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Sample records for p450bm3 oxygen activation

  1. Peptide-Mediated Specific Immobilization of Catalytically Active Cytochrome P450 BM3 Variant.

    PubMed

    Zernia, Sarah; Ott, Florian; Bellmann-Sickert, Kathrin; Frank, Ronny; Klenner, Marcus; Jahnke, Heinz-Georg; Prager, Andrea; Abel, Bernd; Robitzki, Andrea; Beck-Sickinger, Annette G

    2016-04-20

    Cytochrome P450 BM3 (CYP102A1) from Bacillus megaterium is an interesting target for biotechnological applications, because of its vast substrate variety combined with high P450 monooxygenase activity. The low stability in vitro could be overcome by immobilization on surfaces. Here we describe a novel method for immobilization on metal surfaces by using selectively binding peptides. A P450 BM3 triple mutant (3M-P450BM3: A74G, F87V, L188Q) was purified as protein thioester and ligated to indium tin oxide or gold binding peptides (BP) named HighSP-BP and Cys-BP, respectively. The ligation products were characterized by Western Blot and tryptic digestion combined with mass spectrometry, and displayed high affinity binding on the depicted surfaces. Next, we could demonstrate by benzyloxyresorufin O-dealkylation assay (BROD assay) that the activity of immobilized ligation products is higher than for the soluble form. The study provides a new tool for selective modification and immobilization of P450 variants. PMID:26967204

  2. Peroxidase activity stabilization of cytochrome P450(BM3) by rational analysis of intramolecular electron transfer.

    PubMed

    Vidal-Limón, Abraham; Águila, Sergio; Ayala, Marcela; Batista, Cesar V; Vazquez-Duhalt, Rafael

    2013-05-01

    Combined quantum mechanical and molecular mechanical (QM/MM) calculations were used to explore the electron pathway involved in the suicide inactivation of cytochrome P450BM3 from Bacillus megaterium. The suicide inactivation is a common phenomenon observed for heme peroxidases, in which the enzyme is inactivated as a result of self-oxidation mediated by highly oxidizing enzyme intermediates formed during the catalytic cycle. The selected model was a mutant comprising only the heme domain (CYPBM3 21B3) that had been previously evolved to efficiently catalyze hydroxylation reactions with hydrogen peroxide (H2O2) as electron acceptor. An extensive mapping of residues involved in electron transfer routes was obtained from density functional calculations on activated heme (i.e. Compound I) and selected amino acid residues. Identification of oxidizable residues (electron donors) was performed by selectively activating/deactivating different quantum regions. This method allowed a rational identification of key oxidizable targets in order to replace them for less oxidizable residues by site-directed mutagenesis. The residues W96 and F405 were consistently predicted by the QM/MM electron pathway to hold high spin density; single and double mutants of P450BM3 on these positions (W96A, F405L, W96A/F405L) resulted in a more stable variants in the presence of hydrogen peroxide, displaying a similar reaction rate than P450BM3 21B3. Furthermore, mass spectrometry confirmed these oxidation sites and corroborated the possible routes described by QM/MM electron transfer (ET) pathways. PMID:23425936

  3. Active site substitution A82W improves the regioselectivity of steroid hydroxylation by cytochrome P450 BM3 mutants as rationalized by spin relaxation nuclear magnetic resonance studies.

    PubMed

    Rea, V; Kolkman, A J; Vottero, E; Stronks, E J; Ampt, K A M; Honing, M; Vermeulen, N P E; Wijmenga, S S; Commandeur, J N M

    2012-01-24

    Cytochrome P450 BM3 from Bacillus megaterium is a monooxygenase with great potential for biotechnological applications. In this paper, we present engineered drug-metabolizing P450 BM3 mutants as a novel tool for regioselective hydroxylation of steroids at position 16β. In particular, we show that by replacing alanine at position 82 with a tryptophan in P450 BM3 mutants M01 and M11, the selectivity toward 16β-hydroxylation for both testosterone and norethisterone was strongly increased. The A82W mutation led to a ≤42-fold increase in V(max) for 16β-hydroxylation of these steroids. Moreover, this mutation improves the coupling efficiency of the enzyme, which might be explained by a more efficient exclusion of water from the active site. The substrate affinity for testosterone increased at least 9-fold in M11 with tryptophan at position 82. A change in the orientation of testosterone in the M11 A82W mutant as compared to the orientation in M11 was observed by T(1) paramagnetic relaxation nuclear magnetic resonance. Testosterone is oriented in M11 with both the A- and D-ring protons closest to the heme iron. Substituting alanine at position 82 with tryptophan results in increased A-ring proton-iron distances, consistent with the relative decrease in the level of A-ring hydroxylation at position 2β. PMID:22208729

  4. Application of a cocktail approach to screen cytochrome P450 BM3 libraries for metabolic activity and diversity.

    PubMed

    Reinen, Jelle; Postma, Geert; Tump, Cornelis; Bloemberg, Tom; Engel, Jasper; Vermeulen, Nico P E; Commandeur, Jan N M; Honing, Maarten

    2016-02-01

    In the present study, the validity of using a cocktail screening method in combination with a chemometrical data mining approach to evaluate metabolic activity and diversity of drug-metabolizing bacterial Cytochrome P450 (CYP) BM3 mutants was investigated. In addition, the concept of utilizing an in-house-developed library of CYP BM3 mutants as a unique biocatalytic synthetic tool to support medicinal chemistry was evaluated. Metabolic efficiency of the mutant library towards a selection of CYP model substrates, being amitriptyline (AMI), buspirone (BUS), coumarine (COU), dextromethorphan (DEX), diclofenac (DIC) and norethisterone (NET), was investigated. First, metabolic activity of a selection of CYP BM3 mutants was screened against AMI and BUS. Subsequently, for a single CYP BM3 mutant, the effect of co-administration of multiple drugs on the metabolic activity and diversity towards AMI and BUS was investigated. Finally, a cocktail of AMI, BUS, COU, DEX, DIC and NET was screened against the whole in-house CYP BM3 library. Different validated quantitative and qualitative (U)HPLC-MS/MS-based analytical methods were applied to screen for substrate depletion and targeted product formation, followed by a more in-depth screen for metabolic diversity. A chemometrical approach was used to mine all data to search for unique metabolic properties of the mutants and allow classification of the mutants. The latter would open the possibility of obtaining a more in-depth mechanistic understanding of the metabolites. The presented method is the first MS-based method to screen CYP BM3 mutant libraries for diversity in combination with a chemometrical approach to interpret results and visualize differences between the tested mutants. PMID:26753974

  5. Activation of phosphorothionate pesticides based on a cytochrome P450 BM-3 (CYP102 A1) mutant for expanded neurotoxin detection in food using acetylcholinesterase biosensors.

    PubMed

    Schulze, Holger; Schmid, Rolf D; Bachmann, Till T

    2004-03-15

    A novel enzymatic in vitro activation method for phosphorothionates has been developed to allow their detection with acetylcholinesterase (AChE) biosensors. Activation is necessary because this group of insecticides shows nearly no inhibitory effect toward AChE in their pure nonmetabolized form. In contrast, they exert a strong inhibitory effect on AChE after oxidation as it takes place by metabolic activation in higher organisms. Standard chemical methods to oxidize phosphorothionates showed inherent disadvantages that impede their direct use in food analysis. In contrast, a genetically engineered triple mutant of P450 BM-3 (CYP102 A1) could convert the two frequently used insecticides parathion and chlorpyrifos into their oxo variants as was confirmed by GC/MS measurements. The wild-type protein was unable to do so. In the case of chlorpyrifos, the enzymatic activation was as good as the chemical oxidation. In the case of parathion, the P450 activation was more efficient than the oxidation by NBS but neither activation method yielded an AChE inhibition that was as high as with paraoxon. The application of the method to infant food in combination with a disposable AChE biosensor enabled detection of chlorpyrifos and parathion at concentrations down to 20 microg/kg within an overall assay time of 95 min. PMID:15018574

  6. Engineering bacterial cytochrome P450 (P450) BM3 into a prototype with human P450 enzyme activity using indigo formation.

    PubMed

    Park, Sun-Ha; Kim, Dong-Hyun; Kim, Dooil; Kim, Dae-Hwan; Jung, Heung-Chae; Pan, Jae-Gu; Ahn, Taeho; Kim, Donghak; Yun, Chul-Ho

    2010-05-01

    Human cytochrome P450 (P450) enzymes metabolize a variety of endogenous and xenobiotic compounds, including steroids, drugs, and environmental chemicals. In this study, we examine the possibility that bacterial P450 BM3 (CYP102A1) mutants with indole oxidation activity have the catalytic activities of human P450 enzymes. Error-prone polymerase chain reaction was carried out on the heme domain-coding region of the wild-type gene to generate a CYP102A1 DNA library. The library was transformed into Escherichia coli for expression of the P450 mutants. A colorimetric colony-based method was adopted for primary screening of the mutants. When the P450 activities were measured at the whole-cell level, some of the blue colonies, but not the white colonies, possessed apparent oxidation activity toward coumarin and 7-ethoxycoumarin, which are typical human P450 substrates that produce fluorescent products. Coumarin is oxidized by the CYP102A1 mutants to produce two metabolites, 7-hydroxycoumarin and 3-hydroxycoumarin. In addition, 7-ethoxycoumarin is simultaneously oxidized to 7-hydroxycoumarin by O-deethylation reaction and to 3-hydroxy,7-ethoxycoumarin by 3-hydroxylation reactions. Highly active mutants are also able to metabolize several other human P450 substrates, including phenacetin, ethoxyresorufin, and chlorzoxazone. These results indicate that indigo formation provides a simple assay for identifying CYP102A1 mutants with a greater potential for human P450 activity. Furthermore, our computational findings suggest a correlation between the stabilization of the binding site and the catalytic efficiency of CYP102A1 mutants toward coumarin: the more stable the structure in the binding site, the lower the energy barrier and the higher the catalytic efficiency. PMID:20100815

  7. Kinetics and Activation Parameters for Oxidations of Styrene by Compounds I from Cytochrome P450BM-3 (CYP102A1) Heme Domain and from CYP119†

    PubMed Central

    Yuan, Xinting; Wang, Qin; Horner, John H.; Sheng, Xin; Newcomb, Martin

    2009-01-01

    Cytochrome P450 (CYP or P450) enzymes are ubiquitous in nature where they catalyze a vast array of oxidation reactions. The active oxidants in P450s have long been assumed to be iron(IV)-oxo porphyrin radical cations termed Compounds I, but P450 Compounds I have proven difficult to prepare. The recent development of an entry to these transients by photo-oxidation of the corresponding iron(IV)-oxo neutral porphyrin species (Compounds II) permits spectroscopic and kinetic studies. We report here application of the photo-oxidation method for production of Compound I from the heme domain of CYP102A1 (cytochrome P450BM-3), and product and kinetic studies of reactions of styrene with this Compound I transient and also Compound I from CYP119. The studies were performed at low temperatures in 1:1 (v:v) mixtures of glycerol--phosphate buffer. Single turnover reactions at 0 °C gave styrene oxide in good yields. In kinetic studies conducted between −10 and −50 °C, both Compounds I displayed saturation kinetics permitting determinations of binding constants and first-order oxidation rate constants. Temperature-dependent functions for the binding constants and rate constants were determined for both Compounds I. In the temperature range studied, the Compound I transient from CYP102A1 heme domain bound styrene more strongly than Compound I from CYP119, but the rate constants for oxidations of styrene by the latter were somewhat larger than those for the former. The temperature dependent functions for the first-order oxidation reactions are log k = 13.2 – 15.2/2.303RT and log k = 13.3 – 14.6/2.303RT (kcal/mol) for Compounds I from CYP102A1 heme domain and CYP119, respectively. PMID:19708688

  8. Subtle structural changes in the Asp251Gly/Gln307His P450 BM3 mutant responsible for new activity toward diclofenac, tolbutamide and ibuprofen.

    PubMed

    Di Nardo, Giovanna; Dell'Angelo, Valentina; Catucci, Gianluca; Sadeghi, Sheila J; Gilardi, Gianfranco

    2016-07-15

    This paper reports the structure of the double mutant Asp251Gly/Gln307His (named A2) generated by random mutagenesis, able to produce 4'-hydroxydiclofenac, 2-hydroxyibuprofen and 4-hydroxytolbutamide from diclofenac, ibuprofen and tolbutamide, respectively. The 3D structure of the substrate-free mutant shows a conformation similar to the closed one found in the substrate-bound wild type enzyme, but with a higher degree of disorder in the region of the G-helix and F-G loop. This is due to the mutation Asp251Gly that breaks the salt bridge between Aps251 on I-helix and Lys224 on G-helix, allowing the G-helix to move away from I-helix and conferring a higher degree of flexibility to this element. This subtle structural change is accompanied by long-range structural rearrangements of the active site with the rotation of Phe87 and a reorganization of catalytically important water molecules. The impact of these structural features on thermal stability, reduction potential and electron transfer is investigated. The data demonstrate that a single mutation far from the active site triggers an increase in protein flexibility in a key region, shifting the conformational equilibrium toward the closed form that is ready to accept electrons and enter the P450 catalytic cycle as soon as a substrate is accepted. PMID:26718083

  9. Insights into electron leakage in the reaction cycle of cytochrome P450 BM3 revealed by kinetic modeling and mutagenesis.

