activated by ROS. The structure of LNM E1 also reveals critical new insights into LNM biosynthesis, setting the stage to investigate sulfur incorporation, as well as the tailoring steps that convert the nascent hybrid peptide–polyketide biosynthetic intermediate into LNM. PMID:26056295

  12. Effect of dissolved oxygen and temperature on macromolecular composition and PHB storage of activated sludge.

    PubMed

    Reyes, Paula; Urtubia, Alejandra; Schiappacasse, María C; Chamy, Rolando; Montalvo, Silvio; Borja, Rafael

    2014-01-01

    The macromolecular composition of activated sludge (lipids, intracellular proteins and intracellular polysaccharides) was studied together with its capacity to store macromolecules such as polyhydroxybutyrate (PHB) in a conventional activated sludge system fed with synthetic sewage water at an organic load rate of 1.0 kg COD/(m(3)·d), varying the dissolved oxygen (DO) and temperature. Six DO concentrations (0.8, 1.0, 1.5, 2.0, 2.5 and 8 mg/L) were studied at 20°C with a sludge retention time (SRT) of 6 days. In addition, four temperatures (10ºC, 15ºC, 20ºC and 30ºC) were assessed at constant DO (2 mg/L) with 2 days SRT in a second experimental run. The highest lipid content in the activated sludge was 95.6 mg/g VSS, obtained at 30°C, 2 mg/L of DO and a SRT of 2 days. The highest content of intracellular proteins in the activated sludge was 87.8 mg/g VSS, obtained at 20°C, 8 mg/L of DO and a SRT of 6 days. The highest content of intracellular polysaccharides in the activated sludge was 76.6 mg/g VSS, which was achieved at 20°C, a SRT of 6 days and a wide range of DO. The activated sludge PHB storage was very low for all the conditions studied.

  13. Anti-tumor and immunomodulatory activity of iron hepta-tungsten phosphate oxygen clusters complex.

    PubMed

    Zhang, Bisong; Qiu, Jianping; Wu, Changsheng; Li, Yunxia; Liu, Zhenxiang

    2015-12-01

    Polyoxometalates (POMs) have attracted a considerable attention due to their unique structural characteristics, physicochemical properties and biological activities. In this study, iron hepta-tungsten phosphate oxygen clusters complex Na12H[Fe(HPW7O28)2]·44H2O (IHTPO) was synthesized and evaluated for in vitro cytotoxic activities on human hepatoma HepG2, leukemia K562, lung carcinoma A549, and large cell lung cancer NCI-H460 cells, therapeutic efficacies on mice transplantable tumor, and immunomodulatory potentials on the immune response in tumor-bearing mice. IHTPO exhibited lower in vitro cytotoxic activities against four human tumor cell lines, with the IC50 values being higher than 62.5μM (ca. 300μg/ml). IHTPO, however, significantly inhibited the growth of S180 sarcoma transplanted in mice. It was further showed that IHTPO could not only significantly promote splenocytes proliferation, NK cell and CTL activity from splenocytes, but remarkably enhance serum antigen-specific IgG, IgG2a and IgG2b antibody levels in S180-bearing mice. IHTPO also significantly promoted Th1 cytokines IFN-γ and IL-2 production, and up-regulated the mRNA expression levels of IFN-γ, IL-2 and Th1 transcription factors T-bet and STAT-4 in splenocytes from the S180-bearing mice. These results suggested that IHTPO significantly inhibited the growth of mice transplantable tumor, and that its in vivo antitumor activity might be achieved by improving Th1 protective cell-mediated immunity. IHTPO could act as antitumor agent with immunomodulatory activity.

  14. Coupled oxygenation oscillation measured by NIRS and intermittent cerebral activation on EEG in premature infants.

    PubMed

    Roche-Labarbe, N; Wallois, F; Ponchel, E; Kongolo, G; Grebe, R

    2007-07-01

    Electroencephalography of premature neonates shows a physiological discontinuity of electrical activity during quiet sleep. Near infrared spectroscopy (NIRS) shows spontaneous oscillations of hemoglobin oxygenation and volume. Similar oscillations are visible in term neonates and adults, with NIRS and other functional imaging techniques (fMRI, Doppler, etc.), but are generally thought to result from vasomotion and to be a physiological artifact of limited interest. The origin and possible relationship to neuronal activity of the baseline changes in the NIRS signal have not been established. We carried out simultaneous EEG-NIRS recordings on six healthy premature neonates and four premature neonates presenting neurological distress, to determine whether changes in the concentration of cerebral oxy- and deoxy- and total hemoglobin were related to the occurrence of spontaneous bursts of cerebral electric activity. Bursts of electroencephalographic activity in neonates during quiet sleep were found to be coupled to a transient stereotyped hemodynamic response involving a decrease in oxy-hemoglobin concentration, sometimes beginning a few seconds before the onset of electroencephalographic activity, followed by an increase, and then a return to baseline. This pattern could be either part of the baseline oscillations or superimposed changes to this baseline, influencing its shape and phase. The temporal patterns of NIRS parameters present an unique configuration, and tend to be different between our healthy and pathological subjects. Studies of physiological activities and of the effects of intrinsic regulation on the NIRS signal should increase our understanding of these patterns and EEG-NIRS studies should facilitate the integration of NIRS into the set of clinical tools used in neurology.

  15. Existence, Functional Impairment, and Lung Repair Potential of Endothelial Colony-Forming Cells in Oxygen-Induced Arrested Alveolar Growth

    PubMed Central

    Alphonse, Rajesh S.; Vadivel, Arul; Fung, Moses; Shelley, William Chris; Critser, Paul John; Ionescu, Lavinia; O’Reilly, Megan; Ohls, Robin K.; McConaghy, Suzanne; Eaton, Farah; Zhong, Shumei; Yoder, Merv; Thébaud, Bernard

    2014-01-01

    Background Bronchopulmonary dysplasia and emphysema are life-threatening diseases resulting from impaired alveolar development or alveolar destruction. Both conditions lack effective therapies. Angiogenic growth factors promote alveolar growth and contribute to alveolar maintenance. Endothelial colony-forming cells (ECFCs) represent a subset of circulating and resident endothelial cells capable of self-renewal and de novo vessel formation. We hypothesized that resident ECFCs exist in the developing lung, that they are impaired during arrested alveolar growth in experimental bronchopulmonary dysplasia, and that exogenous ECFCs restore disrupted alveolar growth. Methods and Results Human fetal and neonatal rat lungs contain ECFCs with robust proliferative potential, secondary colony formation on replating, and de novo blood vessel formation in vivo when transplanted into immunodeficient mice. In contrast, human fetal lung ECFCs exposed to hyperoxia in vitro and neonatal rat ECFCs isolated from hyperoxic alveolar growth–arrested rat lungs mimicking bronchopulmonary dysplasia proliferated less, showed decreased clonogenic capacity, and formed fewer capillary-like networks. Intrajugular administration of human cord blood–derived ECFCs after established arrested alveolar growth restored lung function, alveolar and lung vascular growth, and attenuated pulmonary hypertension. Lung ECFC colony- and capillary-like network-forming capabilities were also restored. Low ECFC engraftment and the protective effect of cell-free ECFC-derived conditioned media suggest a paracrine effect. Long-term (10 months) assessment of ECFC therapy showed no adverse effects with persistent improvement in lung structure, exercise capacity, and pulmonary hypertension. Conclusions Impaired ECFC function may contribute to arrested alveolar growth. Cord blood–derived ECFC therapy may offer new therapeutic options for lung diseases characterized by alveolar damage. PMID:24710033

  16. Iridium-Tin oxide solid-solution nanocatalysts with enhanced activity and stability for oxygen evolution

    NASA Astrophysics Data System (ADS)

    Li, Guangfu; Yu, Hongmei; Yang, Donglei; Chi, Jun; Wang, Xunying; Sun, Shucheng; Shao, Zhigang; Yi, Baolian

    2016-09-01

    Addressing major challenges from the material cost, efficiency and stability, it is highly desirable to develop high-performance catalysts for oxygen evolution reaction (OER). Herein we explore a facile surfactant-assisted approach for fabricating Irsbnd Sn (Ir/Sn = 0.6/0.4, by mol.) nano-oxide catalysts with good morphology control. Direct proofs from XRD and X-ray photoelectron spectra indicate hydrophilic triblock polymer (TBP, like Pluronic® F108) surfactant can boost the formation of stable solid-solution structure. With the TBP hydrophilic and block-length increase, the fabricated Irsbnd Sn oxides undergoing the rod-to-sphere transition obtain the relatively lower crystallization, decreased crystallite size, Ir-enriched surface and incremental available active sites, all of which can bolster the OER activity and stability. Meanwhile, it is observed that the coupled Ir oxidative etching takes a crucial role in determining the material structure and performance. Compared with commercial Ir black, half-cell tests confirm F108-assistant catalysts with over 40 wt% Ir loading reduction show 2-fold activity enhancement as well as significant stability improvement. The lowest cell voltage using 0.88 mg cm-2 Ir loading is only 1.621 V at 1000 mA cm-2 and 80 °C with a concomitant energy efficiency of 75.8% which is beyond the DOE 2017 efficiency target of 74%.