    PubMed

    Lim, Joseph B; Barker, Kimberly A; Eller, Kristen A; Jiang, Linda; Molina, Veronica; Saifee, Jessica F; Sikes, Hadley D

    2015-11-01

    As a single polypeptide, cytochrome P450 BM3 fuses oxidase and reductase domains and couples each domain's function to perform catalysis with exceptional activity upon binding of substrate for hydroxylation. Mutations introduced into the enzyme to change its substrate specificity often decrease coupling efficiency between the two domains, resulting in unproductive consumption of cofactors and formation of water and/or reactive species. This phenomenon can correlate with leakage, in which P450 BM3 uses electrons from NADPH to reduce oxygen to water and/or reactive species even without bound substrate. The physical basis for leakage is not yet well understood in this particular member of the cytochrome P450 family. To clarify the relationship between leakage and coupling, we used simulations to illustrate how different combinations of kinetic parameters related to substrate-free consumption of NADPH and substrate hydroxylation can lead to either minimal effects on coupling or a dramatic decrease in coupling as a result of leakage. We explored leakage in P450 BM3 by introducing leakage-enhancing mutations and combining these mutations to assess whether doing so increases leakage further. The variants in this study provide evidence that while a transition to high spin may be vital for coupled hydroxylation, it is not required for enhanced leakage; substrate binding and the consequent shift in spin state are not necessary as a redox switch for catalytic oxidation of NADPH. Additionally, the variants in this study suggest a tradeoff between leakage and stability and thus evolvability, as the mutations we investigated were far more deleterious than other mutations that have been used to change substrate specificity. PMID:26311413

  10. Chromogenic nitrophenolate-based substrates for light-driven hybrid P450 BM3 enzyme assay.

    PubMed

    Lam, Quan; Cortez, Alejandro; Nguyen, Thanh Truc; Kato, Mallory; Cheruzel, Lionel

    2016-05-01

    The incorporation of a p-nitrophenoxy moiety in substrates has enabled the development of colorimetric assays to rapidly screen for O-demethylation activity of P450 enzymes. For the light-driven hybrid P450 BM3 enzymes, where a Ru(II) photosensitizer powers the enzyme upon visible light irradiation, we have investigated a family of p-nitrophenoxy derivatives as useful chromogenic substrates compatible with the light-driven approach. The validation of this assay and its adaptability to a 96-well plate format will enable the screening of the next generation of hybrid P450 BM3 enzymes towards C-H bond functionalization of non-natural substrates. PMID:26712653

  11. Biotransformation of the sesquiterpene (+)-valencene by cytochrome P450cam and P450BM-3.

    PubMed

    Sowden, Rebecca J; Yasmin, Samina; Rees, Nicholas H; Bell, Stephen G; Wong, Luet-Lok

    2005-01-01

    The sesquiterpenoids are a large class of naturally occurring compounds with biological functions and desirable properties. Oxidation of the sesquiterpene (+)-valencene by wild type and mutants of P450cam from Pseudomonas putida, and of P450BM-3 from Bacillus megaterium, have been investigated as a potential route to (+)-nootkatone, a fine fragrance. Wild type P450cam did not oxidise (+)-valencene but the mutants showed activities up to 9.8 nmol (nmol P450)(-1) min(-1), with (+)-trans-nootkatol and (+)-nootkatone constituting >85% of the products. Wild type P450BM-3 and mutants had higher activities (up to 43 min(-1)) than P450cam but were much less selective. Of the many products, cis- and trans-(+)-nootkatol, (+)-nootkatone, cis-(+)-valencene-1,10-epoxide, trans-(+)-nootkaton-9-ol, and (+)-nootkatone-13S,14-epoxide were isolated from whole-cell reactions and characterised. The selectivity patterns suggest that (+)-valencene has one binding orientation in P450cam but multiple orientations in P450BM-3. PMID:15602599

  12. A Novel Semi-biosynthetic Route for Artemisinin Production Using Engineered Substrate-Promiscuous P450BM3

    SciTech Connect

    Dietrich, Jeffrey; Yoshikuni, Yasuo; Fisher, Karl; Woolard, Frank; Ockey, Denise; McPhee, Derek; Renninger, Neil; Chang, Michelle; Baker, David; Keasling, Jay

    2009-11-30

    Production of fine heterologus pathways in microbial hosts is frequently hindered by insufficient knowledge of the native metabolic pathway and its cognate enzymes; often the pathway is unresolved and enzymes lack detailed characterization. An alternative paradigm to using native pathways is de novo pathway design using well-characterized, substrate-promiscuous enzymes. We demonstrate this concept using P450BM3 from Bacillus megaterium. Using a computer model, we illustrate how key P450BM3 activ site mutations enable binding of non-native substrate amorphadiene, incorporating these mutations into P450BM3 enabled the selective oxidation of amorphadiene arteminsinic-11s,12-epoxide, at titers of 250 mg L"1 in E. coli. We also demonstrate high-yeilding, selective transformations to dihydroartemisinic acid, the immediate precursor to the high value anti-malarial drug artemisinin.

  13. Effect of Mutation and Substrate Binding on the Stability of Cytochrome P450BM3 Variants.

    PubMed

    Geronimo, Inacrist; Denning, Catherine A; Rogers, W Eric; Othman, Thaer; Huxford, Tom; Heidary, David K; Glazer, Edith C; Payne, Christina M

    2016-06-28

    Cytochrome P450BM3 is a heme-containing enzyme from Bacillus megaterium that exhibits high monooxygenase activity and has a self-sufficient electron transfer system in the full-length enzyme. Its potential synthetic applications drive protein engineering efforts to produce variants capable of oxidizing nonnative substrates such as pharmaceuticals and aromatic pollutants. However, promiscuous P450BM3 mutants often exhibit lower stability, thereby hindering their industrial application. This study demonstrated that the heme domain R47L/F87V/L188Q/E267V/F81I pentuple mutant (PM) is destabilized because of the disruption of hydrophobic contacts and salt bridge interactions. This was directly observed from crystal structures of PM in the presence and absence of ligands (palmitic acid and metyrapone). The instability of the tertiary structure and heme environment of substrate-free PM was confirmed by pulse proteolysis and circular dichroism, respectively. Binding of the inhibitor, metyrapone, significantly stabilized PM, but the presence of the native substrate, palmitic acid, had no effect. On the basis of high-temperature molecular dynamics simulations, the lid domain, β-sheet 1, and Cys ligand loop (a β-bulge segment connected to the heme) are the most labile regions and, thus, potential sites for stabilizing mutations. Possible approaches to stabilization include improvement of hydrophobic packing interactions in the lid domain and introduction of new salt bridges into β-sheet 1 and the heme region. An understanding of the molecular factors behind the loss of stability of P450BM3 variants therefore expedites site-directed mutagenesis studies aimed at developing thermostability. PMID:27267136

  14. Colorimetric high-throughput assay for alkene epoxidation catalyzed by cytochrome P450 BM-3 variant 139-3.

    PubMed

    Alcalde, Miguel; Farinas, Edgardo T; Arnold, Frances H

    2004-03-01

    Cytochrome P450 BM-3 variant 139-3 is highly active in the hydroxylation of alkanes and fatty acids (AGlieder, ET Farinas, and FH Arnold, Nature Biotech 2002;20:1135-1139); it also epoxidizes various alkenes, including styrene. Here the authors describe a colorimetric, high-throughput assay suitable for optimizing this latter activity by directed evolution. The product of styrene oxidation by 139-3, styrene oxide, reacts with the nucleophile gamma-(4-nitrobenzyl)pyridine (NBP) to form a purple-colored precursor dye, which can be monitored spectrophotometrically in cell lysates. The sensitivity limit of this assay is 50-100 microM of product, and the detection limit for P450 BM-3 139-3 is ~0.2 microM of enzyme. To validate the assay, activities in a small library of random mutants were compared to those determined using an NADPH depletion assay for initial turnover rates. PMID:15006137

  15. Crystal Structure of Inhibitor-Bound P450BM-3 Reveals Open Conformation of Substrate Access Channel

    SciTech Connect

    Haines, Donovan C.; Chen, Baozhi; Tomchick, Diana R.; Bondlela, Muralidhar; Hegde, Amita; Machius, Mischa; Peterson, Julian A.

    2008-08-19

    P450BM-3 is an extensively studied P450 cytochrome that is naturally fused to a cytochrome P450 reductase domain. Crystal structures of the heme domain of this enzyme have previously generated many insights into features of P450 structure, substrate binding specificity, and conformational changes that occur on substrate binding. Although many P450s are inhibited by imidazole, this compound does not effectively inhibit P450BM-3. {omega}-Imidazolyl fatty acids have previously been found to be weak inhibitors of the enzyme and show some unusual cooperativity with the substrate lauric acid. We set out to improve the properties of these inhibitors by attaching the {omega}-imidazolyl fatty acid to the nitrogen of an amino acid group, a tactic that we used previously to increase the potency of substrates. The resulting inhibitors were significantly more potent than their parent compounds lacking the amino acid group. A crystal structure of one of the new inhibitors bound to the heme domain of P450BM-3 reveals that the mode of interaction of the amino acid group with the enzyme is different from that previously observed for acyl amino acid substrates. Further, required movements of residues in the active site to accommodate the imidazole group provide an explanation for the low affinity of imidazole itself. Finally, the previously observed cooperativity with lauric acid is explained by a surprisingly open substrate-access channel lined with hydrophobic residues that could potentially accommodate lauric acid in addition to the inhibitor itself.

  16. High throughput assay for cytochrome P450 BM3 for screening libraries of substrates and combinatorial mutants.

    PubMed

    Tsotsou, Georgia Eleni; Cass, Anthony Edward George; Gilardi, Gianfranco

    2002-01-01

    A rapid method for identifying compounds that are potential substrates for the drug metabolising enzyme cytochrome P450 is described. The strategy is based on the detection of a degradation product of NAD(P)H oxidation during substrate turnover by the enzyme expressed in Escherichia coli cells spontaneously lysed under the experimental conditions. The performance of the method has been tested on two known substrates of the wild-type cytochrome P450 BM3, arachidonic (AA) and lauric (LA) acids, and two substrates with environmental significance, the anionic surfactant sodium dodecyl sulfate (SDS), and the solvent 1,1,2,2-tetrachloroethane (TCE). The minimal background signal given from cells expressing cytochrome P450 BM3 in the absence of added substrate is only 3% of the signal in the presence of saturating substrate. Control experiments have proven that this method is specifically detecting NADPH oxidation by catalytic turnover of P450 BM3. The assay has been adapted to a microtitre plate format and used to screen a series of furazan derivatives as potential substrates. Three derivatives were identified as substrates. The method gave a significant different signal for two isomeric furazan derivatives. All results found on the cell lysate were verified and confirmed with the purified enzyme. This strategy opens the way to automated high throughput screening of NAD(P)H-linked enzymatic activity of molecules of pharmacological and biotechnological interest and libraries of random mutants of NAD(P)H-dependent biocatalysts. PMID:11742743

  17. Regio- and stereoselective hydroxylation of 10-undecenoic acid with a light-driven P450 BM3 biocatalyst yielding a valuable synthon for natural product synthesis

    PubMed Central

    Kato, Mallory; Nguyen, Daniel; Gonzalez, Melissa; Cortez, Alejandro; Mullen, Sarah E.; Cheruzel, Lionel E.

    2014-01-01

    We report herein the selective hydroxylation of 10-undecenoic acid with a light-activated hybrid P450 BM3 enzyme. Under previously developed photocatalytic reaction conditions, only a monohydroxylated product is detected by gas chromatography. Hydroxylation occurs exclusively at the allylic position as confirmed from a synthesized authentic standard. Investigation into the stereochemistry of the reaction indicates that the R enantiomer is obtained in 85% ee. The (R)-9-hydroxy-10-undecenoic acid obtained enzymatically is a valuable synthon en route to various natural products further expanding the light-activated P450 BM3 biocatalysis and highlighting the advantages over traditional methods. PMID:24938497

  18. Cytochrome P450BM-3 reduces aldehydes to alcohols through a direct hydride transfer

    SciTech Connect

    Kaspera, Ruediger; Sahele, Tariku; Lakatos, Kyle; Totah, Rheem A.

    2012-02-17

    Highlights: Black-Right-Pointing-Pointer Cytochrome P450BM-3 reduced aldehydes to alcohols efficiently (k{sub cat} {approx} 25 min{sup -1}). Black-Right-Pointing-Pointer Reduction is a direct hydride transfer from R-NADP{sup 2}H to the carbonyl moiety. Black-Right-Pointing-Pointer P450 domain variants enhance reduction through potential allosteric/redox interactions. Black-Right-Pointing-Pointer Novel reaction will have implications for metabolism of xenobiotics. -- Abstract: Cytochrome P450BM-3 catalyzed the reduction of lipophilic aldehydes to alcohols efficiently. A k{sub cat} of {approx}25 min{sup -1} was obtained for the reduction of methoxy benzaldehyde with wild type P450BM-3 protein which was higher than in the isolated reductase domain (BMR) alone and increased in specific P450-domain variants. The reduction was caused by a direct hydride transfer from preferentially R-NADP{sup 2}H to the carbonyl moiety of the substrate. Weak substrate-P450-binding of the aldehyde, turnover with the reductase domain alone, a deuterium incorporation in the product from NADP{sup 2}H but not D{sub 2}O, and no inhibition by imidazole suggests the reductase domain of P450BM-3 as the potential catalytic site. However, increased aldehyde reduction by P450 domain variants (P450BM-3 F87A T268A) may involve allosteric or redox mechanistic interactions between heme and reductase domains. This is a novel reduction of aldehydes by P450BM-3 involving a direct hydride transfer and could have implications for the metabolism of endogenous substrates or xenobiotics.

  19. Key Mutations Alter the Cytochrome P450 BM3 Conformational Landscape and Remove Inherent Substrate Bias*

    PubMed Central

    Butler, Christopher F.; Peet, Caroline; Mason, Amy E.; Voice, Michael W.; Leys, David; Munro, Andrew W.

    2013-01-01

    Cytochrome P450 monooxygenases (P450s) have enormous potential in the production of oxychemicals, due to their unparalleled regio- and stereoselectivity. The Bacillus megaterium P450 BM3 enzyme is a key model system, with several mutants (many distant from the active site) reported to alter substrate selectivity. It has the highest reported monooxygenase activity of the P450 enzymes, and this catalytic efficiency has inspired protein engineering to enable its exploitation for biotechnologically relevant oxidations with structurally diverse substrates. However, a structural rationale is lacking to explain how these mutations have such effects in the absence of direct change to the active site architecture. Here, we provide the first crystal structures of BM3 mutants in complex with a human drug substrate, the proton pump inhibitor omeprazole. Supported by solution data, these structures reveal how mutation alters the conformational landscape and decreases the free energy barrier for transition to the substrate-bound state. Our data point to the importance of such “gatekeeper” mutations in enabling major changes in substrate recognition. We further demonstrate that these mutants catalyze the same 5-hydroxylation reaction as performed by human CYP2C19, the major human omeprazole-metabolizing P450 enzyme. PMID:23828198

  20. Induction of cytochrome P-450 BM-3 (CYP 102) by non-steroidal anti-inflammatory drugs in Bacillus megaterium.

    PubMed Central

    English, N; Hughes, V; Wolf, C R

    1996-01-01

    Bacillus megaterium contains a cytochrome P-450 fatty acid mono-oxygenase which is inducible with barbiturate drugs. We have demonstrated that this enzyme system is inducible with peroxisome proliferators. In mammals, peroxisome proliferators also induce mono-oxygenases in the CYP4A gene family. In this paper we demonstrate that the non-steroidal anti-inflammatory drugs ibuprofen, ketoprofen and indomethacin are potent inducers of fatty acid mono-oxygenase activity as well as of P-450BM-3 protein in B. megaterium. The levels of induction of P-450 protein were 11.8-, 3.9- and 3.0-fold respectively. In addition, we demonstrate that these inducing agents interact with a transcriptional repressor, Bm3R1, which leads to its dissociation from its operator sequence. This provides a rational mechanism for the induction process. This is the first report which demonstrates that non-steroidal anti-inflammatory drugs can interact directly with a transcription factor to initiate gene expression, and further substantiates the structure-activity relationships that identify inducers of cytochrome P-450BM-3 and compounds that have the potential to act as peroxisome proliferators and induce CYP4A expression in mammals. PMID:8645218

  1. Probing Steroidal Substrate Specificity of Cytochrome P450 BM3 Variants.

    PubMed

    Liu, Xing; Wang, Zhi-Biao; Wang, Ya-Nan; Kong, Jian-Qiang

    2016-01-01

    M01A82W, M11A82W and M01A82WS72I are three cytochrome P450 BM3 (CYP102A1) variants. They can catalyze the hydroxylation of testosterone (TES) and norethisterone at different positions, thereby making them promising biocatalysts for steroid hydroxylation. With the aim of obtaining more hydroxylated steroid precursors it is necessary to probe the steroidal substrate diversity of these BM3 variants. Here, three purified BM3 variants were first incubated with eight steroids, including testosterone (TES), methyltestosterone (MT), cholesterol, β-sitosterol, dehydroepiandrosterone (DHEA), diosgenin, pregnenolone and ergosterol. The results indicated that the two 3-keto-Δ⁴-steroids TES and MT can be hydroxylated at various positions by the three BM3 mutants, respectively. On the contrary, the three enzymes displayed no any activity toward the remaining six 3-hydroxy-Δ⁵-steroids. This result indicates that the BM3 mutants prefer 3-keto-Δ⁴-steroids as hydroxylation substrates. To further verify this notion, five other substrates, including two 3-hydroxy-Δ⁵-steroids and three 3-keto-Δ⁴-steroids, were carefully selected to incubate with the three BM3 variants. The results indicated the three 3-keto-Δ⁴-steroids can be metabolized to form hydroxysteroids by the three BM3 variants. On the other hand, the two 3-hydroxy-Δ⁵-steroids cannot be hydroxylated at any position by the BM3 mutants. These results further support the above conclusion, therefore demonstrating the 3-keto-Δ⁴-steroid substrate preference of BM3 mutants, and laying a foundation for microbial production of more hydroxylated steroid intermediates using BM3 variants. PMID:27294908

  2. Structure, dynamics, and function of the monooxygenase P450 BM-3: insights from computer simulations studies

    NASA Astrophysics Data System (ADS)

    Roccatano, Danilo

    2015-07-01

    The monooxygenase P450 BM-3 is a NADPH-dependent fatty acid hydroxylase enzyme isolated from soil bacterium Bacillus megaterium. As a pivotal member of cytochrome P450 superfamily, it has been intensely studied for the comprehension of structure-dynamics-function relationships in this class of enzymes. In addition, due to its peculiar properties, it is also a promising enzyme for biochemical and biomedical applications. However, despite the efforts, the full understanding of the enzyme structure and dynamics is not yet achieved. Computational studies, particularly molecular dynamics (MD) simulations, have importantly contributed to this endeavor by providing new insights at an atomic level regarding the correlations between structure, dynamics, and function of the protein. This topical review summarizes computational studies based on MD simulations of the cytochrome P450 BM-3 and gives an outlook on future directions.

  3. Optimization of the Bacterial Cytochrome P450 BM3 System for the Production of Human Drug Metabolites

    PubMed Central

    Di Nardo, Giovanna; Gilardi, Gianfranco

    2012-01-01

    Drug metabolism in human liver is a process involving many different enzymes. Among them, a number of cytochromes P450 isoforms catalyze the oxidation of most of the drugs commercially available. Each P450 isoform acts on more than one drug, and one drug may be oxidized by more than one enzyme. As a result, multiple products may be obtained from the same drug, and as the metabolites can be biologically active and may cause adverse drug reactions (ADRs), the metabolic profile of a new drug has to be known before this can be commercialized. Therefore, the metabolites of a certain drug must be identified, synthesized and tested for toxicity. Their synthesis must be in sufficient quantities to be used for metabolic tests. This review focuses on the progresses done in the field of the optimization of a bacterial self-sufficient and efficient cytochrome P450, P450 BM3 from Bacillus megaterium, used for the production of metabolites of human enzymes. The progress made in the improvement of its catalytic performance towards drugs, the substitution of the costly NADPH cofactor and its immobilization and scale-up of the process for industrial application are reported. PMID:23443101

  4. Molecular Dynamics and QM/MM Calculations Predict the Substrate-Induced Gating of Cytochrome P450 BM3 and the Regio- and Stereoselectivity of Fatty Acid Hydroxylation.

    PubMed

    Dubey, Kshatresh Dutta; Wang, Binju; Shaik, Sason

    2016-01-27

    Theory predicts herein enzymatic activity from scratch. We show that molecular dynamics (MD) simulations and quantum-mechanical/molecular mechanics (QM/MM) calculations of the fatty acid hydroxylase P450 BM3 predict the binding mechanism of the fatty acid substrate and its enantio/regioselective hydroxylation by the active species of the enzyme, Compound I. The MD simulations show that the substrate's entrance involves hydrogen-bonding interactions with Pro25, Glu43, and Leu188, which induce a huge conformational rearrangement that closes the substrate channel by pulling together the A helix and the β1 sheet to the F/G loop. In turn, at the bottom of the substrate's channel, residue Phe87 controls the regioselectivity by causing the substrate's chain to curl up and juxtapose its CH2 positions ω-1/ω-2/ω-3 to Compound I while preventing access to the endmost position, ω-CH3. Phe87 also controls the stereoselectivity by the enantioselective steric blocking of the pro-S C-H bond, thus preferring R hydroxylation. Indeed, the MD simulations of the mutant Phe87Ala predict predominant ω hydroxylation. These findings, which go well beyond the X-ray structural data, demonstrate the predictive power of theory and its insight, which can potentially be used as a partner of experiment for eventual engineering of P450 BM3 with site-selective C-H functionalization capabilities. PMID:26716578

  5. CO photodissociation dynamics in cytochrome P450BM3 studied by subpicosecond visible and mid-infrared spectroscopy.

    PubMed

    Rupenyan, Alisa; Commandeur, Jan; Groot, Marie Louise

    2009-07-01

    Cytochrome P450BM3 is a bacterial enzyme with a heme cofactor that binds small diatomic ligands. Here we report the first study of carbon monoxide (CO) photodissociation and rebinding in ferrous P450BM3 on an ultrafast time scale. We monitored dissociation of carbon monoxide upon Soret band excitation using visible and infrared femtosecond spectroscopy between 100 fs and 4 ns. The dynamics of the ferric P450 was probed for reference in the visible spectral region. In the photodissociated ferrous P450-CO complex, the vibrational hot deligated ground state is populated in 0.2 ps and relaxes on a picosecond time scale. The onset of geminate recombination of CO with the heme is observed on a nanosecond time scale. In the mid-infrared spectral region, the bleached absorption due to the bound C=O stretch vibration is constant on the picosecond to 1 ns time scale, indicating that the photodissociation yield is 100% and that rebinding occurs after 1 ns. In the infrared absorption difference spectra, we additionally resolve two small bands of dissociated CO molecules at 2092 and 2114 cm(-1). This indicates that the escape of photolyzed CO to solvent and the geminate recombination are preceded by transient docking within the protein in a manner similar to that of globins. The bands partially decay with a time constant of 1 ps, possibly due to a relaxation of the protein around the CO docking site, allowing for greater orientational freedom of the CO molecules. PMID:19492790

  6. The role of tryptophan 97 of cytochrome P450 BM3 from Bacillus megaterium in catalytic function. Evidence against the 'covalent switching' hypothesis of P-450 electron transfer.

    PubMed Central

    Munro, A W; Malarkey, K; McKnight, J; Thomson, A J; Kelly, S M; Price, N C; Lindsay, J G; Coggins, J R; Miles, J S

    1994-01-01

    The 'Covalent Switching' hypothesis suggests that a strongly conserved tryptophan residue acts as a mediator of electron-transfer flow between redox partners in cytochrome P-450 systems [Baldwin, Morris and Richards (1991) Proc. R. Soc. London B 245, 43-51]. We have investigated the effect of alteration of the conserved tryptophan (Trp-97) in cytochrome P-450 BM3 (P-450 102) from Bacillus megaterium. Replacement of Trp-97 with Ala, Phe or Tyr results in a decrease in the natural haem content and alters the resting spin state of the remaining haem in the purified mutant enzymes. However, kinetic analyses indicate that the mutant enzymes retain high levels of catalytic activity. C.d. and e.p.r. spectroscopy also reveal little alteration in secondary structure or change in the pattern of haem ligation. These findings cast doubt on the covalent switching mechanism of intermolecular electron flow in the P-450s, but indicate that this residue plays a role in the association of the haem prosthetic group. PMID:7980400

  7. Subzero-temperature stabilization and spectroscopic characterization of homogeneous oxyferrous complexes of the cytochrome P450 BM3 (CYP102) oxygenase domain and holoenzyme

    SciTech Connect

    Perera, Roshan; Sono, Masanori; Raner, Gregory M.; Dawson, John H. . E-mail: dawson@sc.edu

    2005-12-09

    We describe herein for the first time the formation and spectroscopic characterization of homogeneous oxyferrous complexes of the cytochrome P450 BM3 (CYP102) holoenzyme and heme domain (BMP) at -55 {sup o}C using a 70/30 (v/v) glycerol/buffer cryosolvent. The choice of buffer is a crucial factor with Tris [tris(hydroxymethyl)aminomethane] buffer being significantly more effective than phosphate. The oxyferrous complexes have been characterized with magnetic circular dichroism spectroscopy and the resulting spectra compared to those of the more well-characterized oxyferrous cytochrome P450-CAM. The formation of a stable substrate-bound oxyferrous CYP BM3 holoenzyme, despite the fact that it has the necessary reducing equivalents for turnover, indicates that electron transfer from the flavin domain to the oxyferrous center is very slow at this temperature. The ability to prepare stable homogeneous oxyferrous derivatives of both BMP and the CYP BM3 holoenzyme will enable these species to be used as starting materials for mechanistic investigation of dioxygen activation.

  8. Enzyme-substrate complementarity governs access to a cationic reaction manifold in the P450(BM3)-catalysed oxidation of cyclopropyl fatty acids.

    PubMed

    Cryle, Max J; Hayes, Patricia Y; De Voss, James J

    2012-12-01

    The products of cytochrome P450(BM3)-catalysed oxidation of cyclopropyl-containing dodecanoic acids are consistent with the presence of a cationic reaction intermediate, which results in efficient dehydrogenation of the rearranged probes by the enzyme. These results highlight the importance of enzyme-substrate complementarity, with a cationic intermediate occurring only when the probes used begin to diverge from ideal substrates for this enzyme. This also aids in reconciling literature reports supporting the presence of cationic intermediates with certain cytochrome P450 enzyme/substrate pairs. PMID:23109039

  9. Kinetics of electron transfer in the complex of cytochrome P450 3A4 with the flavin domain of cytochrome P450BM-3 as evidence of functional heterogeneity of the heme protein

    PubMed Central

    Fernando, Harshica; Halpert, James R.; Davydov, Dmitri R.

    2008-01-01

    We used a rapid scanning stop-flow technique to study the kinetics of reduction of cytochrome P450 3A4 (CYP3A4) by the flavin domain of cytochrome P450-BM3 (BMR), which was shown to form a stoichiometric complex (KD = 0.48 µM) with CYP3A4. In the absence of substrates only about 50% of CYP3A4 was able to accept electrons from BMR. Whereas the high-spin fraction was completely reducible, the reducibility of the low-spin fraction did not exceed 42%. Among four substrates tested (testosterone, 1-pyrenebutanol, bromocriptine, or α-naphthoflavone (ANF)) only ANF is capable of increasing the reducibility of the low-spin fraction to 75%. Our results demonstrate that the pool of CYP3A4 is heterogeneous, and not all P450 is competent for electron transfer in the complex with reductase. The increase in the reducibility of the enzyme in the presence of ANF may represent an important element of the mechanism of action of this activator. PMID:18086551

  10. The role of Barbie box sequences as cis-acting elements involved in the barbiturate-mediated induction of cytochromes P450BM-1 and P450BM-3 in Bacillus megaterium.