  17. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    DOE PAGES

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; et al

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shownmore » to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.« less

  18. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    PubMed Central

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-01-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability. PMID:26133469

  19. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    DOE PAGES

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; et al

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can bemore » attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.« less

  20. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; Adzic, Radoslav R.; Liu, Ping

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.

  1. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  2. Oxygen uptake, muscle activity and ground reaction force during water aerobic exercises.

    PubMed

    Alberton, C L; Pinto, S S; Cadore, E L; Tartaruga, M P; Kanitz, A C; Antunes, A H; Finatto, P; Kruel, L F M

    2014-12-01

    This study aimed to compare the oxygen uptake (VO2), the muscle activity of lower limbs, and the vertical ground reaction force (V-GRF) of women performing water aerobic exercises at different intensities. 12 young women performed the experimental protocol, which consisted of 3 water exercises (stationary running [SR], frontal kick [FK] and cross country skiing [CCS]) at 3 intensities (first and second ventilatory thresholds and maximum effort). A two-way repeated measures ANOVA was used. Regarding VO2, different responses between intensities (p<0.001) were found, and values between exercises were similar. For electromyographic activity (EMG), differences between intensities for all muscles (p<0.001) were found. Greater EMG signals were observed in the FK compared to SR for rectus femoris, semitendinosus, vastus lateralis and biceps femoris muscles (p<0.05). Regarding V-GRF, there was an increase in the V-GRF at greater intensities compared to the first ventilatory threshold (p=0.001). In addition, lower values were found during CCS compared to the SR and FK exercises (p<0.001). Thus, greater cardiorespiratory and neuromuscular responses were observed with increasing intensity. Exercises such as CCS could be used to attenuate the V-GRF; if the purpose is to reduce the muscular activity of lower limbs at a specific intensity, SR could be recommended.

  3. The characteristics of alumina scales formed on HVOF-sprayed MCrAlY coatings[High Velocity Oxygen Fuel

    SciTech Connect

    Toma, D.; Brandl, W.; Koester, U.

    2000-02-01

    HVOF MCrAlY (M = Ni, Co) coatings were isothermally oxidized in synthetic air between 850 and 1050 C for times up to 167 hr. During thermal spraying, aluminum and yttrium oxidized to form a fine oxide dispersion. The HVOF MCrAlY coatings exhibited a microstructure similar to ODS alloys. The fine dispersion consisted of Al{sub 2}O{sub 3} and aluminum-yttrium oxides. The oxidation experiments showed that the oxidation rate of HVOF coatings was two times slower than the oxidation rate of VPS MCrAlY coatings. The oxidation mechanism changed mainly in the transient-stage (no metastable modification of Al{sub 2}O{sub 3} formed) and it was assumed that the oxide dispersion hindered diffusion of various elements from the bulk material during oxidation. The formation of the fine oxide dispersion also influenced the adherence of the oxide scale. The microstructures of the transient oxide scales were examined by X-ray diffraction (XRD) scanning electron microscopy (SEM), and transmission electron microscopy (TEM).

  4. Mechanistic Investigation into Olefin Epoxidation with H2O2 Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position

    PubMed Central

    Ci, Chenggang; Liu, Hongsheng

    2016-01-01

    Abstract Aqua‐coordinated sandwich‐type polyoxometalates (POMs), {[WZnTM2(H2O)2](ZnW9O34)2}n− (TM=RhIII, PdII, and PtII), catalyze olefin epoxidation with hydrogen peroxide and have been well established, and they present an advance toward the utilization of olefins. To elucidate the epoxidation mechanism, we systematically performed density functional calculations. The reaction proceeds through a two‐step mechanism: activation of H2O2 and oxygen transfer. The aqua‐coordinated complexes show two distinct H2O2 activation pathways: “two‐step” and “concerted”. The concerted processes are more facile and proceed with similar and rate‐determining energy barriers at the Rh‐, Pd‐, and Pt‐containing transition states, which agrees well with the experimental results. Next, the resulting TM−OH−(μ‐OOH) intermediate transfers an O atom to olefin to form an epoxide. The higher reactivity of the Rh‐containing POM is attributed to more interactions between the Rh and hydroperoxo unit. We also calculated all active oxygen positions to locate the most favorable pathway. The higher reactivity of the two‐metal‐bonded oxygen position is predominantly ascribed to its lower stereoscopic hindrance. Furthermore, the presence of one and two explicit water solvent molecules significantly reduces the energy barriers, making these sandwich POMs very efficient for the olefin epoxidation with H2O2. PMID:27777840

  5. A key parameter on the adsorption of diluted aniline solutions with activated carbons: The surface oxygen content.

    PubMed

    Pardo, Beatrice; Ferrer, Nabí; Sempere, Julià; Gonzalez-Olmos, Rafael

    2016-11-01

    A total of 11 different commercial activated carbons (AC) with well characterized textural properties and oxygen surface content were tested as adsorbents for the removal of aniline as a target water pollutant. The maximum adsorption capacity of aniline for the studied AC was from 138.9 to 257.9 mg g(-1) at 296.15 K and it was observed to be strongly related to the textural properties of the AC, mainly with the BET surface area and the micropore volume. It was not observed any influence of the oxygen surface content of the AC on the maximum adsorption capacity. However, it was found that at low aniline aqueous concentration, the presence of oxygen surface groups plays a dominant role during the adsorption. A high concentration of oxygen surface groups, mainly carboxylic and phenolic groups, decreases the aniline adsorption regardless of the surface area of the AC. PMID:27497348

  6. A key parameter on the adsorption of diluted aniline solutions with activated carbons: The surface oxygen content.

    PubMed

    Pardo, Beatrice; Ferrer, Nabí; Sempere, Julià; Gonzalez-Olmos, Rafael

    2016-11-01

    A total of 11 different commercial activated carbons (AC) with well characterized textural properties and oxygen surface content were tested as adsorbents for the removal of aniline as a target water pollutant. The maximum adsorption capacity of aniline for the studied AC was from 138.9 to 257.9 mg g(-1) at 296.15 K and it was observed to be strongly related to the textural properties of the AC, mainly with the BET surface area and the micropore volume. It was not observed any influence of the oxygen surface content of the AC on the maximum adsorption capacity. However, it was found that at low aniline aqueous concentration, the presence of oxygen surface groups plays a dominant role during the adsorption. A high concentration of oxygen surface groups, mainly carboxylic and phenolic groups, decreases the aniline adsorption regardless of the surface area of the AC.

  7. Study on an oxygen sensing rhenium(I) complex with enlarged sensing/active area: fabrication, photophysical parameters and molecular oxygen sensing performance.

    PubMed

    Xu, Guiying; Lu, Mang; Huang, Can; Wang, Yaoqiong; Ge, Shuping

    2014-04-01

    In this paper, we synthesize a novel 1,10-phenanthroline-derived (Phen-derived) diamine ligand of benzo[f][1,10]phenanthroline-6,7-dicarbonitrile (Phen-CN) with enlarged conjugation planar and its corresponding Re(I) complex of Re(CO)3Cl(Phen-CN), hoping to achieve an optical sensor owing large sensing/active area. Its geometric and electronic structures are investigated, which suggests that the effective sensing/active area of Re(CO)3Cl(Phen-CN) is enlarged by the successful formation of conjugation planar. The promising photophysical parameters of Re(CO)3Cl(Phen-CN), including large sensing/active area and long excited state lifetime, make it a potential probe for oxygen detection. By doping Re(CO)3Cl(Phen-CN) into a polymer matrix of poly(vinylpyrrolidone), oxygen sensing performances of the resulted composite materials are investigated. Finally, a high sensitivity of 17.1 is realized, with short response/recovery time of 9s/32s.

  8. Effect of the solution temperature in a singlet-oxygen generator on the formation of active medium in an ejector oxygen - iodine laser

    SciTech Connect

    Zagidullin, M V; Nikolaev, V D; Svistun, M I; Khvatov, N A; Palina, N Yu

    2002-02-28

    The influence of the solution temperature in a singlet-oxygen generator on the formation of the active medium in the ejector oxygen - iodine laser is investigated. The following parameters of the active medium at the solution temperature -20{sup 0}C are obtained: the gain is 7.2 x 10{sup -3} cm{sup -1}, the Mach number is M=2, the temperature is 205 K, and the static pressure is 9.3 mmHg. As the solution temperature is increased to -4{sup 0}C, the gain decreases to 5 x 10{sup 3} cm{sup -1}, the Mach number decreases to 1.78, while the temperature and the static pressure increase to 241 K and 10.7 mmHg, respectively. As the solution temperature increases from -20 to -4{sup 0}C, the losses in O{sub 2}({sup 1}{Delta}) increase by less than 20%, while the dissociation efficiency of molecular iodine decreases by less than 21%. (lasers, active media)

  9. AMPK is involved in mediation of erythropoietin influence on metabolic activity and reactive oxygen species production in white adipocytes.

    PubMed

    Wang, Li; Di, Lijun; Noguchi, Constance Tom

    2014-09-01

    Erythropoietin, discovered for its indispensable role during erythropoiesis, has been used in therapy for selected red blood cell disorders in erythropoietin-deficient patients. The biological activities of erythropoietin have been found in animal models to extend to non-erythroid tissues due to the expression of erythropoietin receptor. We previously demonstrated that erythropoietin promotes metabolic activity and white adipocytes browning to increase mitochondrial function and energy expenditure via peroxisome proliferator-activated receptor alpha and Sirtuin1. Here we report that AMP-activated protein kinase was activated by erythropoietin possibly via Ca(2+)/calmodulin-dependent protein kinase kinase in adipocytes as well as in white adipose tissue from diet induced obese mice. Erythropoietin increased cellular nicotinamide adenine dinucleotide via increased AMP-activated protein kinase activity, possibly leading to Sirtuin1 activation. AMP-activated protein kinase knock down reduced erythropoietin mediated increase in cellular oxidative function including the increased oxygen consumption rate, fatty acid utilization and induction of key metabolic genes. Under hypoxia, adipocytes were found to generate more reactive oxygen species, and erythropoietin reduced the reactive oxygen species and increased antioxidant gene expression, suggesting that erythropoietin may provide protection from oxidative stress in adipocytes. Erythropoietin also reversed increased nicotinamide adenine dinucleotide by hypoxia via increased AMP-activated protein kinase. Additionally, AMP-activated protein kinase is found to be involved in erythropoietin stimulated increase in oxygen consumption rate, fatty acid oxidation and mitochondrial gene expression. AMP-activated protein kinase knock down impaired erythropoietin stimulated increases in antioxidant gene expression. Collectively, our findings identify the AMP-activated protein kinase involvement in erythropoietin signaling in

  10. Reactive Oxygene Species and Thioredoxin Activity in Plants at Development of Hypergravity and Oxidative Stresses

    NASA Astrophysics Data System (ADS)

    Jadko, Sergiy

    Early increasing of reactive oxygen species (ROS) content, including H2O2, occurs in plant cells under various impacts and than these ROS can function as signaling molecules in starting of cell stress responses. At the same time thioredoxins (TR) are significant ROS and H2O2 sensors and transmitters to activation of various redox sensitive proteins, transcription factors and MAP kinases. This study was aimed to investigate early increasing of ROS and H2O2 contents and TR activity in the pea roots and in tissue culture under hypergravity and oxidative stresses. Pea roots of 3-5 days old seedlings and 12-14 days old tissue culture of Arabidopsis thaliana were studied. The pea seedlings were grown on wet filter paper and the tissue culture was grown on MS medium in dark conditions under 24oC. Hypergravity stress was induced by centrifugation at 10 and 15 g. Chemiluminescence (ChL) intensity for ROS concentration, H2O2 content and TR activity were determined. All experiments were repeated by 3-5 times. Early and reliable increasing of ChL intensity and H2O2 contents in the pea roots and in the tissue culture took place under hypergravity and oxidative stresses to 30, 60 and 90 min. At the same time TR activity increased on 11 and 19 percents only to 60 and 90 min. Thus under hypergravity and oxidative stresses in both investigated plants take place early increasing of ROS and H2O2 contents which as second messengers lead to increasing of TR activity with creating of ROS-TR stress signaling pathway.

  11. Density Functional Theory Study of Oxygen Reduction Activity on Ultrathin Platinum Nanotubes

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2012-07-13

    The structure, stability, and catalytic activity of a number of single- and double-wall platinum (n,m) nanotubes ranging in diameter from 0.3 to 2.0 nm were studied using plane-wave based density functional theory in the gas phase and water environment. The change in the catalytic activity toward the oxygen reduction reaction (ORR) with the size and chirality of the nanotube was studied by calculating equilibrium adsorption potentials for ORR intermediates and by constructing free energy diagrams in the ORR dissociative mechanism network. In addition, the stability of the platinum nanotubes is investigated in terms of electrochemical dissolution potentials and by determining the most stable state of the material as a function of pH and potential, as represented in Pourbaix diagrams. Our results show that the catalytic activity and the stability toward electrochemical dissolution depend greatly on the diameter and chirality of the nanotube. On the basis of the estimated overpotentials for ORR, we conclude that smaller, approximately 0.5 nm in diameter single-wall platinum nanotubes consistently show a huge, up to 400 mV larger overpotential than platinum, indicating very poor catalytic activity toward ORR. This is the result of substantial structural changes induced by the adsorption of any chemical species on these tubes. Single-wall n = m platinum nanotubes with a diameter larger than 1 nm have smaller ORR overpotentials than bulk platinum for up to 180 mV and thus show improved catalytic activity relative to bulk. We also predict that these nanotubes can endure the highest cell potentials but dissolution potentials are still for 110 mV lower than for the bulk, indicating a possible corrosion problem.

  12. Implication of reactive oxygen species in the antibacterial activity against Salmonella typhimurium of hepatocyte cell lines.

    PubMed

    Lajarin, F; Rubio, G; Lorenzo, N; Gámiz, P; Hernandez-Caselles, T; Garcia-Peñarrubia, P

    1999-11-01

    We recently described the antibacterial activity of a murine hepatocyte cell line stimulated with interferon-gamma (IFN-gamma), interleukin-1 (IL-1), and lipopolysaccharide (LPS) against intracellular Salmonella organisms. Here we show for the first time the existence of basal antibacterial activity in cultured hepatocyte cell lines. Thus treatment of resting and stimulated hepatocytes with catalase or superoxide dismutase increased bacterial number recovered per monolayer, which suggests that the mechanism involved with antibacterial activity of hepatocytes is mediated by reactive oxygen species (ROS). Also, the capacity of these cell lines to generate intracellular peroxides under resting and stimulated conditions was investigated. This revealed that IL-1 and LPS did not induce any increase in the amount of intracellular peroxides by themselves, but they primed IFN-gamma for maximal induction of peroxides. The intracellular amount of peroxides was highly increased on stimulation with IFN-gamma, IL-1, and LPS, and it was strongly inhibited by catalase. This explains that the mechanism whereby this enzyme inhibits antibacterial activity takes place by decreasing the intracellular pool of peroxides. In turn, experiments performed in the presence of several inhibitors of metabolic pathways involved in ROS generation suggested that cyclo-oxygenase are a source of these species in hepatocyte cell lines. These results attribute a prominent role to the generation of peroxides as effector molecules of antibacterial activity in hepatocyte cell lines. Thus these cells displayed a moderate basal level, which increased on stimulation with proinflammatory cytokines such as IFN-gamma, IL-1, and bacterial products such as LPS. Finally, it has been also shown for the first time that IFN-gamma stimulation induces production of peroxides in human and murine hepatocyte cell lines.

  13. Carbon and oxygen abundances from recombination lines in low-metallicity star-forming galaxies. Implications for chemical evolution

    NASA Astrophysics Data System (ADS)

    Esteban, C.; García-Rojas, J.; Carigi, L.; Peimbert, M.; Bresolin, F.; López-Sánchez, A. R.; Mesa-Delgado, A.

    2014-09-01

    We present deep echelle spectrophotometry of the brightest emission-line knots of the star-forming galaxies He 2-10, Mrk 1271, NGC 3125, NGC 5408, POX 4, SDSS J1253-0312, Tol 1457-262, Tol 1924-416 and the H II region Hubble V in the Local Group dwarf irregular galaxy NGC 6822. The data have been taken with the Very Large Telescope Ultraviolet-Visual Echelle Spectrograph in the 3100-10420 Å range. We determine electron densities and temperatures of the ionized gas from several emission-line intensity ratios for all the objects. We derive the ionic abundances of C2+ and/or O2+ from faint pure recombination lines in several of the objects, permitting to derive their C/H and C/O ratios. We have explored the chemical evolution at low metallicities analysing the C/O versus O/H, C/O versus N/O and C/N versus O/H relations for Galactic and extragalactic H II regions and comparing with results for Galactic halo stars and damped Lyα systems. We find that H II regions in star-forming dwarf galaxies occupy a different locus in the C/O versus O/H diagram than those belonging to the inner discs of spiral galaxies, indicating their different chemical evolution histories, and that the bulk of C in the most metal-poor extragalactic H II regions should have the same origin than in halo stars. The comparison between the C/O ratios in H II regions and in stars of the Galactic thick and thin discs seems to give arguments to support the merging scenario for the origin of the Galactic thick disc. Finally, we find an apparent coupling between C and N enrichment at the usual metallicities determined for H II regions and that this coupling breaks in very low metallicity objects.