    PubMed

    Liang, Q; He, J S; Fulco, A J

    1995-03-01

    In a previous publication (He, J.-S., and Fulco, A. J. (1991) J. Biol. Chem. 266, 7864-7869), we reported that a 15-17-base pair DNA sequence (designated a Barbie box element) in the 5'-regulatory regions of cytochrome P450BM-1 and P450BM-3 genes from Bacillus megaterium was recognized by a barbiturate-regulated protein. It is now recognized that essentially all eukaryotic and prokaryotic genes whose 5'-flanking regions are known and that encode barbiturate-inducible proteins contain the Barbie box element. A 4-base pair sequence (AAAG) is found in the same relative position in all Barbie box elements. In B. megaterium, mutation of the Barbie box located in the P450BM-1 gene leads to the constitutive synthesis of cytochrome P450BM-1 and a 10-fold increase of expression of Bm1P1, a small gene located upstream of the P450BM-1 gene, that encodes a putative regulatory protein. Mutation of the P450BM-3 Barbie box significantly increased the expression of both P450BM-3 and Bm3P1 (another small gene located upstream of the P450BM-3 gene that encodes a second putative regulatory protein) in response to pentobarbital induction but left the basal levels unaffected. In gel mobility shift assays, Bm3R1, a repressor of the P450BM-3 gene, was found to specifically interact with the Barbie box sequences of the B. megaterium P450 genes. Mutated Barbie boxes showed a decreased binding affinity for Bm3R1 compared to their wild type (unmutated) counterparts. Barbie box sequences were also shown to specifically interact with putative positive regulatory factors of B. megaterium cells. These putative positive factors were induced by pentobarbital and were also present at high levels during late stationary phase of B. megaterium cell cultures grown in the absence of barbiturates. The mutated Barbie box sequences had greater binding affinity for these positive factors than did unmutated Barbie box sequences. DNase I footprinting analysis of the 5'-flanking region of the P450BM-1 gene

  11. In vivo roles of Bm3R1 repressor in the barbiturate-mediated induction of the cytochrome P450 genes (P450(BM-3) and P450(BM-)1) of Bacillus megaterium.

    PubMed

    Liang, Q; Chen, L; Fulco, A J

    1998-04-10

    We previously showed [Q. Liang, A.J. Fulco, J. Biol. Chem., 270 (1995) 18606-18614) that the binding of Bm3R1 repressor to Barbie box elements and operator sites in the 5'-flanking regions of the P450BM-3 and P450BM-1 (CYP102 and CYP106) genes in Bacillus megaterium was a critical factor in their regulation at the level of transcription. We now describe experiments that delineate specific roles for Bm3R1 in the barbiturate-mediated induction of these genes. We directly demonstrate the interaction of Bm3R1 with Barbie box and operator sequences and show that high in vivo levels of Bm3R1 prevent putative positive factors from binding to Barbie box elements, strongly inhibit the expression of the P450 genes, prolong the lag phase of growth in Bacillus megaterium cultures and increase the sensitivity of the cells to the growth-inhibitory effects of barbiturates. Finally, our data suggest that there may be two forms of Bm3R1, either of which can interact with OIII, the bicistronic operator sequence. PMID:9565684

  12. Engineering cytochrome P450 BM3 of Bacillus megaterium for terminal oxidation of palmitic acid.

    PubMed

    Brühlmann, Fredi; Fourage, Laurent; Ullmann, Christophe; Haefliger, Olivier P; Jeckelmann, Nicolas; Dubois, Cédric; Wahler, Denis

    2014-08-20

    Directed evolution via iterative cycles of random and targeted mutagenesis was applied to the P450 domain of the subterminal fatty acid hydroxylase CYP102A1 of Bacillus megaterium to shift its regioselectivity towards the terminal position of palmitic acid. A powerful and versatile high throughput assay based on LC-MS allowed the simultaneous detection of primary and secondary oxidation products, which was instrumental for identifying variants with a strong preference for the terminal oxidation of palmitic acid. The best variants identified acquired up to 11 amino acid alterations. Substitutions at F87, I263, and A328, relatively close to the bound substrate based on available crystallographic information contributed significantly to the altered regioselectivity. However, non-obvious residues much more distant from the bound substrate showed surprising strong contributions to the increased selectivity for the terminal position of palmitic acid. PMID:24833423

  13. Improved cyclopropanation activity of histidine-ligated cytochrome P450 enables the enantioselective formal synthesis of levomilnacipran.

    PubMed

    Wang, Z Jane; Renata, Hans; Peck, Nicole E; Farwell, Christopher C; Coelho, Pedro S; Arnold, Frances H

    2014-06-23

    Engineering enzymes capable of modes of activation unprecedented in nature will increase the range of industrially important molecules that can be synthesized through biocatalysis. However, low activity for a new function is often a limitation in adopting enzymes for preparative-scale synthesis, reaction with demanding substrates, or when a natural substrate is also present. By mutating the proximal ligand and other key active-site residues of the cytochrome P450 enzyme from Bacillus megaterium (P450-BM3), a highly active His-ligated variant of P450-BM3 that can be employed for the enantioselective synthesis of the levomilnacipran core was engineered. This enzyme, BM3-Hstar, catalyzes the cyclopropanation of N,N-diethyl-2-phenylacrylamide with an estimated initial rate of over 1000 turnovers per minute and can be used under aerobic conditions. Cyclopropanation activity is highly dependent on the electronic properties of the P450 proximal ligand, which can be used to tune this non-natural enzyme activity. PMID:24802161

  14. Free radicals and activated oxygen.

    PubMed

    Famaey, J P

    1982-01-01

    Superoxide anion (0(-2)), hydrogen peroxide (H2O2) and hydroxyl radical (OH.) are products of the biological reduction of 0(2). They are very reactive and poorly tolerated within living systems and enzymes that catalytically scavenge these products have been evolved as defense mechanisms. These include superoxide dismutases (SOD), catalase and peroxidases. Large amounts of O-2 are produced by different enzymatic and non enzymatic biological processes. Large amounts of activated oxygens are produced by phagocytosing cells such as macrophages and polymorphonuclear cells. This production is associated with the bactericidal actions of these cells but it also largely contributes to exacerbate and sustain the inflammation where these cells congregate. The arachidonic acid pathway triggered by the inflammatory stimuli is also a source for these oxidizing radicals. The production of activated oxygens has been associated with the normal aging process but also with various toxic reactions (e.g. the toxicity of the herbicide paraquat, of the ionizing radiations, of certain antibiotics such as streptonigrin, etc. . . .). O-2 induces the depolymerization of hyaluronic acid which lends viscosity and lubricating properties to synovial fluids. SOD possess antiinflammatory properties and a bovine SOD, orgotein, has now been largely investigated by intramuscular and intraarticular injections in the treatment of rheumatic diseases. Various antiinflammatory compounds (e.g. the salicylates) are able either to inhibit the production of these oxygen radicals or to scavenge them which seems of importance for their antiinflammatory properties. Singlet oxygen, another activated oxygen, might also play a role in the inflammatory process. PMID:6295769

  15. 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.

  16. Constrained water access to the active site of cytochrome P450 from the piezophilic bacterium Photobacterium profundum

    NASA Astrophysics Data System (ADS)

    Sineva, Elena V.; Davydov, Dmitri R.

    2010-12-01

    Living species inhabiting ocean deeps must adapt to high hydrostatic pressure. This adaptation, which must enable functioning under conditions of promoted protein hydration, is especially important for proteins such as cytochromes P450 that exhibit functionally important hydration-dehydration dynamics. Here we study the interactions of substrates with cytochrome P450-SS9, a putative fatty acid hydroxylase from the piezophilic bacterium Photobacterium profundum SS9, and characterize the protein's barotropic properties. Comparison of P450-SS9 with cytochrome P450BM-3, a mesophilic fatty acid hydroxylase, suggests that P450-SS9 is characterized by severely confined accessibility and low water occupancy of the active site. This feature may reveal a mechanism for the structural adaptation of the piezophilic enzyme. We also demonstrate that saturated and unsaturated fatty acids exert opposite effects on solvent accessibility and hydration of the active site. Modulation of the protein conformation by fatty acids is hypothesized to have an important physiological function in the piezophile.

  17. 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.

  18. 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 ...

  19. SAFETY ASPECTS OF OXYGEN AERATION ACTIVATED SLUDGE SYSTEMS

    EPA Science Inventory

    This project was carried out to assess the impact of the use of oxygen and oxygen-enriched air for aeration of activated sludge systems on the safety of municipal waste-water treatment plants and their personnel. The tasks included (1) determination of oxygen combustion hazards f...

  20. 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.

  1. PARALLEL EVALUATION OF AIR- AND OXYGEN-ACTIVATED SLUDGE

    EPA Science Inventory

    To provide data on the relative merits of air and oxygen in the activated sludge process, two 1900-cu m/day (0.5-mgd) activated sludge pilot plant, one air and one oxygen system, were operated side-by-side at the Joint Water Pollution Control Plant, Carson, California. Both of th...

  2. 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

  3. Oxygen-independent induction of enzyme activities related to oxygen metabolism in yeast by copper.

    PubMed

    Galiazzo, F; Schiesser, A; Rotilio, G

    1988-04-14

    Aerobic growth of Saccharomyces cerevisiae in the presence of CuSO4 (between 0.1 and 1 mM) caused a generalized induction of major enzyme activities involved in 'housekeeping' routes of oxygen metabolism (cytochrome oxidase, glutathione peroxidases and catalase) which were comparable to or higher than that observed with Cu,Zn-superoxide dismutase. Fumarase and glutathione transferase, tested as controls for oxygen-unrelated activities, were found to decrease under the same conditions. In the absence of oxygen, copper addition to yeast resulted in significant increases of Cu,Zn-superoxide dismutase and glutathione peroxidases and a slight increase of cytochrome oxidase, with catalase remaining undetectable irrespective of whether or not copper was present. Other metal ions tested (Mn2+, Co2+) were unable to produce such effects. It is concluded that copper has a general inducing effect on enzymes related to metabolism of oxygen and oxygen derivatives, which is mediated neither by formation of O2-. and H2O2 nor by interaction with copper-specific apoproteins. These results point to a general role of copper as regulator of the expression of major enzyme activities involved in biological oxygen activation. PMID:2831994

  4. 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.

  5. Leukocytic oxygen activation and microbicidal oxidative toxins.

    PubMed

    Hurst, J K; Barrette, W C

    1989-01-01

    Following a brief introduction of cellular response to stimulation comprising leukocyte activation, three major areas are discussed: (1) the neutrophil oxidase; (2) myeloperoxidase (MPO)-dependent oxidative microbicidal reactions; and (3) MPO-independent oxidative reactions. Topics included in section (A) are current views on the activation mechanism, redox composition, structural and topographic organization of the oxidase, and its respiratory products. In section (B), emphasis is placed on recent research on cidal mechanisms of HOCl, including the oxidative biochemistry of active chlorine compounds, identification of sites of lesions in bacteria, and attendant metabolic consequences. In section (C), we review the (bio)chemistry of H2O2 and .OH microbicidal reactions, with particular attention being given to addressing the controversial issue of probe methods to identify .OH radical and critical assessment of the recent proposal that MPO-independent killing arises from site-specific metal-catalyzed Fenton-type chemistry. PMID:2548810

  6. OXYGEN UTILIZATION IN ACTIVATED SLUDGE PLANTS: SIMULATION AND MODEL CALIBRATION

    EPA Science Inventory

    The objective of the research described in the report is to apply recent advances in activated sludge process modeling to the simulation of oxygen utilization rates in full scale activated sludge treatment plants. This is accomplished by calibrating the International Association ...

  7. Oxygen tension limits nitric oxide synthesis by activated macrophages.

    PubMed Central

    McCormick, C C; Li, W P; Calero, M

    2000-01-01

    Previous studies have established that constitutive calcium-dependent ('low-output') nitric oxide synthase (NOS) is regulated by oxygen tension. We have investigated the role of oxygen tension in the synthesis of NO by the 'high-output' calcium-independent NOS in activated macrophages. Hypoxia increased macrophage NOS gene expression in the presence of one additional activator, such as lipopolysaccharide or interferon-gamma, but not in the presence of both. Hypoxia markedly reduced the synthesis of NO by activated macrophages (as measured by accumulation of nitrite and citrulline), such that, at 1% oxygen tension, NO accumulation was reduced by 80-90%. The apparent K(m) for oxygen calculated from cells exposed to a range of oxygen tensions was found to be 10.8%, or 137 microM, O(2) This value is considerably higher than the oxygen tension in tissues, and is virtually identical to that reported recently for purified recombinant macrophage NOS. The decrease in NO synthesis did not appear to be due to diminished arginine or cofactor availability, since arginine transport and NO synthesis during recovery in normoxia were normal. Analysis of NO synthesis during hypoxia as a function of extracellular arginine indicated that an altered V(max), but not K(m)(Arg), accounted for the observed decrease in NO synthesis. We conclude that oxygen tension regulates the synthesis of NO in macrophages by a mechanism similar to that described previously for the calcium-dependent low-output NOS. Our data suggest that oxygen tension may be an important physiological regulator of macrophage NO synthesis in vivo. PMID:10970783

  8. 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

  9. Reactive Oxygen Species Mediated Activation of a Dormant Singlet Oxygen Photosensitizer: From Autocatalytic Singlet Oxygen Amplification to Chemicontrolled Photodynamic Therapy.