  14. Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

    SciTech Connect

    Roman, Yuriy

    2015-09-14

    The objective of this project is to understand the mechanistic aspects behind the cooperative activation of oxygenates by catalytic pairs in aqueous media. Specifically, we will investigate how the reactivity of a solid Lewis acid can be modulated by pairing the active site with other catalytic sites at the molecular level, with the ultimate goal of enhancing activation of targeted functional groups. Although unusual catalytic properties have been attributed to the cooperative effects promoted by such catalytic pairs, virtually no studies exist detailing the use heterogeneous water-tolerant Lewis pairs. A main goal of this work is to devise rational pathways for the synthesis of porous heterogeneous catalysts featuring isolated Lewis pairs that are active in the transformation of biomass-derived oxygenates in the presence of bulk water. Achieving this technical goal will require closely linking advanced synthesis techniques; detailed kinetic and mechanistic investigations; strict thermodynamic arguments; and comprehensive characterization studies of both materials and reaction intermediates. For the last performance period (2014-2015), two technical aims were pursued: 1) C-C coupling using Lewis acid and base pairs in Lewis acidic zeolites. Tin-, zirconium-, and hafnium containing zeolites (e.g., Sn-, Zr-, and Hf-Beta) are versatile solid Lewis acids that selectively activate carbonyl functional groups. In this aim, we demonstrate that these zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. 2) One-pot synthesis of MWW zeolite nanosheets for activation of bulky substrates. Through

  15. Multiple forms of soluble monophenol, dihydroxyphenylalamine: oxygen-oxidoreductase (EC 1.14.18.1) from potato tubers (Solanum tuberosum). II. Partial characterization of the enzyme forms with different molecular weights.

    PubMed

    Matheis, G; Belitz, H D

    1977-04-28

    Gel chromatography on Sephadex G-200 was used to separate a soluble phenoloxidase from potatoes (var. Maritta) into at least six active fractions with dopa (dihydroxyphenylalanine) as substrate. Only high-molecular-weight-enzyme forms exhibited monophenoloxidase activity. Re-chromatography of the highest-molecular-weight form gave the same molecular weight distribution as with the crude enzyme. The molecular weights indicate association phenomena of subunits with a molecular weight of about 36000 daltons. According to polyacrylamide-gel electrophoresis, several monomeric forms with differnt isoelectric points seem to be present. This suggests that the large number of multiple forms of the enzyme arises from various combinations of identical and/or different subunits. SDS polyacrylamide gel electrophoresis failed to show the monomeric forms; the dimer and higher oligomers were obtained. PMID:404778

  16. Low effective activation energies for oxygen release from metal oxides: evidence for mass-transfer limits at high heating rates.

    PubMed

    Jian, Guoqiang; Zhou, Lei; Piekiel, Nicholas W; Zachariah, Michael R

    2014-06-01

    Oxygen release from metal oxides at high temperatures is relevant to many thermally activated chemical processes, including chemical-looping combustion, solar thermochemical cycles and energetic thermite reactions. In this study, we evaluated the thermal decomposition of nanosized metal oxides under rapid heating (~10(5) K s(-1)) with time-resolved mass spectrometry. We found that the effective activation-energy values that were obtained using the Flynn-Wall-Ozawa isoconversional method are much lower than the values found at low heating rates, indicating that oxygen transport might be rate-determining at a high heating rate.

  17. Reactive oxygen species inhibit polycystin-2 (TRPP2) cation channel activity in term human syncytiotrophoblast.

    PubMed

    Montalbetti, N; Cantero, M R; Dalghi, M G; Cantiello, H F

    2008-06-01

    Pregnancy is often associated with oxidative stress (OS) and lower antioxidant defences, which are both implicated in the pathophysiology of preeclampsia, free radical-induced birth defects, and abortions, as well as gestational diabetes mellitus (GDM), where products of lipid peroxidation are increased. The molecular target(s) of increased oxygen free radicals and consequent lipid peroxidation in the human placenta remains ill defined. The human syncytiotrophoblast (hST) expresses abundant polycystin-2 (PC2, TRPP2), a TRP-type Ca(2+)-permeable non-selective cation channel. Here, we explored the effect of reactive oxygen species (ROS) on PC2 channel activity of term hST. Apical membranes of the hST were reconstituted in a lipid bilayer chamber. Addition of either hydrogen-peroxide (H(2)O(2)) or tert-butyl hydroperoxide (tBHP) to the cis chamber (intracellular side) rapidly and completely inhibited PC2-mediated cation channel activity in reconstituted hST vesicles. A dose-response titration with increasing concentrations of H(2)O(2) gave an IC(50)=131 nM. The effect of H(2)O(2) on the isolated protein from in vitro transcribed/translated material was significantly different. H(2)O(2) inhibited PC2 cation channel activity, with a much lower affinity (IC(50)=193 microM). To correlate these findings with H(2)O(2)-induced lipid peroxidation, TBARS where measured in hST apical membranes incubated with H(2)O(2). Increased TBARS by exposure of hST apical membranes to H(2)O(2) (625 microM) returned to control value in the presence of catalase (167 microg/ml). Taken together these data indicate that ROS affect PC2 channel function by targetting both membrane lipids and the channel protein. Thus, OS in human pregnancy may be linked to dysregulation of channels such as PC2, which allow the transport of Ca(2+) into the placenta. Oxidative complications in pregnancy may implicate dysfunctional cation transfer between mother and fetus. PMID:18417208

  18. Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

    NASA Astrophysics Data System (ADS)

    Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

    2013-12-01

    Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

  19. Kinetics of an oxygen - iodine active medium with iodine atoms optically pumped on the 2P1/2 - 2P3/2 transition

    NASA Astrophysics Data System (ADS)

    Zagidullin, M. V.; Malyshev, M. S.; Azyazov, V. N.

    2015-08-01

    The kinetics of the processes occurring in an O2 - I2 - He - H2O gas flow in which photodissociation of molecular iodine at a wavelength close to 500 nm and excitation of atomic iodine on the 2P1/2 - 2P3/2 transition by narrow-band radiation near 1315 nm are implemented successively has been analysed. It is shown that implementation of these processes allows one to form an oxygen - iodine medium with a high degree of dissociation of molecular iodine and a relative content of singlet oxygen O2(a1Δ) exceeding 10%. Having formed a supersonic gas flow with a temperature ~100 K from this medium, one can reach a small-signal gain of about 10-2 cm-1 on the 2P1/2 - 2P3/2 transition in iodine atoms. The specific power per unit flow cross section in the oxygen - iodine laser with this active medium may reach ~100 W cm-2.

  20. Relationship between Active Oxygen Species, Lipid Peroxidation, Necrosis, and Phytoalexin Production Induced by Elicitins in Nicotiana.

    PubMed Central

    Rusterucci, C.; Stallaert, V.; Milat, M. L.; Pugin, A.; Ricci, P.; Blein, J. P.

    1996-01-01

    Excised leaves of Nicotiana tabacum var Xanthi and Nicotiana rustica were treated with cryptogein and capsicein, basic and acidic elicitins, respectively. Both compounds induced leaf necrosis, the intensity of which depended on concentration and duration of treatment. N. tabacum var Xanthi was the most sensitive species and cryptogein was the most active elicitin. Lipid peroxidation in elicitin-treated Nicotiana leaves was closely correlated with the appearance of necrosis. Elicitin treatments induced a rapid and transient burst of active oxygen species (AOS) in cell cultures of both Nicotiana species, with the production by Xanthi cells being 6-fold greater than that by N. rustica. Similar maximum AOS production levels were observed with both elicitins, but capsicein required 10-fold higher concentrations than those of cryptogein. Phytoalexin production was lower in response to both elicitins in N. tabacum var Xanthi cells than in N. rustica cells, and capsicein was the most efficient elicitor of this response. In cryptogein-treated cell suspensions, phytoalexin synthesis was unaffected by diphenyleneiodonium, which inhibited AOS generation, nor was it affected by tiron or catalase, which suppressed AOS accumulation in the extracellular medium. These results suggest that AOS production, lipid peroxidation, and necrosis are directly related, whereas phytoalexin production depends on neither the presence nor the intensity of these responses. PMID:12226334

  1. Electrocatalytic activity of various types of h-BN for the oxygen reduction reaction.

    PubMed

    Elumalai, Ganesan; Noguchi, Hidenori; Uosaki, Kohei

    2014-07-21

    The electrocatalytic activities of various types of h-BN, i.e., spin coated BN nanotubes (BNNTs) and BN nanosheets (BNNSs) and sputter deposited BN, on Au electrodes as well as those of BNNS modified glassy carbon (GC) and Pt electrodes for the oxygen reduction reaction (ORR) were examined in O2 saturated 0.5 M H2SO4 solution based on the theoretical prediction that monolayered BN on a metal substrate may act as an electrocatalyst for ORR even though bulk BN is an insulator with a wide band gap. The overpotential for ORR at Au electrodes was reduced by ca. 100, ca. 270, and ca. 150 mV by spin coating of the dispersion of BNNT and liquid exfoliated BNNS, and sputter deposition of BN, respectively, proving the theoretical prediction. On the other hand, no change in the overpotential was observed at the glassy carbon electrode with BNNS modification and the overpotential even increased at the Pt electrode, suggesting that the interaction between BN and Au plays an important role in BN becoming ORR active.

  2. Electrochemical sensing chemical oxygen demand based on the catalytic activity of cobalt oxide film.

    PubMed

    Wang, Jinqi; Wu, Can; Wu, Kangbing; Cheng, Qin; Zhou, Yikai

    2012-07-29

    Cobalt oxide sensing film was in situ prepared on glassy carbon electrode surface via constant potential oxidation. Controlling at 0.8 V in NaOH solution, the high-valence cobalt catalytically oxidized the reduced compounds, decreasing its surface amount and current signal. The current decline was used as the response signal of chemical oxygen demand (COD) because COD represents the summation of reduced compounds in water. The surface morphology and electrocatalytic activity of cobalt oxide were readily tuned by variation of deposition potential, time, medium and Co(2+) concentration. As confirmed from the atomic force microscopy measurements, the cobalt oxide film, that prepared at 1.3 V for 40 s in pH 4.6 acetate buffer containing 10 mM Co(NO(3))(2), possesses large surface roughness and numerous three-dimensional structures. Electrochemical tests indicated that the prepared cobalt oxide exhibited high electrocatalytic activity to the reduced compounds, accompanied with strong COD signal enhancement. As a result, a novel electrochemical sensor with high sensitivity, rapid response and operational simplicity was developed for COD. The detection limit was as low as 1.1 mg L(-1). The analytical application was studied using a large number of lake water samples, and the accuracy was tested by standard method.

  3. Reactive oxygen species scavenging activity of aminoderivatized chitosan with different degree of deacetylation.

    PubMed

    Je, Jae-Young; Kim, Se-Kwon

    2006-09-01

    Chitosans with different degree of deacetylation were prepared from crab shell chitin in the presence of alkali. Aminoderivatized chitosan derivatives were prepared in addition of amino functional groups at a hydroxyl site in the chitosan backbone. Six kinds of aminoderivatized chitosan such as aminoethyl-chitosan (AEC90), dimethylaminoethyl-chitosan (DMAEC90), and diethylaminoethyl-chitosan (DEAEC90), which were prepared from 90% deacetylated chitosan, and AEC50, DMAEC50 and DEAEC50, which were prepared from 50% deacetylated chitosan, were prepared and their reactive oxygen species (ROS) scavenging activities were investigated against hydroxyl radical, superoxide anion radical and hydrogen peroxide. The electron spin resonance (ESR) spectrum revealed that AEC90 showed the highest scavenging effects against hydroxyl and superoxide anion radical, the effects were 91.67% and 65.34% at 0.25 and 5 mg/mL, respectively. For hydrogen peroxide scavenging effect, DEAEC90 exhibited the strongest activity. These results suggest that the scavenging effect depends on their degree of deacetylation and substituted group.

  4. Mineralization of naphtenic acids with thermally-activated persulfate: The important role of oxygen.

    PubMed

    Xu, Xiyan; Pliego, Gema; Zazo, Juan A; Casas, Jose A; Rodriguez, Juan J

    2016-11-15

    This study reports on the mineralization of model naphtenic acids (NAs) in aqueous solution by catalyst-free thermally-activated persulfate (PS) oxidation. These species are found to be pollutants in oil sands process-affected waters. The NAs tested include saturated-ring (cyclohexanecarboxylic and cyclohexanebutyric acids) and aromatic (2-naphthoic and 1,2,3,4-tetrahydro-2-naphthoic acids) structures, at 50mgL(-1)starting concentration. The effect of PS dose within a wide range (10-100% of the theoretical stoichiometric) and working temperature (40-97°C) was investigated. At 80°C and intitial pH=8 complete mineralization of the four NAs was achieved with 40-60% of the stoichiometric PS dose. This is explained because of the important contribution of oxygen, which was experimentally verified and was found to be more effective toward the NAs with a single cyclohexane ring than for the bicyclic aromatic-ring-bearing ones. The effect of chloride and bicarbonate was also checked. The former showed negative effect on the degradation rate of NAs whereas it was negligible or even positive for bicarbonate. The rate of mineralization was well described by simple pseudo-first order kinetics with values of the rate constants normalized to the PS dose within the range of 0.062-0.099h(-1). Apparent activation energy values between 93.7-105.3kJmol(-1) were obtained. PMID:27442986

  5. Acrolein activates matrix metalloproteinases by increasing reactive oxygen species in macrophages

    SciTech Connect

    O'Toole, Timothy E. Zheng Yuting; Hellmann, Jason; Conklin, Daniel J.; Barski, Oleg; Bhatnagar, Aruni

    2009-04-15

    Acrolein is a ubiquitous component of environmental pollutants such as automobile exhaust, cigarette, wood, and coal smoke. It is also a natural constituent of several foods and is generated endogenously during inflammation or oxidation of unsaturated lipids. Because increased inflammation and episodic exposure to acrolein-rich pollutants such as traffic emissions or cigarette smoke have been linked to acute myocardial infarction, we examined the effects of acrolein on matrix metalloproteinases (MMPs), which destabilize atherosclerotic plaques. Our studies show that exposure to acrolein resulted in the secretion of MMP-9 from differentiated THP-1 macrophages. Acrolein-treatment of macrophages also led to an increase in reactive oxygen species (ROS), free intracellular calcium ([Ca{sup 2+}]{sub i}), and xanthine oxidase (XO) activity. ROS production was prevented by allopurinol, but not by rotenone or apocynin and by buffering changes in [Ca{sup 2+}]{sub I} with BAPTA-AM. The increase in MMP production was abolished by pre-treatment with the antioxidants Tiron and N-acetyl cysteine (NAC) or with the xanthine oxidase inhibitors allopurinol or oxypurinol. Finally, MMP activity was significantly stimulated in aortic sections from apoE-null mice containing advanced atherosclerotic lesions after exposure to acrolein ex vivo. These observations suggest that acrolein exposure results in MMP secretion from macrophages via a mechanism that involves an increase in [Ca{sup 2+}]{sub I}, leading to xanthine oxidase activation and an increase in ROS production. ROS-dependent activation of MMPs by acrolein could destabilize atherosclerotic lesions during brief episodes of inflammation or pollutant exposure.

  6. Chemistry of the catalytic conversion of phthalate into its cis-dihydrodiol during the reaction of oxygen with the reduced form of phthalate dioxygenase.

    PubMed

    Tarasev, Michael; Ballou, David P

    2005-04-26

    The phthalate dioxygenase system, a Rieske non-heme iron dioxygenase, catalyzes the dihydroxylation of phthalate to form the 4,5-dihydro-cis-dihydrodiol of phthalate (DHD). It has two components: phthalate dioxygenase (PDO), a multimer with one Rieske-type [2Fe-2S] and one mononuclear Fe(II) center per monomer, and a reductase (PDR) that contains flavin mononucleotide (FMN) and a plant-type ferredoxin [2Fe-2S] center. This work shows that product formation in steady-state reactions is tightly coupled to electron delivery, with 1 dihydrodiol (DHD) of phthalate formed for every 2 electrons delivered from NADH. However, in reactions of reduced PDO with O(2), only about 0.5 DHD is formed per Rieske center that becomes oxidized. Although the product forms rapidly, its release from PDO is slow in these reactions with oxygen that do not include reductase and NADH. EPR data show that, at the completion of the oxidation, iron in the mononuclear center remains in the ferrous state. In contrast, naphthalene dioxygenase (NDO) [Wolfe, M. D., Parales, J. V., Gibson, D. T., and Lipscomb, J. D. (2001) J. Biol. Chem. 276, 1945-1953] and benzoate dioxygenase (BZDO) [Wolfe, M. D., Altier, D. J., Stubna, A., Popescu, C. V., Munck, E., and Lipscomb, J. D. (2002) Biochemistry, 41, 9611-9626], related Rieske non-heme iron dioxygenases, form 1 DHD per Rieske center oxidized, and the mononuclear center iron ends up ferric. Thus, both electrons from reduced NDO and BZDO monomers are used to form the product, whereas only the reduced Rieske centers in PDO become oxidized during production of DHD. This emphasizes the importance of PDO subunit interaction in catalysis. Electron redistribution was practically unaffected by the presence of oxidized PDR. A scheme is presented that emphasizes some of the differences in the mechanisms involved in substrate hydroxylation employed by PDO and either NDO or BZDO. PMID:15835907

  7. Mechanism of dark decomposition of iodine donor in the active medium of a pulsed chemical oxygen - iodine laser

    SciTech Connect

    Andreeva, Tamara L; Kuznetsova, S V; Maslov, A I; Sorokin, Vadim N

    2002-06-30

    A scheme is proposed that describes the dark decomposition of iodide - the donor of iodine - and the relaxation of singlet oxygen in the chlorine-containing active medium of a pulsed chemical oxygen - iodine laser (COIL). For typical compositions of the active media of pulsed COILs utilising CH{sub 3}I molecules as iodine donors, a branching chain reaction of the CH{sub 3}I decomposition accompanied by the efficient dissipation of singlet oxygen is shown to develop even at the stage of filling the active volume. In the active media with CF{sub 3}I as the donor, a similar chain reaction is retarded due to the decay of CF{sub 3} radicals upon recombination with oxygen. The validity of this mechanism is confirmed by a rather good agreement between the results of calculations and the available experimental data. The chain decomposition of alkyliodides accompanied by an avalanche production of iodine atoms represents a new way of efficient chemical production of iodine for a COIL. (active media)