    PubMed

    Durantini, Andrés M; Greene, Lana E; Lincoln, Richard; Martínez, Sol R; Cosa, Gonzalo

    2016-02-01

    Here we show the design, preparation, and characterization of a dormant singlet oxygen ((1)O2) photosensitizer that is activated upon its reaction with reactive oxygen species (ROS), including (1)O2 itself, in what constitutes an autocatalytic process. The compound is based on a two segment photosensitizer-trap molecule where the photosensitizer segment consists of a Br-substituted boron-dipyrromethene (BODIPY) dye. The trap segment consists of the chromanol ring of α-tocopherol, the most potent naturally occurring lipid soluble antioxidant. Time-resolved absorption, fluorescence, and (1)O2 phosphorescence studies together with fluorescence and (1)O2 phosphorescence emission quantum yields collected on Br2B-PMHC and related bromo and iodo-substituted BODIPY dyes show that the trap segment provides a total of three layers of intramolecular suppression of (1)O2 production. Oxidation of the trap segment with ROS restores the sensitizing properties of the photosensitizer segment resulting in ∼40-fold enhancement in (1)O2 production. The juxtaposed antioxidant (chromanol) and prooxidant (Br-BODIPY) antagonistic chemical activities of the two-segment compound enable the autocatalytic, and in general ROS-mediated, activation of (1)O2 sensitization providing a chemical cue for the spatiotemporal control of (1)O2.The usefulness of this approach to selectively photoactivate the production of singlet oxygen in ROS stressed vs regular cells was successfully tested via the photodynamic inactivation of a ROS stressed Gram negative Escherichia coli strain. PMID:26789198

  10. 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)

  11. Prolyl Hydroxylase PHD3 Activates Oxygen-dependent Protein Aggregation

    PubMed Central

    Rantanen, Krista; Pursiheimo, Juha; Högel, Heidi; Himanen, Virpi; Metzen, Eric

    2008-01-01

    The HIF prolyl hydroxylases (PHDs/EGLNs) are central regulators of the molecular responses to oxygen availability. One isoform, PHD3, is expressed in response to hypoxia and causes apoptosis in oxygenated conditions in neural cells. Here we show that PHD3 forms subcellular aggregates in an oxygen-dependent manner. The aggregation of PHD3 was seen under normoxia and was strongly reduced under hypoxia or by the inactivation of the PHD3 hydroxylase activity. The PHD3 aggregates were dependent on microtubular integrity and contained components of the 26S proteasome, chaperones, and ubiquitin, thus demonstrating features that are characteristic for aggresome-like structures. Forced expression of the active PHD3 induced the aggregation of proteasomal components and activated apoptosis under normoxia in HeLa cells. The apoptosis was seen in cells prone to PHD3 aggregation and the PHD3 aggregation preceded apoptosis. The data demonstrates the cellular oxygen sensor PHD3 as a regulator of protein aggregation in response to varying oxygen availability. PMID:18337469

  12. 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

  13. 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

  14. 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

  15. Activated oxygen alters cerebral microvascular responses in newborn pigs

    SciTech Connect

    Leffler, C.W.; Busiia, D.W.; Armstead, W.M.; Mirro, R.; Thelin, O. )

    1990-02-26

    In piglets, cerebral ischemia/reperfusion blocks prostanoid dependent cerebral vasodilation to hypercapnia (CO{sub 2}) and hypotension but not prostanoid independent dilation to isoproterenol (Isu) or constriction to norepinephrine (NE). Ischemia/reperfusion increases activated-O{sub 2} production by piglet brains. Using cranial windows in piglets, the authors investigated the hypothesis that activated oxygen can block prostanoid dependent cerebral vasodilator responses to CO{sub 2} and hypotension without altering responses to Isu and NE. Exposure to an activated oxygen generating system of xanthine oxidase, hypoxanthine, and Fe that made about 3 times the activated-O{sub 2} on the brain surface as ischemia/reperfusion caused reversible pial arteriolar dilation. After exposure, pial arteriolar dilation was reduced to CO{sub 2} and hypotension but not to Isu. NE constrictor responses were also unaltered. H{sub 2}O{sub 2} or H{sub 2}O{sub 2} + Fe caused constriction followed by reversible dilation. After exposure, pial arteriolar dilation in response to CO{sub 2} and hypotension was not altered. However, addition of xanthine oxidase and hypoxanthine with H{sub 2}O{sub 2} and Fe totally eliminated pial arteriolar dilator responses to CO{sub 2} and hypotension but did not decrease dilation caused by Isu or constriction caused by NE. The authors conclude that activated oxygen could produce the altered prostanoid dependent pial arteriolar responses observed following ischemia in piglets.

  16. Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts.

    PubMed

    Widmann, D; Behm, R J

    2014-03-18

    Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently. This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even at the extremely low concentrations present under realistic reaction conditions. Different types of pulse experiments were performed, during which the highly dispersed, realistic powder catalysts are exposed to very low amounts of reactants, CO and/or O2, in order to form and reactively remove Oact species and gain information on their formation, nature, and the active site for Oact formation. Our investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 °C and higher is a highly stable atomic species, which at 80 °C is formed only at the perimeter of the Au-oxide interface and whose reactive removal by CO is activated, but not its formation. From these findings, it is concluded that surface lattice oxygen represents the Oact species for the CO oxidation. Accordingly, the CO oxidation proceeds via a Au-assisted Mars-van Krevelen mechanism, during which surface lattice oxygen close to the Au NPs is removed by reaction

  17. 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.

  18. Charge transfer induced activity of graphene for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Shen, Anli; Xia, Weijun; Zhang, Lipeng; Dou, Shuo; Xia, Zhenhai; Wang, Shuangyin

    2016-05-01

    Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR.

  19. Effects of MCI-186 upon neutrophil-derived active oxygens.

    PubMed

    Sumitomo, K; Shishido, N; Aizawa, H; Hasebe, N; Kikuchi, K; Nakamura, M

    2007-01-01

    Reactions of 3-methyl-1-phenyl-2-pyrazoline-5-one (MCI-186) with hypochlorous acid and superoxide were analysed by spectrophotometry and mass spectrometry. The results were applied to the neutrophil system to evaluate the scavenging activity of neutrophil-derived active oxygen species by MCI-186. MCI-186 reacted rapidly with hypochlorous acid (1 x 10(6) M(-1)s(-1)) to form a chlorinated intermediate, followed by a slow conversion to a new spectrum. MCI-186 consumed 3 moles of hypochlorous acid and did not react with superoxide. The newly synthesized fluorescence probes, 2-[6-(4'-amino)-phenoxy-3H-xanthen-3-on-9-yl]benzoic acid (APF) and 2-[6-(4'-hydroxy)phenoxy-3H-anthen-3-on-9-yl]benzoic acid (HPF) successfully detected neutrophil-derived active oxygens (Setsukinai K, Urano Y, Kakinuma K, Majima HJ, Nagano T. Development of novel fluorescence probes that can reliably detect reactive oxygen species and distinguish specific species. J Biol Chem 2003; 278: 3170-3175). The rate constants for the reaction of hypochlorous acid with MCI-186 and fluorescence probes was in the order of MCI-186 > APF > HPF. Fluorescence due to the oxidation of APF and HPF was observed with the stimulated neutrophils. The result that the intensity from APF oxidation was higher than that from HPF oxidation is compatible with reports that APF selectively reacts with hypochlorous acid. Fluorescence due to oxidation of both APF and HPF decreased when the reactions were carried out in the presence of a fluorescence probe and MCI-186 in a dose-dependent manner. These results indicate that MCI-186 effectively scavenges neutrophil-derived hypochlorous acid and other active oxygens. PMID:17705989

  20. Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles.

    PubMed

    Vayssilov, Georgi N; Lykhach, Yaroslava; Migani, Annapaola; Staudt, Thorsten; Petrova, Galina P; Tsud, Nataliya; Skála, Tomáš; Bruix, Albert; Illas, Francesc; Prince, Kevin C; Matolín, Vladimír; Neyman, Konstantin M; Libuda, Jörg

    2011-04-01

    Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general. PMID:21423188

  1. Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles

    NASA Astrophysics Data System (ADS)

    Vayssilov, Georgi N.; Lykhach, Yaroslava; Migani, Annapaola; Staudt, Thorsten; Petrova, Galina P.; Tsud, Nataliya; Skála, Tomáš; Bruix, Albert; Illas, Francesc; Prince, Kevin C.; MatolíN, VladimíR.; Neyman, Konstantin M.; Libuda, Jörg

    2011-04-01

    Interactions of metal particles with oxide supports can radically enhance the performance of supported catalysts. At the microscopic level, the details of such metal-oxide interactions usually remain obscure. This study identifies two types of oxidative metal-oxide interaction on well-defined models of technologically important Pt-ceria catalysts: (1) electron transfer from the Pt nanoparticle to the support, and (2) oxygen transfer from ceria to Pt. The electron transfer is favourable on ceria supports, irrespective of their morphology. Remarkably, the oxygen transfer is shown to require the presence of nanostructured ceria in close contact with Pt and, thus, is inherently a nanoscale effect. Our findings enable us to detail the formation mechanism of the catalytically indispensable Pt-O species on ceria and to elucidate the extraordinary structure-activity dependence of ceria-based catalysts in general.

  2. On the determination of oxygen abundances in chromospherically active stars

    NASA Astrophysics Data System (ADS)

    Morel, T.; Micela, G.

    2004-08-01

    We discuss oxygen abundances derived from [O I] λ6300s and the O I triplet in stars spanning a wide range in chromospheric activity level, and show that these two indicators yield increasingly discrepant results with higher chromospheric/coronal activity measures. While the forbidden and permitted lines give fairly consistent results for solar-type disk dwarfs, spuriously high O I triplet abundances are observed in young Hyades and Pleiades stars, as well as in individual components of RS CVn binaries (up to 1.8 dex). The distinct behaviour of the [O I]-based abundances which consistently remain near-solar suggests that this phenomenon mostly results from large departures from LTE affecting the O I triplet at high activity level that are currently unaccounted for, but also possibly from a failure to adequately model the atmospheres of K-type stars. These results suggest that some caution should be exercised when interpreting oxygen abundances in active binaries or young open cluster stars. Based on observations collected at the European Southern Observatory, Chile (Proposals 64.L-0249 and 071.D-0260). Table \\ref{tab_data} is only available in electronic form at http://www.edpsciences.org

  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. 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

  6. 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

  7. 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. PMID:26701120

  8. Activated carbon becomes active for oxygen reduction and hydrogen evolution reactions.

    PubMed

    Yan, Xuecheng; Jia, Yi; Odedairo, Taiwo; Zhao, Xiaojun; Jin, Zhao; Zhu, Zhonghua; Yao, Xiangdong

    2016-06-21

    We utilized a facile method for creating unique defects in the activated carbon (AC), which makes it highly active for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The ORR activity of the defective AC (D-AC) is comparable to the commercial Pt/C in alkaline medium, and the D-AC also exhibits excellent HER activity in acidic solution. PMID:27277286

  9. 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.

  10. 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

  11. 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

  12. Oxygen reduction reaction activity on Pt{111} surface alloys.

    PubMed

    Attard, Gary A; Brew, Ashley; Ye, Jin-Yu; Morgan, David; Sun, Shi-Gang

    2014-07-21

    PtM overlayers (where M=Fe, Co or Ni) supported on Pt{111} are prepared via thermal annealing in either a nitrogen/water or hydrogen ambient of dilute aqueous droplets containing M(Z+) cations directly attached to the electrode. Two different PtM phases are detected depending on the nature of the post-annealing cooling environment. The first of these consists of small (<20 nm), closely packed microcrystals comprised of a central metallic core and a shell (several monolayers thick) of mixed metal oxides/hydroxides. The second type of PtM phase is prepared by cooling in a stream of hydrogen gas. Although this second phase also consists of numerous microcrystals covering the Pt{111} electrode surface, these are both flatter than before and moreover are entirely metallic in character. A positive shift in the onset of PtM oxide formation correlates with increased activity towards the oxygen reduction reaction (ORR), which we ascribe to the greater availability of platinum metallic sites under ORR conditions. PMID:24986646

  13. New platform for cytochrome p450 reaction combining in situ immobilization on biopolymer.

    PubMed

    Lee, Jae Hyung; Nam, Dong Heon; Lee, Sahng Ha; Park, Jong Hyun; Park, Si Jae; Lee, Seung Hwan; Park, Chan Beum; Jeong, Ki Jun

    2014-12-17

    We describe an efficienct chemical conversion platform with in situ immobilization of P450-BM3 on poly(3-hydroxybutyrate) granules. Through fusion with phasin, P450-BM3 is easily immobilized on poly(3-hydroxybutyrate) granules in Escherichia coli. In our work, the immobilized P450 exhibited higher stability and catalytic activity compared to free P450 against changes of pH, temperature, and concentrations of urea and ions. Through quick recovery of immobilized enzyme, the P450-P(3HB) complex successfully catalyzed an O-dealkylation reaction several times with maintained activity. Using the robust P450-P(3HB) complex, we performed a P450-catalyzed reaction on a preparative reactor scale (100 mL) and high-level production (12.3 μM) of 7-hydroxycoumarine from 7-ethoxycoumarin could be achieved. PMID:25322062

  14. 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.

  15. Exploring the Electron Transfer Properties of Neuronal Nitric-oxide Synthase by Reversal of the FMN Redox Potential*

    PubMed Central

    Li, Huiying; Das, Aditi; Sibhatu, Hiruy; Jamal, Joumana; Sligar, Stephen G.; Poulos, Thomas L.

    2008-01-01

    In nitric-oxide synthase (NOS) the FMN can exist as the fully oxidized (ox), the one-electron reduced semiquinone (sq), or the two-electron fully reduced hydroquinone (hq). In NOS and microsomal cytochrome P450 reductase the sq/hq redox potential is lower than that of the ox/sq couple, and hence it is the hq form of FMN that delivers electrons to the heme. Like NOS, cytochrome P450BM3 has the FAD/FMN reductase fused to the C-terminal end of the heme domain, but in P450BM3 the ox/sq and sq/hq redox couples are reversed, so it is the sq that transfers electrons to the heme. This difference is due to an extra Gly residue found in the FMN binding loop in NOS compared with P450BM3. We have deleted residue Gly-810 from the FMN binding loop in neuronal NOS (nNOS) to give ΔG810 so that the shorter binding loop mimics that in cytochrome P450BM3. As expected, the ox/sq redox potential now is lower than the sq/hq couple. ΔG810 exhibits lower NO synthase activity but normal levels of cytochrome c reductase activity. However, unlike the wild-type enzyme, the cytochrome c reductase activity of ΔG810 is insensitive to calmodulin binding. In addition, calmodulin binding to ΔG810 does not result in a large increase in FMN fluorescence as in wild-type nNOS. These results indicate that the FMN domain in ΔG810 is locked in a unique conformation that is no longer sensitive to calmodulin binding and resembles the “on” output state of the calmodulin-bound wild-type nNOS with respect to the cytochrome c reduction activity. PMID:18852262

  16. 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

  17. A mechanism of oxygen sensing in yeast. Multiple oxygen-responsive steps in the heme biosynthetic pathway affect Hap1 activity.