  8. Microspheres assembled by KMn8O16 nanorods and their catalytic oxygen reduction activity in direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Fang, Yuan; Yang, Xiaodong; Wang, Li; Liu, Yongning

    2014-12-01

    Microspheres assembled using cryptomelane-type KMn8O16 nanorods are synthesized via a facile template-free, single-step hydrothermal technique. The synthesized KMn8O16 generates nanorods 10-20 nm in diameter and approximately 300-1000 nm long. The rods self-assemble to form microspheres of 2-6 μm in diameters. The electron transfer number for KMn8O16 during the ORR is approximately 3.98 at 0.5 V vs. Hg/HgO, and the H2O2 percentage is 0.66%. Moreover, a direct methanol fuel cell (DMFC) is built using KMn8O16 as cathodic catalyst, PtRu/C alloy as the anodic catalyst and a polymer fiber membrane (PFM) instead of a conventional polymer electrolyte membrane (PEM). The peak power densities (43.3 mW cm-2 and 153.9 mW cm-2) have been achieved at 25 °C and 70 °C, respectively. KMn8O16 shows good electrocatalytic activity and stability during oxygen reduction in alkaline solutions and demonstrates tolerance toward methanol poisoning.

  9. Arylhydrocarbon receptor (AhR) activation in airway epithelial cells induces MUC5AC via reactive oxygen species (ROS) production.

    PubMed

    Chiba, Takahito; Uchi, Hiroshi; Tsuji, Gaku; Gondo, Hisaki; Moroi, Yoichi; Furue, Masutaka

    2011-02-01

    The dioxins and dioxin-like compounds in cigarette smoke regulate various immunological responses via the arylhydrocarbon receptor (AhR). These environmental toxicants are known to cause bronchitis, asthma, chronic obstructive pulmonary disease (COPD), and lung cancer. Recent studies have demonstrated that AhR activation upregulates the expression of mucin 5AC, oligomeric mucus/gel-forming (MUC5AC) in the airway epithelial cell line. However, the mechanism for the production of mucin has not been clarified. In this study, we investigated the role and pathway of AhR in airway epithelial cells by using selective agonists and antagonists. After stimulation with or without benzopyrene (B[a]P), an AhR agonist, MUC5AC expression was measured by real-time RT-PCR. The mechanism of AhR-induced MUC5AC expression in airway epithelial cells was studied in terms of the production of cytokine and reactive oxygen species (ROS). Treatment with B[a]P increased ROS generation in NCI-H₂₉₂ cells. Furthermore, B[a]P-induced MUC5AC upregulation and mucin production were inhibited by AhR siRNA or the use of an antioxidative agent. These results suggest that the AhR-induced increase of mucin production is partially mediated by ROS generation. An antioxidant therapy approach may help to cure AhR-induced mucus hypersecretory diseases. PMID:20709182

  10. Diffusion Limitation of Oxygen Uptake and Nitrogenase Activity in the Root Nodules of Parasponia rigida Merr. and Perry 1

    PubMed Central

    Tjepkema, John D.; Cartica, Robert J.

    1982-01-01

    Parasponia is the first non-legume genus proven to form nitrogen-fixing root nodules induced by rhizobia. Infiltration with India ink demonstrated that intercellular air spaces are lacking in the inner layers of the nodule cortex. Oxygen must diffuse through these layers to reach the cells containing the rhizobia, and it was calculated that most of the gradient in O2 partial pressure between the atmosphere and rhizobia occurs at the inner cortex. This was confirmed by O2 microelectrode measurements which showed that the O2 partial pressure was much lower in the zone of infected cells than in the cortex. Measurements of nitrogenase activity and O2 uptake as a function of temperature and partial pressure of O2 were consistent with diffusion limitation of O2 uptake by the inner cortex. In spite of the presumed absence of leghemoglobin in nodules of Parasponia rigida Merr. and Perry, energy usage for nitrogen fixation was similar to that in legume nodules. The results demonstrate that O2 regulation in legume and Parasponia nodules is very similar and differs from O2 regulation in actionorhizal nodules. Images PMID:16662284

  11. Study on the killing of oceanic harmful micro-organisms in ship's ballast water using oxygen active particles

    NASA Astrophysics Data System (ADS)

    Chen, C.; Meng, X. Y.; Bai, M. D.; Tian, Y. P.; Jing, Y.

    2013-03-01

    Global Environment Facility has identified that the spread of marine invasive alien species is one of the four major risk factors threatening the safety of global marine environments. Ballast water discharge is the main cause of biological invasion. With physical methods of strong electric field ionization discharge at atmospheric pressure, O2 and sea water (gaseous) were ionized, and then dissociated to a number of oxygen active particles (ROS) such as ·OH, O2+, H2O+, etc. ROS was injected into 0.6 t h-1 ballast water treatment system to form high concentration ROS solution in order to kill the harmful micro-organisms in ballast water. According to the land-based test standard of International Maritime Organization (IMO) Guidelines for Approval of Ballast Water Management Systems (G8), this paper concludes that single-cell algae of 3.0 × 104 cell ml-1 and bacteria of 2.0 × 104 cfu ml-1 were killed by ROS solution of 2.0 ppm. Death rate could reach almost 100%. The results meet the requirements of Regulation D-2 of International Convention for the Control and Management of Ships' Ballast Water and Sediments completely.

  12. 75 FR 16895 - Reports, Forms and Record Keeping Requirements; Agency Information Collection Activity Under OMB...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-02

    ... National Highway Traffic Safety Administration Reports, Forms and Record Keeping Requirements; Agency Information Collection Activity Under OMB Review AGENCY: National Highway Traffic Safety Administration.... Mary Versailles, Office of Rulemaking, National Highway Traffic Safety Administration, 1200 New...

  13. 77 FR 47162 - Reports, Forms and Recordkeeping Requirements; Agency Information Collection Activity Under OMB...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-07

    ... National Highway Traffic Safety Administration Reports, Forms and Recordkeeping Requirements; Agency Information Collection Activity Under OMB Review AGENCY: National Highway Traffic Safety Administration, DOT...- 5378. SUPPLEMENTARY INFORMATION: National Highway Traffic Safety Administration Title:...

  14. 76 FR 41331 - Reports, Forms and Recordkeeping Requirements; Agency Information Collection Activity Under OMB...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-13

    ... TRANSPORTATION National Highway Traffic Safety Administration Reports, Forms and Recordkeeping Requirements; Agency Information Collection Activity Under OMB Review AGENCY: National Highway Traffic Safety... and fax number is (202) 366-7002. SUPPLEMENTARY INFORMATION: National Highway Traffic...

  15. 77 FR 72321 - Agency Information Collection Activities: Proposed Collection; Comment Request; Supplemental Form...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-05

    ... Food and Nutrition Service Agency Information Collection Activities: Proposed Collection; Comment Request; Supplemental Form for Collecting Taxpayer Identifying Numbers AGENCY: Food and Nutrition Service... Porter, Director, Office of Internal Controls, Audits and Investigations, Food and Nutrition Service,...

  16. 76 FR 52014 - Agency Information Collection Activities: Applicant Information Form (1-783)

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-19

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF JUSTICE Federal Bureau of Investigation Agency Information Collection Activities: Applicant Information Form (1-783) ACTION: 30-Day Notice of Information Collection. The Department of Justice (DOJ), Federal...

  17. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    SciTech Connect

    Ju, Hua; Li, Zhihu; Xu, Yanhui

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  18. Role of Reactive Oxygen Species in the Abrogation of Oxaliplatin Activity by Cetuximab in Colorectal Cancer

    PubMed Central

    Santoro, Valeria; Jia, Ruochen; Thompson, Hannah; Nijhuis, Anke; Jeffery, Rosemary; Kiakos, Konstantinos; Silver, Andrew R.; Hartley, John A.