    PubMed

    Hon, Thomas; Dodd, Athena; Dirmeier, Reinhard; Gorman, Nadia; Sinclair, Peter R; Zhang, Li; Poyton, Robert O

    2003-12-12

    Heme plays central roles in oxygen sensing and utilization in many living organisms. In yeast, heme mediates the effect of oxygen on the expression of many genes involved in using or detoxifying oxygen. However, a direct link between intracellular heme level and oxygen concentration has not been vigorously established. In this report, we have examined the relationships among oxygen levels, heme levels, Hap1 activity, and HAP1 expression. We found that Hap1 activity is controlled in vivo by heme and not by its precursors and that heme activates Hap1 even in anoxic cells. We also found that Hap1 activity exhibits the same oxygen dose-response curves as Hap1-dependent aerobic genes and that these dose-response curves have a sharp break at approximately 1 microM O2. The results show that the intracellular signaling heme level, reflected as Hap1 activity, is closely correlated with oxygen concentration. Furthermore, we found that bypass of all heme synthetic steps but ferrochelatase by deuteroporphyrin IX does not circumvent the need for oxygen in Hap1 full activation by heme, suggesting that the last step of heme synthesis, catalyzed by ferrochelatase, is also subjected to oxygen control. Our results show that multiple heme synthetic steps can sense oxygen concentration and provide significant insights into the mechanism of oxygen sensing in yeast. PMID:14512429

  18. Cell death induced by direct laser activation of singlet oxygen at 1270 nm

    NASA Astrophysics Data System (ADS)

    Anquez, F.; El Yazidi Belkoura, I.; Suret, P.; Randoux, S.; Courtade, E.

    2013-02-01

    Singlet oxygen plays a major role in many chemical and biological photo-oxidation processes. It has a high chemical reactivity, which is commonly harnessed for therapeutic issues. Indeed, singlet oxygen is recognized as the major cytotoxic agent in photodynamic therapy. In this treatment of cancer, singlet oxygen is created, among other reactive species, by an indirect transfer of energy from light to molecular oxygen via excitation of a photosensitizer. In this paper, we show that the conventional singlet oxygen production scheme can be simplified. Production of singlet oxygen is achieved in living cells from photosensitizer-free 1270 nm laser excitation of the electronic ground state of molecular oxygen. The quantity of singlet oxygen produced in this way is sufficient to induce an oxidative stress leading to cell death. Other effects such as thermal stress are discriminated, and we conclude that cell death is only due to singlet oxygen creation. This new simplified scheme of singlet oxygen activation can be seen as a breakthrough for phototherapies of malignant diseases and/or as a non-invasive possibility to generate reactive oxygen species in a tightly controlled manner.

  19. 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.

  20. 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…

  1. Atmospheric oxygen plasma activation of silicon (100) surfaces

    SciTech Connect

    Habib, Sara B.; Gonzalez, Eleazar II; Hicks, Robert F.

    2010-05-15

    Silicon (100) surfaces were converted to a hydrophilic state with a water contact angle of <5 deg. by treatment with a radio frequency, atmospheric pressure helium, and oxygen plasma. A 2 in. wide plasma beam, operating at 250 W, 1.0 l/min O{sub 2}, 30 l/min He, and a source-to-sample distance of 3{+-}0.1 mm, was scanned over the sample at 100{+-}2 mm/s. Plasma oxidation of HF-etched silicon caused the dispersive component of the surface energy to decrease from 55.1 to 25.8 dyn/cm, whereas the polar component of the surface energy increased from 0.3 to 42.1 dyn/cm. X-ray photoelectron spectroscopy revealed that the treatment generated a monolayer of covalently bonded oxygen on the Si(100) surface 0.15{+-}0.10 nm thick. The surface oxidation kinetics have been measured by monitoring the change in water contact angle with treatment time, and are consistent with a process that is limited by the mass transfer of ground-state oxygen atoms to the silicon surface.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Oxygen activation with transition metal complexes in aqueous solution

    SciTech Connect

    Bakac, Andreja

    2010-04-12

    Coordination to transition-metal complexes changes both the thermodynamics and kinetics of oxygen reduction. Some of the intermediates (superoxo, hydroperoxo, and oxo species) are close analogues of organic oxygen-centered radicals and peroxides (ROO{sm_bullet}, ROOH, and RO{sm_bullet}). Metal-based intermediates are typically less reactive, but more persistent, than organic radicals, which makes the two types of intermediates similarly effective in their reactions with various substrates. The self-exchange rate constant for hydrogen-atom transfer for the couples Cr{sub aq}OO{sup 2+}/Cr{sub aq}OOH{sup 2+} and L{sup 1}(H{sub 2}O)RhOO{sup 2+}/L{sup 1}(H{sub 2}O)RhOOH{sup 2+} was estimated to be 10{sup 1 {+-} 1} M{sup -1} s{sup -1}. The use of this value in the simplified Marcus equation for the Cr{sub aq}O{sup 2+}/Cr{sub aq}OOH{sup 2+} cross reaction provided an upper limit k{sub CrO,CrOH} {le} 10{sup (-2{+-}1)} M{sup -1} s{sup -1} for Cr{sub aq}O{sup 2+}/Cr{sub aq}OH{sup 2+} self-exchange. Even though superoxo complexes react very slowly in bimolecular self-reactions, extremely fast cross reactions with organic counterparts, i.e., acylperoxyl radicals, have been observed. Many of the intermediates generated by the interaction of O{sub 2} with reduced metal complexes can also be accessed by alternative routes, both thermal and photochemical.

  9. 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.

  10. Inactivation of Pathogenic Bacteria on Seeds by Active Oxygen Species Generated in Low-Pressure Plasma

    NASA Astrophysics Data System (ADS)

    Ono, Reoto; Uchida, Shohei; Hayashi, Nobuya; Kosaka, Rina; Soeda, Yasutaka

    2015-09-01

    The inactivation of bacteria on seeds by active oxygen species generated by a low-pressure oxygen plasma is investigated. Species of active oxygen contributing to the inactivation of bacteria are attempted to be identified. Cylindrical stainless chamber with the internal volume of 17 L is used and RF antenna is set inside the chamber. The oxygen gas pressure is 20-100 Pa. RF power of 13.56 MHz is supplied to RF antenna and CCP is generated. After irradiation, bacteria are extracted from seeds and cultivated on nutrient agars. The number of colonies on these agars is counted after 48 h incubation. The number of bacteria on seeds decreases to less than 10-3 after plasma irradiation for 45 min comparing with that of control. The tendency of the reduction rate of bacteria on seeds has positive correlation with that of the light emission intensity of the singlet excited oxygen molecule as the oxygen gas pressure is varied. It is supposed that the singlet excited oxygen molecule would be one of the major factors for the inactivation of bacteria on seeds.

  11. DESIGN PROCEDURES FOR DISSOLVED OXYGEN CONTROL OF ACTIVATED SLUDGE PROCESSES

    EPA Science Inventory

    This report presents design procedures and guidelines for the selection of aeration equipment and dissolved (DO) control systems for activated sludge treatment plants. Aeration methods, equipment and application techniques are examined and selection procedures offered. Various DO...

  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. SIMPLIFIED INJECTION OF OXYGEN GAS INTO AN ACTIVATED SLUDGE PROCESS

    EPA Science Inventory

    The Las Virgenes Municipal Water District conducted a pilot investigation of the Simplox process at their Tapia Water Reclamation Facility in Calabasas, California. The Simplox process, developed by the Cosmodyne Division of Cordon International, involves covering an activated sl...

  14. Activity-induced tissue oxygenation changes in rat cerebellar cortex: interplay of postsynaptic activation and blood flow

    PubMed Central

    Offenhauser, Nikolas; Thomsen, Kirsten; Caesar, Kirsten; Lauritzen, Martin

    2005-01-01

    Functional neuroimaging relies on the robust coupling between neuronal activity, metabolism and cerebral blood flow (CBF), but the physiological basis of the neuroimaging signals is still poorly understood. We examined the mechanisms of activity-dependent changes in tissue oxygenation in relation to variations in CBF responses and postsynaptic activity in rat cerebellar cortex. To increase synaptic activity we stimulated the monosynaptic, glutamatergic climbing fibres that excite Purkinje cells via AMPA receptors. We used local field potentials to indicate synaptic activity, and recorded tissue oxygen partial pressure (Ptiss,O2) by polarographic microelectrodes, and CBF using laser-Doppler flowmetry. The disappearance rate of oxygen in the tissue increased linearly with synaptic activity. This indicated that, without a threshold, oxygen consumption increased as a linear function of synaptic activity. The reduction in Ptiss,O2 preceded the rise in CBF. The time integral (area) of the negative Ptiss,O2 response increased non-linearly showing saturation at high levels of synaptic activity, concomitant with a steep rise in CBF. This was accompanied by a positive change in Ptiss,O2. Neuronal nitric oxide synthase inhibition enhanced the initial negative Ptiss,O2 response (‘dip’), while attenuating the evoked CBF increase and positive Ptiss,O2 response equally. This indicates that increases in CBF counteract activity-induced reductions in Ptiss,O2, and suggests the presence of a tissue oxygen reserve. The changes in Ptiss,O2 and CBF were strongly attenuated by AMPA receptor blockade. Our findings suggest an inverse relationship between negative Ptiss,O2 and CBF responses, and provide direct in vivo evidence for a tight coupling between activity in postsynaptic AMPA receptors and cerebellar oxygen consumption. PMID:15774524

  15. 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

  16. 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%.

  17. [Effect of substances which change the proton-motive force on activity of methane microbe oxygenation].

    PubMed

    Malashenko, Iu P; Sokolov, I G; Rokitko, P V; Romanovskaia, V A

    2006-01-01

    High extracellular concentration of K+ stimulated methane oxygenation with Methylomonas rubra 15 [Russian character: see text], Methylococcus thermophilus 111 [Russian character: see text] and Methylococcus capsulatus 494 at neutral value of pH. That was determined by K+ arrival to the cells at neutral medium pH that resulted in the increase of pH difference between the exterior and interior sides of the membrane (ApH) and, respectively, in the increase of the methane oxygenation rate. Thus, methane monooxygenation depends on the availability of ion gradients on a membrane. Ionophores valinomycin and monensin inhibited methane oxygenation by the cells of Methylomonas rubra 15 [Russian character: see text] that evidenced for the methane oxygenation dependence on the protone-motive force which could be formed as the result both of protons displacement with oxygenation of methane monooxygenation products and of the gradient of potassium and sodium ions. Protonophore FCCP suppressed completely methane oxygenation in Methylococcus capsulatus 494 and M. thermophilus 111 [Russian character: see text] at neutral pH, and took no effect at the alkaline values of pH. This suggests that FCCP dissipates the proton-motive force and does not inhibit methane monooxygenase activity. The results obtained indicate that the process of methane oxygenation should be combined with energy generation in a form of the transmembrane electric charge (delta psi) and proton gradient (deltapH). PMID:17243361

  18. NADPH Oxidase- and Mitochondria-derived Reactive Oxygen Species in Proinflammatory Microglial Activation: A Bipartisan Affair?

    PubMed Central

    Bordt, Evan A.; Polster, Brian M.

    2014-01-01

    Microglia are the resident immune cells of the brain and play major roles in central nervous system development, maintenance, and disease. Brain insults cause microglia to proliferate, migrate, and transform into one or more activated states. Classical M1 activation triggers the production of proinflammatory factors such as tumor necrosis factor- α (TNF-α), interleukin-1β (IL-1β), nitric oxide (NO), and reactive oxygen species which, in excess, can exacerbate brain injury. The mechanisms underlying microglial activation are not fully understood, yet reactive oxygen species are increasingly implicated as mediators of microglial activation. In this review, we highlight studies linking reactive oxygen species, in particular hydrogen peroxide derived from NADPH oxidase-generated superoxide, to the classical activation of microglia. In addition, we critically evaluate controversial evidence suggesting a specific role for mitochondrial reactive oxygen species in the activation of the NLRP3 inflammasome, a multiprotein complex that mediates the production of IL-1β and IL-18. Finally, the limitations of common techniques used to implicate mitochondrial ROS in microglial and inflammasome activation, such as the use of the mitochondrially-targeted ROS indicator MitoSOX and the mitochondrially-targeted antioxidant MitoTEMPO, are also discussed. PMID:25091898

  19. Novel water-resistant UV-activated oxygen indicator for intelligent food packaging.

    PubMed

    Vu, Chau Hai Thai; Won, Keehoon

    2013-09-01

    For the first time, alginate polymer has been applied to prevent dyes from leaching out of colorimetric oxygen indicator films, which enable people to notice the presence of oxygen in the package in an economic and simple manner. The dye-based oxygen indicator film suffers from dye leaching upon contact with water. In this work, UV-activated visual oxygen indicator films were fabricated using thionine, glycerol, P25 TiO2, and zein as a redox dye, a sacrificial electron donor, UV-absorbing semiconducting photocatalyst, and an encapsulation polymer, respectively. When this zein-coated film was immersed in water for 24h, the dye leakage was as high as 80.80±0.45%. However, introduction of alginate (1.25%) as the coating polymer considerably diminished the dye leaching to only 5.80±0.06%. This is because the ion-binding ability of alginate could prevent the cation dye from leaching into water. This novel water-resistant UV-activated oxygen indicator was also successfully photo-bleached and regained colour fast in the presence of oxygen. PMID:23578614

  20. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction

    PubMed Central

    Chung, Hoon T.; Won, Jong H.; Zelenay, Piotr

    2013-01-01

    Nanostructured carbon-based materials, such as nitrogen-doped carbon nanotube arrays, Co3O4/nitrogen-doped graphene hybrids and carbon nanotube–graphene complexes have shown respectable oxygen reduction reaction activity in alkaline media. Although certainly promising, the performance of these materials does not yet warrant implementation in the energy conversion/storage devices utilizing basic electrolytes, for example, alkaline fuel cells, metal-air batteries and certain electrolysers. Here we demonstrate a new type of nitrogen-doped carbon nanotube/nanoparticle composite oxygen reduction reaction electrocatalyst obtained from iron acetate as an iron precursor and from cyanamide as a nitrogen and carbon nanotube precursor in a simple, scalable and single-step method. The composite has the highest oxygen reduction reaction activity in alkaline media of any non-precious metal catalysts. When used at a sufficiently high loading, this catalyst also outperforms the most active platinum-based catalysts. PMID:23715281

  1. Evaluation of the catalytic activity and cytotoxicity of palladium nanocubes: the role of oxygen.

    PubMed

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

    2015-05-13

    Recently, it has been reported that palladium nanocubes (PdNC) are capable of generating singlet oxygen without photoexcitation 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 3,3',5,5'-tetramethylbenzidine (TMB), and 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 toward the oxidation of TMB is very high and shows direct two-electron oxidation when the surface of the 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

  2. 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

  3. Air-activated chemical warming devices: effects of oxygen and pressure.

    PubMed

    Raleigh, G; Rivard, R; Fabus, S

    2005-01-01

    Air-activated chemical warming devices use an exothermic chemical reaction of rapidly oxidizing iron to generate heat for therapeutic purposes. Placing these products in a hyperbaric oxygen environment greatly increases the supply of oxidant and thus increases the rate of reaction and maximum temperature. Testing for auto-ignition and maximum temperatures attained by ThermaCare Heat Wraps, Playtex Heat Therapy, and Heat Factory disposable warm packs under ambient conditions and under conditions similar to those encountered during hyperbaric oxygen treatments in monoplace and multiplace hyperbaric chambers (3 atm abs and > 95% oxygen) revealed a maximum temperature of 269 degrees F (132 degrees C) with no spontaneous ignition. The risk of thermal burn injury to adjacent skin may be increased significantly if these devices are used under conditions of hyperbaric oxygen. PMID:16509287

  4. 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

  5. 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.

  6. Apogossypolone targets mitochondria and light enhances its anticancer activity by stimulating generation of singlet oxygen and reactive oxygen species

    PubMed Central

    Hu, Zhe-Yu; Wang, Jing; Cheng, Gang; Zhu, Xiao-Feng; Huang, Peng; Yang, Dajun; Zeng, Yi-Xin

    2011-01-01

    Apogossypolone (ApoG2), a novel derivative of gossypol, has been shown to be a potent inhibitor of antiapoptotic Bcl-2 family proteins and to have antitumor activity in multiple types of cancer cells. Recent reports suggest that gossypol stimulates the generation of cellular reactive oxygen species (ROS) in leukemia and colorectal carcinoma cells; however, gossypol-mediated cell death in leukemia cells was reported to be ROS-independent. This study was conducted to clarify the effect of ApoG2-induced ROS on mitochondria and cell viability, and to further evaluate its utility as a treatment for nasopharyngeal carcinoma (NPC). We tested the photocytotoxicity of ApoG2 to the poorly differentiated NPC cell line CNE-2 using the ROS-generating TL/10 illumination system. The rapid ApoG2-induced cell death was partially reversed by the antioxidant N-acetyl-L-cysteine (NAC), but the ApoG2-induced reduction of mitochondrial membrane potential (MMP) was not reversed by NAC. In the presence of TL/10 illumination, ApoG2 generated massive amounts of singlet oxygen and was more effective in inhibiting cell growth than in the absence of illumination. We also determined the influence of light on the anti-proliferative activity of ApoG2 using a CNE-2–xenograft mouse model. ApoG2 under TL/10 illumination healed tumor wounds and suppressed tumor growth more effectively than ApoG2 treatment alone. These results indicate that the ApoG2-induced CNE-2 cell death is partly ROS-dependent. ApoG2 may be used with photodynamic therapy (PDT) to treat NPC. PMID:21192843

  7. 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.

  8. REVIEW: Excited states in the active media of oxygen — iodine lasers

    NASA Astrophysics Data System (ADS)

    Azyazov, V. N.

    2009-11-01

    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 O2 and I2 molecules are considered, and dissociation mechanisms of I2 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.

  9. 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

  10. Respiratory muscle activity and oxygenation during sleep in patients with muscle weakness.

    PubMed

    White, J E; Drinnan, M J; Smithson, A J; Griffiths, C J; Gibson, G J

    1995-05-01

    Patients with respiratory muscle weakness show nocturnal hypoventilation, with oxygen desaturation particularly during rapid eye movement (REM) sleep, but evidence in individuals with isolated bilateral diaphragmatic paresis (BDP) is conflicting. The effect of sleep on relative activity of the different respiratory muscles of such patients and, consequently, the precise mechanisms causing desaturation have not been clarified. We have studied eight patients, four with generalized muscle weakness and four with isolated BDP during nocturnal sleep with measurements including oxygen saturation and surface electromyographic (EMG) activity of various respiratory muscle groups. Nocturnal oxygenation correlated inversely with postural fall in vital capacity, an index of diaphragmatic strength. During REM sleep, hypopnoea and desaturation occurred particularly during periods of rapid eye movements (phasic REM sleep). In most subjects, such events were "central" in type and associated with marked suppression of intercostal muscle activity, but two subjects had recurrent desaturation due to "obstructive" hypopnoea and/or apnoea. Expiratory activity of the external oblique muscle was present whilst awake and during non-rapid eye movement (NREM) sleep in seven of the eight subjects in the semirecumbent posture. This probably represents an "accessory inspiratory" effect, which aids passive caudal diaphragmatic motion as the abdominal muscles relax at the onset of inspiration. Expiratory abdominal muscle activity was suppressed in phasic REM sleep, suggesting that loss of this "accessory inspiratory" effect may contribute to "central" hypopnoea. We conclude that, in patients with muscle weakness, nocturnal oxygenation correlates with diaphragmatic strength.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7656954

  11. 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

  12. Active medium gain study of electric-discharge oxygen-iodine laser

    NASA Astrophysics Data System (ADS)

    Kolobyanin, Yuriy; Adamenkov, Yuriy; Vyskubenko, Boris; Goryachev, Leonid; Ilyin, Sergey; Kalashnik, Anatoliy; Rakhimova, Tatiana; Rogozhnikov, Georgiy

    2007-05-01

    The paper reports on experimental studies of the active medium gain in supersonic electric-discharge oxygen-iodine laser (DOIL) based on traveling mw discharge. The measurements have included: absolute concentration, yield, and energy efficiency of production of SO in pure oxygen and oxygen-helium mixes at an oxygen partial pressure 3 to 15 Torr. For the gas flow to get rid of atomic oxygen, both heterogeneous mercury oxide coatings of the tube walls and homogeneous additives to the work mix, such as nitrogen oxide, have been used. The active medium of DOIL was formed using a nozzle array of the type of ejector sized as 10*50 mm2. The singlet oxygen-helium mix was supplied through three rows of sonic cylindrical nozzles, while the iodine-carrier gas mix - through two rows of supersonic conical nozzles with a half-opening angle of 10°(arc). The gas-phase iodine was produced in a quartz cell filled with iodine crystals. Room-temperature iodine vapors were picked up with a carrier gas (nitrogen or helium) and thus delivered into the nozzle array. The active medium was investigated by the high-resolution laser diode spectroscopy approach that used the laser type Vortex 6025 purchased from New Focus, Inc. The laser medium gain factor was determined by the intra-cavity approach having a sensitivity about 1*10 -6 cm -1. The static temperature of the medium was determined from the measurements of gain half-width. The gain of the active medium of electric-discharge OIL has been investigated. The DOIL in use was operating on a mix composed as O II:He=1:1 at a total pressure of 6 Torr and flowrate - about 1 mmol/s. With helium as an iodine carrier gas at a flowrate ~3 mmol/s, we have recorded a positive gain in the DOIL medium.

  13. 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.

  14. In vivo imaging of brain metabolism activity using a phosphorescent oxygen-sensitive probe

    PubMed Central

    Tsytsarev, Vassiliy; Arakawa, Hiroyuki; Borisov, Sergei; Pumbo, Elena; Erzurumlu, Reha S.; Papkovsky, Dmitri B.

    2013-01-01

    Several approaches have been adopted for real-time imaging of neural activity in vivo. We tested a new cell-penetrating phosphorescent oxygen-sensitive probe, NanO2-IR, to monitor temporal and spatial dynamics of oxygen metabolism in the neocortex following peripheral sensory stimulation. Probe solution was applied to the surface of anesthetized mouse brain; optical imaging was performed using a MiCAM-02 system. Trains of whisker stimuli were delivered and associated changes in phosphorescent signal were recorded in the contralateral somatosensory (“barrel”) cortex. Sensory stimulation led to changes in oxygenation of activated areas of the barrel cortex. The oxygen imaging results were compared to those produced by the voltage-sensitive dye RH-1691. While the signals emitted by the two probes differed in shape and amplitude, they both faithfully indicated specific whisker evoked cortical activity. Thus, NanO2-IR probe can be used as a tool in visualization and realtime analysis of sensory- evoked neural activity in vivo. PMID:23624034

  15. FULL-SCALE DEMONSTRATION OF OPEN TANK OXYGEN ACTIVATED SLUDGE TREATMENT

    EPA Science Inventory

    This report presents an operating summary of a full-scale demonstration of the FMC open tank pure oxygen (FMC O2) activated sludge system, conducted at the facilities of the Metropolitan Denver Sewage Disposal District No. 1 (Metro) in Denver, Colorado. The system was operated ov...

  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. OXYGEN-ACTIVATED SLUDGE PLANT COMPLETES TWO YEARS OF SUCCESSFUL OPERATION

    EPA Science Inventory

    A detailed report of the conversion to and operational performance of an oxygen-activated sludge system at the Westgate wastewater treatment plant in Fairfax County, Virginia, is given in this report. It is presented in the form of a case history including the time span leading u...

  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. Activation energies for oxygen reduction on platinum alloys: theory and experiment.

    PubMed

    Anderson, Alfred B; Roques, Jérôme; Mukerjee, Sanjeev; Murthi, Vivek S; Markovic, Nenad M; Stamenkovic, Vojislav

    2005-01-27

    A combined theoretical and experimental analysis of the electrode potential dependencies of activation energies is presented for the first step in oxygen reduction over platinum and platinum alloy catalysts in both polycrystalline and carbon supported form. Tafel data for several of the catalysts are used to predict potential-dependent activation energies for oxygen reduction over the 0.6-0.9 V range in strong and weak acid. Comparisons with the theoretical curve show good agreement above 0.8 V, suggesting a fairly constant preexponential factor. Arrhenius determinations of activation energies over the 0.7-0.9 V range yield little trend for weak acid, possibly because of the larger uncertainties in the Arrhenius fits, but the strong acid results have smaller uncertainties and for them the measured activation energies trend up with potential. PMID:16851081

  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. PMID:26544169

  1. 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. PMID:26465962

  2. 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. PMID:26313467

  3. 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

  4. Effects of oxygen concentration on the nitrifying activity of an aerobic hybrid granular sludge reactor.

    PubMed

    Filali, Ahlem; Bessiere, Yolaine; Sperandio, Mathieu

    2012-01-01

    The aim of the work was to quantify the influence of the simultaneous presence of flocs and granules in the nitrifying activity in a sequencing batch airlift reactor (SBAR). The nitrification rate and oxygen limitation of flocs, granules and hybrid sludge was investigated using respirometric assays at different dissolved oxygen concentrations. The spatial distribution of Ammonium Oxidizing Bacteria (AOB) and Nitrite Oxidizing Bacteria (NOB) was investigated using fluorescence in situ hybridization (FISH). Results showed that the nitrification rate was much less sensitive to oxygen limitation in systems containing a fraction of flocs than in pure granular sludge. Ammonium Oxidizing Bacteria (AOB) were found to be distributed in similar quantities in flocs and granules whereas the Nitrite Oxidizing Bacteria (NOB) were located preferentially in granules. This study showed that the presence of flocs with granules could increase the robustness of the process to transitory reductions of aeration. PMID:22233907

  5. 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

  6. Increased oxygen consumption following activation of brain: theoretical footnotes using spectroscopic data from barrel cortex.