    2016-01-01

    Background: The antibody cetuximab, targeting epidermal growth factor receptor (EGFR), is used to treat metastatic colorectal cancer (mCRC). Clinical trials suggest reduced benefit from the combination of cetuximab with oxaliplatin. The aim of this study was to investigate potential negative interactions between cetuximab and oxaliplatin. Methods: Thiazolyl blue tetrazolium bromide (MTT) assay and Calcusyn software were used to characterize drug interactions. Reactive oxygen species (ROS) were measured by flow cytometry and real-time polymerase chain reaction oxidative stress arrays identified genes regulating ROS production. Chromatin immunoprecipitation (ChIP) measured signal transducer and activator of transcription 1 (STAT-1) binding to dual oxidase 2 (DUOX2) promoter. SW48, DLD-1 KRAS wild-type cell lines and DLD-1 xenograft models exposed to cetuximab, oxaliplatin, or oxaliplatin + cetuximab (control [saline]; n = 3 mice per treatment group) were used. Statistical tests were two-sided. Results: Cetuximab and oxaliplatin exhibited antagonistic effects on cellular proliferation and apoptosis (caspase 3/7 activity reduced by 1.4-fold, 95% confidence interval [CI] = 0.78 to 2.11, P = .003) as opposed to synergistic effects observed with the irinotecan metabolite 7-Ethyl-10-hydroxycamptothecin (SN-38). Although both oxaliplatin and SN-38 produced ROS, only oxaliplatin-mediated apoptosis was ROS dependent. Production of ROS by oxaliplatin was secondary to STAT1-mediated transcriptional upregulation of DUOX2 (3.1-fold, 95% CI = 1.75 to 2.41, P < .001). Inhibition of DUOX2 induction and p38 activation by cetuximab reduced oxaliplatin cytotoxicity. Conclusions: Inhibition of STAT1 and DUOX2-mediated ROS generation by cetuximab impairs p38-dependent apoptosis by oxaliplatin in preclinical models and may contribute to reduced efficacy in clinical settings. Understanding the rationale for unexpected trial results will inform improved rationales for combining EGFR

  19. 78 FR 19726 - Agency Information Collection Activities: Visa Waiver Program Carrier Agreement (CBP Form I-775)

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-04-02

    ... SECURITY U.S. Customs and Border Protection Agency Information Collection Activities: Visa Waiver Program... requirement concerning the Visa Waiver Program Carrier Agreement (CBP Form I-775). This request for comment is... information collection: Title: Visa Waiver Program Carrier Agreement. OMB Number: 1651-0110. Form Number:...

  20. 40 CFR 761.205 - Notification of PCB waste activity (EPA Form 7710-53).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... handler must renotify the Agency include, but are not limited to the following: the company changes... CFR PART 761” on the manifests, records, and reports which they shall prepare under this subpart... using EPA Form 7710-53 and those activities change, the facility must resubmit EPA Form 7710-53...

  1. 78 FR 24187 - Commission Information Collection Activities (FERC Form 6-Q); Comment Request

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-04-24

    ... Energy Regulatory Commission Commission Information Collection Activities (FERC Form 6-Q); Comment... Energy Regulatory Commission (Commission or FERC) is submitting the information collection FERC Form 6-Q... issued a Notice in the Federal Register (78 FR 8500, 2/6/2013) requesting public comments. FERC...

  2. 78 FR 52824 - Proposed Information Collection (Bowel and Bladder Care Billing Form) Activity: Comment Request

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-26

    ... AFFAIRS Proposed Information Collection (Bowel and Bladder Care Billing Form) Activity: Comment Request... evaluate the Bowel and Bladder Care Billing Form used by caregivers of eligible Veterans to document time spent providing services related specifically to bowel and bladder care. DATES: Written comments...

  3. 77 FR 23271 - Agency Information Collection Activities: Form I-881; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-04-18

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-881... (DHS), U.S. Citizenship and Immigration Services (USCIS) will be submitting the following information... component of the Department of Homeland Security sponsoring the collection: Form I-881; U.S. Citizenship...

  4. 75 FR 51096 - Agency Information Collection Activities: Form N-400; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-400... Department of Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be submitting the... of Homeland Security sponsoring the collection: Form N-400; U.S. Citizenship and Immigration...

  5. 77 FR 16047 - Agency Information Collection Activities: Form I-589; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-19

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-589.... 1615-0067. The Department Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be...: Form I-589; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will be asked...

  6. 75 FR 51094 - Agency Information Collection Activities: Form N-600; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-600... Collection under Review; Form N- 600, Application for Certificate of Citizenship; OMB Control No. 1615- 0057. The Department of Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will...

  7. 75 FR 51095 - Agency Information Collection Activities: Form N-336; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-336... Section 336; OMB Control No. 1615-0050. The Department of Homeland Security, U.S. Citizenship and... sponsoring the collection: Form N-336; U.S. Citizenship and Immigration Services (USCIS). (4) Affected...

  8. 77 FR 36285 - Agency Information Collection Activities: Form I-693, Revision of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-18

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-693... Control No. 1615-0033. The Department of Homeland Security (DHS), U.S. Citizenship and Immigration... of the Department of Homeland Security sponsoring the collection: Form I-693. U.S. Citizenship...

  9. 76 FR 55081 - Agency Information Collection Activities: Form I-129S; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-06

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-129S... Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be submitting the following... collection: Form I-129S; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will...

  10. 76 FR 63322 - Agency Information Collection Activities: Form G-28, Revision of an Approved Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-12

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form G-28.... The Department of Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be... Department of Homeland Security sponsoring the collection: Form G-28. U.S. Citizenship and...

  11. 75 FR 54646 - Agency Information Collection Activities: Form I-914; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-09-08

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-914.... Citizenship and Immigration Services (USCIS) will be submitting the following information collection request... of the Department of Homeland Security sponsoring the collection: Form I-914; U.S. Citizenship...

  12. 77 FR 12071 - Agency Information Collection Activities: Form I-601, Revision of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-28

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-601... Department of Homeland Security, U.S. Citizenship and Immigration Services will be submitting the following... sponsoring the collection: Form I-601. U.S. Citizenship and Immigration Services. (4) Affected public...

  13. 76 FR 58029 - Agency Information Collection Activities: Form N-600K, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-19

    ... collection was previously published in the Federal Register on June 29, 2011, at 76 FR 38197, allowing for a... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-600K... Information Collection Under Review: Form N- 600K; Application for Citizenship and Issuance of...

  14. 75 FR 51096 - Agency Information Collection Activities: Form N-470; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-470.... 1615-0056. The Department of Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will...: Form N-470; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will be asked...

  15. 76 FR 17144 - Agency Information Collection Activities: Form N-300; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-28

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-300.... The Department Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be submitting... collection: Form N-300; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will...

  16. 77 FR 27473 - Agency Information Collection Activities: Form I-924; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-10

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-924... Department of Homeland Security (DHS), U.S. Citizenship and Immigration Services (USCIS) will be submitted... sponsoring the collection: Form I-924; U.S. Citizenship and Immigration Services. (4) Affected public...

  17. 77 FR 34398 - Agency Information Collection Activities: Form N-565, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-11

    ..., 2012, at 77 FR 18255, allowing for a 60-day public comment period. USCIS did not receive any comments... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-565... Information Collection Under Review: Form N- 565, Application for Replacement...

  18. 77 FR 12072 - Agency Information Collection Activities: Form I-824; Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-28

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-824... Homeland Security, U.S. Citizenship and Immigration Services (USCIS) has submitted the following... collection: Form I-824; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will...

  19. 75 FR 6212 - Agency Information Collection Activities: Form I-129, Revision of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-08

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-129... Department of Homeland Security, U.S. Citizenship and Immigration Services has submitted the following... Security sponsoring the collection: Form I-129. U.S. Citizenship and Immigration Services. (4)...

  20. 78 FR 5477 - Agency Information Collection Activities: InfoPass System, No Form Number; Extension, Without...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-01-25

    ... information collection notice was previously published in the Federal Register on October 31, 2012, at 77 FR... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: InfoPass... Collection. (2) Title of the Form/Collection: InfoPass System. (3) Agency form number, if any, and...

  1. Tunable growth of nanodendritic silver by galvanic-cell mechanism on formed activated carbon.

    PubMed

    Wang, Fei; Lai, Yijian; Zhao, Binyuan; Hu, Xiaobin; Zhang, Di; Hu, Keao

    2010-06-01

    Well-defined silver dendritic nanostructures have been prepared in large quantities in an ambient environment using formed activated carbon (FAC) only. A reasonable mechanism (step 1: reduction by surface reductive groups; step 2: growing in the form of a galvanic cell) is suggested.

  2. 77 FR 21104 - Agency Information Collection Activities: Form I-694, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-04-09

    ... a brief abstract: Primary: Individuals and households. USCIS uses the information provided on Form I... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-694, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice...

  3. 75 FR 29780 - Agency Information Collection Activities: Form I-612, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-05-27

    ... the Federal Register on March 12, 2010, at 74 FR 11898, allowing for a 60-day public comment period... abstract: Primary: Individuals or Households. Form I- 612 is used by USCIS to determine eligibility for a... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form...

  4. 76 FR 11808 - Agency Information Collection Activities: Form I-590, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-03

    ... abstract: Primary: Individuals or Households. Form I- 590 provides a uniform method for applicants to apply... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-590, Extension of a Currently Approved Information Collection; Comment Request ACTION: 30-Day Notice...

  5. 76 FR 20361 - Agency Information Collection Activities: Form I-694, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-12

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-694, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 694, Notice of Appeal of Decision Under Section 210 or 245A;...

  6. 77 FR 9259 - Agency Information Collection Activities: Form I-361, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-02-16

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-361, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 361, Affidavit of Financial Support and Intent To Petition...

  7. 75 FR 70016 - Agency Information Collection Activities: Form I-566, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-16

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-566, Extension of a Currently Approved Information Collection; Comment Request ACTION: 30-Day Notice of Information Collection Under Review: Form I- 566, Interagency Record of Individual Requesting...

  8. 76 FR 66944 - Agency Information Collection Activities: Form I-129F; Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-28

    ... SECURITY Citizenship and Immigration Services Agency Information Collection Activities: Form I-129F; Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 129F, Petition for Alien Fiance(e). OMB Control No....

  9. 75 FR 29779 - Agency Information Collection Activities: Form I-918, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-05-27

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-918, Extension of a Currently Approved Information Collection; Comment Request ACTION: 30-Day Notice of Information Collection Under Review: Form I- 918, Petition for U Nonimmigrant Status; and Supplement A and...

  10. 75 FR 76745 - Agency Information Collection Activities: Form I-601, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-09

    ... 75 FR 74071, mistakenly announcing the revision of the Form I-601. The 60-day notice should have... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-601, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice...

  11. 76 FR 16800 - Agency Information Collection Activities: Form I-601, Revision of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-25

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-601, Revision of a Currently Approved Information Collection; Comment Request ACTION: 30-Day Notice of Information Collection Under Review: Form I- 601, Application for Waiver of Grounds of Inadmissibility;...

  12. 76 FR 71056 - Agency Information Collection Activities: Form I-566, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-16

    ... Information Collection Under Review: Form I- 566, Interagency Record of Request, A, G or NATO Dependent... Federal Register on August 18, 2011, at 76 FR 51382, allowing for a 60-day public comment period. USCIS... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form...

  13. 75 FR 41215 - Agency Information Collection Activities: Form I-821, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-15

    ... required to respond, as well as a brief abstract: Primary: Individuals or Households. Form I- 821 is... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-821, Extension of a Currently Approved Information Collection; Comment Request ACTION: 30-Day Notice...

  14. 75 FR 37821 - Agency Information Collection Activities: Form I-751, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-06-30

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-751, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 751, Petition to Remove Conditions on Residence; OMB Control...

  15. 76 FR 45845 - Agency Information Collection Activities: Form I-777, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-01

    ... published in the Federal Register on May 19, 2011, at 76 FR 28800, allowing for a 60-day public comment...: Primary: Individuals or Households. Form I- 777 is used by applicants applying for a Northern Marina... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form...

  16. 76 FR 20361 - Agency Information Collection Activities: Form I-907, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-04-12

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-907, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-day notice of information collection under review: Form I- 907, Request for Premium Processing Service; OMB Control No....

  17. 75 FR 11898 - Agency Information Collection Activities: Form I-612, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-12

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-612, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 612, Application for Waiver of the Foreign Residence...

  18. 75 FR 74071 - Agency Information Collection Activities: Form I-601, Revision of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-30

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-601, Revision of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 601, Application for Waiver of Grounds of Inadmissibility;...

  19. 76 FR 66946 - Agency Information Collection Activities: Form I-539, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-28

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-539, Extension of a Currently Approved Information Collection; Comment Request ACTION: 60-Day Notice of Information Collection Under Review: Form I- 539, Application to Extend/Change Nonimmigrant Status....

  20. 75 FR 57049 - Agency Information Collection Activities: Form I-777, Application for Replacement of Northern...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-09-17

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-777, Application for Replacement of Northern Mariana Card ACTION: Correction to 30-day notice of Information Collection Under Review: Form I-777, Application for Replacement of Northern Mariana Card; OMB Control...

  1. 76 FR 52961 - Agency Information Collection Activities: Form N-300; Revision of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-24

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-300.... The Department Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be submitting... collection: Form N-300; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will...

  2. 76 FR 70747 - Agency Information Collection Activities: Form I-90; Revision of a Currently Approved Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-15

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form I-90... Department of Homeland Security, U.S. Citizenship and Immigration Services (USCIS) will be submitting the...: Form I-90; U.S. Citizenship and Immigration Services (USCIS). (4) Affected public who will be asked...

  3. 76 FR 9805 - Agency Information Collection Activities: Form G-845 and Supplement; Revision of a Currently...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-22

    ... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form G-845 and.... Citizenship and Immigration Services (USCIS) will be submitting the following information collection request... collection: Form G-845 and Supplement. U.S. Citizenship and Immigration Services. (4) Affected public...

  4. 76 FR 48874 - Agency Information Collection Activities: Form G-884, Extension of an Existing Information...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-09

    ... the Federal Register on March 17, 2011, at 76 FR 28444, allowing for a 60- day public comment period... SECURITY Citizenship and Immigration Services Agency Information Collection Activities: Form G-884... Collection Under Review: Form G- 884, Request for the Return of Original Document(s). The Department...

  5. 76 FR 39415 - Agency Information Collection Activities: Form N-644, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-06

    ... was previously published in the Federal Register on April 19, 2011, at 76 FR 21913, allowing for a 60... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-644... Information Collection Under Review: Form N- 644, Application for Posthumous Citizenship; OMB Control No....

  6. 75 FR 70278 - Agency Information Collection Activities: Form N-600, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-17

    ... collection was previously published in the Federal Register on August 18, 2010, at 75 FR 51094, allowing for... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-600... Information Collection Under Review: Form N- 600, Application for Certificate of Citizenship; OMB Control...

  7. 76 FR 45844 - Agency Information Collection Activities: Form N-426, Extension of a Currently Approved...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-01

    ... published in the Federal Register on May 10, 2011, at 76 FR 27078, allowing for a 60-day public comment... SECURITY U.S. Citizenship and Immigration Services Agency Information Collection Activities: Form N-426... Information Collection Under Review: Form N- 426, Request for Certification of Military or Naval Service....

  8. 77 FR 128 - Agency Information Collection Activities: Form N-600, Revision of a Currently Approved...

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    2012-01-03

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  15. Apparatus and method for preparing oxygen-15 labeled water H.sub.2 [.sup.15 O] in an injectable form for use in positron emission tomography

    DOEpatents

    Ferrieri, Richard A.; Schlyer, David J.; Alexoff, David

    1996-01-09

    A handling and processing apparatus for preparing Oxygen-15 labeled water (H.sub.2 [.sup.15 O]) in injectable form for use in Positron Emission Tomography from preferably H.sub.2 [.sup.15 O] produced by irradiating a flowing gas target of nitrogen and hydrogen. The apparatus includes a collector for receiving and directing a gas containing H.sub.2 [.sup.15 O] gas and impurities, mainly ammonia (NH.sub.3) gas into sterile water to trap the H.sub.2 [.sup.15 O] and form ammonium (NH.sub.4.sup.+) in the sterile water. A device for displacing the sterile water containing H.sub.2 [.sup.15 O] and NH.sub.4.sup.+ through a cation resin removes NH.sub.4.sup.+ from the sterile water. A device for combining the sterile water containing H.sub.2 [.sup.15 O] with a saline solution produces an injectable solution. Preferably, the apparatus includes a device for delivering the solution to a syringe for injection into a patient. Also, disclosed is a method for preparing H.sub.2 [.sup.15 O] in injectable form for use in Positron Emission Tomography in which the method neither requires isotopic exchange reaction nor application of high temperature.

  16. Apparatus and method for preparing oxygen-15 labeled water H{sub 2}[{sup 15}O] in an injectable form for use in positron emission tomography

    DOEpatents

    Ferrieri, R.A.; Schlyer, D.J.; Alexoff, D.

    1996-01-09

    A handling and processing apparatus is revealed for preparing Oxygen-15 labeled water (H{sub 2}[{sup 15}O]) in injectable form for use in Positron Emission Tomography from preferably H{sub 2}[{sup 15}O] produced by irradiating a flowing gas target of nitrogen and hydrogen. The apparatus includes a collector for receiving and directing a gas containing H{sub 2}[{sup 15}O] gas and impurities, mainly ammonia (NH{sub 3}) gas into sterile water to trap the H{sub 2}[{sup 15}O] and form ammonium (NH{sub 4}{sup +}) in the sterile water. A device for displacing the sterile water containing H{sub 2}[{sup 15}O] and NH{sub 4}{sup +} through a cation resin removes NH{sub 4}{sup +} from the sterile water. A device for combining the sterile water containing H{sub 2}[{sup 15}O] with a saline solution produces an injectable solution. Preferably, the apparatus includes a device for delivering the solution to a syringe for injection into a patient. Also, disclosed is a method for preparing H{sub 2}[{sup 15}O] in injectable form for use in Positron Emission Tomography in which the method neither requires isotopic exchange reaction nor application of high temperature. 7 figs.

  17. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries.

    PubMed

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

    2016-01-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries. PMID:27363944

  18. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

    DOE PAGES

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Chen, Yan; An, Ke; Zhu, Yimei; et al

    2016-07-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high asmore » 301 mAh g–1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g–1 still remains without any obvious decay in voltage. Lastly, this study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.« less

  19. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

    2016-07-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g-1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g-1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

  20. Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries.

    PubMed

    Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

    2016-01-01

    Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.