    PubMed

    Mayhew, J; Johnston, D; Martindale, J; Jones, M; Berwick, J; Zheng, Y

    2001-06-01

    Optical imaging spectroscopy (OIS) and laser Doppler flowmetry (LDF) data sequences from anesthetized rats were used to determine the relationship between changes in oxy-and deoxygenated hemoglobin concentration and changes in blood volume and flow in the presence and absence of stimulation. The data from Jones et al. (accompanying paper) were used to explore the differences between two theoretical models of flow activation coupling. The essential difference between the two models is the extension of the model of Buxton and Frank by Hyder et al. (1998, J. Appl. Physiol. 85: 554--564) to incorporate change in capillary diffusivity coupled to flow. In both models activation-increased flow changes increase oxygen transport from the capillary; however, in Hyder et al.'s model the diffusivity of the capillary itself is increased. Hyder et al. proposed a parameter (Omega), a scaling "constant" linking increased blood flow and oxygen "diffusivity" in the capillary bed. Thus, in Buxton and Frank's theory, Omega = 0; i.e., there are no changes in diffusivity. In Hyder et al.'s theory, 0 < Omega < 1, and changes in diffusivity are assumed to be linearly related to flow changes. We elaborate the theoretical position of both models to show that, in principle, the different predictions from the two theories can be evaluated using optical imaging spectroscopy data. We find that both theoretical positions have limitations when applied to data from brief stimulation and when applied to data from mild hypercapnia. In summary, the analysis showed that although Hyder et al.'s proposal that diffusivity increased during activation did occur; it was shown to arise from an implementation of Buxton and Frank's theory under episodes of brief stimulation. The results also showed that the scaling parameter Omega is not a constant as the Hyder et al. model entails but in fact varies over the time course of the flow changes. Data from experiments in which mild hypercapnia was administered also

  7. Scavenging activity of "beta catechin" on reactive oxygen species generated by photosensitization of riboflavin.

    PubMed

    Kumari, M V; Yoneda, T; Hiramatsu, M

    1996-05-01

    "beta CATECHIN", a preparation containing green tea extract, ascorbic acid, sunflower seed extract, dunaliella carotene and natural vitamin E, has been designed as a model "universal antioxidant" that offers protection via its scavenging action on a wide range of free radicals, both water-soluble and fat-soluble. Reactive oxygen species like singlet oxygen, hydroxyl and superoxide radicals, are often generated in biological systems during photosensitized oxidation reactions. We report on the simultaneous effect of "beta CATECHIN" on active oxygen species generated during the photosensitized oxidation of riboflavin using 2,2,6,6-tetramethyl-4-piperidone (TMPD) as a "spin-trapping" agent. The intensities of the resulting stable nitroxide radical adduct, 2,2,6,6-tetramethyl-4-piperidone-1-oxyl (TEMPONE), were detected by electron spin resonance (ESR) spectroscopy. Results show simultaneous, nonspecific and complete scavenging action of reactive oxygen species generated in our in vitro model system by "beta CATECHIN". It is therefore suggested that "beta CATECHIN" could offer protection against free radical insult and in preventing cancer and other diseases that are mediated by reactive oxygen species. PMID:8739038

  8. 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

  9. LASERS: Efficient chemical oxygen — iodine laser with a high total pressure of the active medium

    NASA Astrophysics Data System (ADS)

    Zagidullin, M. V.; Nikolaev, V. D.; Svistun, M. I.; Khvatov, N. A.; Heiger, G. D.; Madden, T. J.

    2001-01-01

    A new concept of obtaining a high total pressure of the active medium of a chemical oxygen — iodine laser (OIL) is proposed and verified. The nozzle unit of the laser consists of the alternating vertical arrays of cylindrical nozzles to produce high-pressure nitrogen jets, plane slotted nozzles for the flow of O2(1Δ) oxygen, and vertical arrays of cylindrical nozzles to inject the N2 — I2 mixture between the first two streams. For a molar chlorine flow rate of 39.2 mmol s-1, the output power was 700 W and the chemical efficiency was 19.7 %. The combined use of the ejector nozzle unit proposed to obtain the active medium and a super-sonic diffuser allows a significant simplification of the ejection system for the exhaust active medium of the OIL.

  10. [Light-induced production and consumption of oxygen by chloroplasts: activation and inhibition].

    PubMed

    Chan Van, N i; Nikandrov, V V; Brin, G P; Krasnovskii, A A

    1977-07-01

    Light-induced production and consumption of oxygen by pea chloroplasts are activated at certain concentrations of the solvents (diethyl ester, methyl alcohol, dimethylsulfoxide) and detergent Triton X-100. At higher concentrations of the compounds studied both reactions are inhibited. The uncouplers (methylamine and carbonyl cyanide-3-chlorophenylhydrazone) activate these processes. The agents studied have a similar effect on the processes of light-induced production and consumption of oxygen, which are limited by a common link bound to the phosphorylation site in photosystem I. The effects observed suggest that the inhibition may be due to inhibition of photosystem II, whereas the activation may be largely due to an action on photosystem I. PMID:907797

  11. 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.

  12. 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. PMID:22044022

  13. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability.

    PubMed

    Stamenkovic, Vojislav R; Fowler, Ben; Mun, Bongjin Simon; Wang, Guofeng; Ross, Philip N; Lucas, Christopher A; Marković, Nenad M

    2007-01-26

    The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption. PMID:17218494

  14. 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

  15. Applications of microbial cytochrome P450 enzymes in biotechnology and synthetic biology.

    PubMed

    Girvan, Hazel M; Munro, Andrew W

    2016-04-01

    Cytochrome P450 enzymes (P450s) are a superfamily of monooxygenase enzymes with enormous potential for synthetic biology applications. Across Nature, their substrate range is vast and exceeds that of other enzymes. The range of different chemical transformations performed by P450s is also substantial, and continues to expand through interrogation of the properties of novel P450s and by protein engineering studies. The ability of P450s to introduce oxygen atoms at specific positions on complex molecules makes these enzymes particularly valuable for applications in synthetic biology. This review focuses on the enzymatic properties and reaction mechanisms of P450 enzymes, and on recent studies that highlight their broad applications in the production of oxychemicals. For selected soluble bacterial P450s (notably the high-activity P450-cytochrome P450 reductase enzyme P450 BM3), variants with a multitude of diverse substrate selectivities have been generated both rationally and by random mutagenesis/directed evolution approaches. This highlights the robustness and malleability of the P450 fold, and the capacity of these biocatalysts to oxidise a wide range of chemical scaffolds. This article reviews recent research on the application of wild-type and engineered P450s in the production of important chemicals, including pharmaceuticals and drug metabolites, steroids and antibiotics. In addition, the properties of unusual members of the P450 superfamily that do not follow the canonical P450 catalytic pathway are described. PMID:27015292

  16. Oxygen deficient ZnO 1-x nanosheets with high visible light photocatalytic activity.

    PubMed

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

    2015-04-28

    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 ZnO 1-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 ZnO 1-x. The incorporation of oxygen defects could effectively extend the light absorption of ZnO 1-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 ZnO 1-x shows a higher photodegradation of methyl orange (MO) compared to defect-free ZnO under visible light illumination. Additionally, the high content of ˙OH radicals with a strong photo-oxidation capability over the ZnO 1-x nanosheets significantly contributes to the improvement in the photocatalytic performance. Our oxygen deficient ZnO 1-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. PMID:25812132

  17. Hyperbaric oxygen preserves neurotrophic activity of carbon monoxide-exposed astrocytes.

    PubMed

    Jurič, Damijana M; Šuput, Dušan; Brvar, Miran

    2016-06-24

    In astrocytes, carbon monoxide (CO) poisoning causes oxidative stress and mitochondrial dysfunction accompanied by caspase and calpain activation. Impairment in astrocyte function can be time-dependently reduced by hyperbaric (3bar) oxygen (HBO). Due to the central role of astrocytes in maintaining neuronal function by offering neurotrophic support we investigated the hypothesis that HBO therapy may exert beneficial effect on acute CO poisoning-induced impairment in intrinsic neurotrophic activity. Exposure to 3000ppm CO in air followed by 24-72h of normoxia caused a progressive decline of gene expression, synthesis and secretion of nerve growth factor (NGF), brain-derived neurotrophic factor (BDNF) and neurotrophin-3 (NT-3) to different extent. 1h treatment with 100% oxygen disclosed a pressure- and time-dependent efficacy in preserving astrocytic neurotrophic support. The beneficial effect was most evident when the astrocytes were exposed to HBO 1-5h after exposure to CO. The results further support an active role of hyperbaric, not normobaric, oxygenation in reducing dysfunction of astrocytes after acute CO poisoning. By preserving endogenous neurotrophic activity HBO therapy might promote neuronal protection and thus prevent the occurrence of late neuropsychological sequelae. PMID:27113706

  18. Effect of KOH activation on the formation of oxygen structure in activated carbons synthesized from polymeric precursor.

    PubMed

    Park, Soo-Jin; Jung, Woo-Young

    2002-06-01

    In this work, the influence of KOH activation on the surface chemistry of activated carbons (ACs) synthesized from polystyrene-based cation exchangeable resin (PSI) has been investigated. The surface chemistry of ACs has been characterized by using Fourier transformed infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), pH measurement, and Boehm's titration method. As a result, PSI can be successfully converted into ACs with high porosities. The total oxygen content on the ACs studied increases with increasing the KOH-to-PSI ratio. FT-IR and XPS analyses show that the resulting carbons possess a number of oxygen surface functional groups, such as carbonyl, quinone, phenol, ether, and carboxylic acid groups. The highest oxygen content and acid value are observed at a KOH-to-PSI ratio of 4 (KPS-4). However, its pH and surface basicity are higher than those of a KOH-to-PSI ratio of 2 (KPS-2), indicating the formation of basic species, such as quinone and pyrone groups. Although the oxygen-containing groups with basic character exist in the resulting carbons, all the samples are still acidic in character. PMID:16290638

  19. 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

  20. 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}.

  1. 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.

  2. 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

  3. Structural Characterization of Mutations at the Oxygen Activation Site in Monomeric Sarcosine Oxidase

    SciTech Connect

    Schuman Jorns, Marilyn; Chen, Zhi-wei; Mathews, F. Scott

    2010-04-30

    Oxygen reduction and sarcosine oxidation in monomeric sarcosine oxidase (MSOX) occur at separate sites above the si- and re-faces, respectively, of the flavin ring. Mutagenesis studies implicate Lys265 as the oxygen activation site. Substitution of Lys265 with a neutral (Met, Gln, or Ala) or basic (Arg) residue results in an {approx}10{sup 4}- or 250-fold decrease, respectively, in the reaction rate. The overall structure of MSOX and residue conformation in the sarcosine binding cavity are unaffected by replacement of Lys265 with Met or Arg. The side chain of Met265 exhibits the same configuration in each molecule of Lys265Met crystals and is nearly congruent with Lys265 in wild-type MSOX. The side chain of Arg265 is, however, dramatically shifted (4-5 {angstrom}) compared with Lys265, points in the opposite direction, and exhibits significant conformational variability between molecules of the same crystal. The major species in solutions of Lys265Arg is likely to contain a 'flipped-out' Arg265 and exhibit negligible oxygen activation, similar to Lys265Met. The 400-fold higher oxygen reactivity observed with Lys265Arg is attributed to a minor (<1%) 'flipped-in' Arg265 conformer whose oxygen reactivity is similar to that of wild-type MSOX. A structural water (WAT1), found above the si-face of the flavin ring in all previously determined MSOX structures, is part of an apparent proton relay system that extends from FAD N(5) to bulk solvent. WAT1 is strikingly absent in Lys265Met and Lys265Arg, a feature that may account for the apparent kinetic stabilization of a reductive half-reaction intermediate that is detectable with the mutants but not wild-type MSOX.

  4. 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

  5. Highly branched PtCu bimetallic alloy nanodendrites with superior electrocatalytic activities for oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Fu, Shaofang; Zhu, Chengzhou; Shi, Qiurong; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-02-01

    Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst.Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07682j

  6. 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. PMID:26459261

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

    PubMed

    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 (57)Fe 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  9. 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.

  10. 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.

  11. 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

  12. Phenol degradation in heterogeneous system generating singlet oxygen employing light activated electropolymerized phenothiazines

    NASA Astrophysics Data System (ADS)

    Piwowar, Katarzyna; Blacha-Grzechnik, Agata; Bernas, Paulina; Zak, Jerzy

    2015-12-01

    Five selected amine-derivatives of phenothiazine were electropolymerized on an ITO/glass substrate and then used in the daylight-activated process to produce in situ singlet oxygen which degrades phenol in a solution. The phenothiazines were immobilized in a simple electrochemical procedure in an acidic solution which led to the formation of an ultrathin transparent polymeric film. All films obtained on the ITO substrate including azure A (AA), azure C (AC), methylene blue (MB), toluidine blue (TBO), and thionine (Th) had a comparable surface coverage at the level of picomoles/cm2. The activity of these materials was then compared and presented in terms of an efficiency of the phenol degradation process in an aqueous solution by photogenerated singlet oxygen. That efficiency was determined by the UV-vis spectroscopy employing a phenol/4-aminoantipyrine complex. All the phenothiazine ultrathin polymeric films were capable of generating the singlet oxygen in the aqueous solution under daylight activation, which was used in the consecutive process of phenol degradation. The highest efficiency at a level of 51.4% and 45.4% was found for the AC/ITO and MB/ITO layers, respectively.

  13. 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.

  14. 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

  15. Synthesis, Characterization, and Catalytic Oxygen Electroreduction Activities of Carbon-Supported PtW Nanoparticle Catalysts

    SciTech Connect

    Xiong, Liufeng; More, Karren Leslie; He, Ting

    2010-01-01

    Carbon-supported PtW (PtW/C) alloy nanoparticle catalysts with well-controlled particle size, dispersion, and composition uniformity, have been synthesized by wet chemical methods of decomposition of carbonyl cluster complexes, hydrolysis of metal salts, and chemical reactions within a reverse microemulsion. The synthesized PtW/C catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, and energy-dispersive spectroscopy. The catalytic oxygen electroreduction activities were measured by the hydrodynamic rotating disk electrode technique in an acidic electrolyte. The influence of the synthesis method on PtW particle size, size distribution, composition uniformity, and catalytic oxygen electroreduction activity, have been investigated. Among the synthesis methods studied, PtW/C catalysts prepared by the decomposition of carbonyl cluster complexes displayed the best platinum mass activity for oxygen reduction reaction under the current small scale production; a 3.4-fold catalytic enhancement was achieved in comparison to a benchmark Pt/C standard.

  16. Inhibitory activities of soluble and bound millet seed phenolics on free radicals and reactive oxygen species.

    PubMed

    Chandrasekara, Anoma; Shahidi, Fereidoon

    2011-01-12

    Oxidative stress, caused by reactive oxygen species (ROS), is responsible for modulating several pathological conditions and aging. Soluble and bound phenolic extracts of commonly consumed millets, namely, kodo, finger (Ravi), finger (local), foxtail, proso, little, and pearl, were investigated for their phenolic content and inhibition of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and ROS, namely, hydroxyl radical, peroxyl radical, hydrogen peroxide (H(2)O(2)), hypochlorous acid (HOCl), and singlet oxygen ((1)O(2)). Inhibition of DPPH and hydroxyl radicals was detrmined using electron paramagnetic resonance (EPR) spectroscopy. The peroxyl radical inhibitory activity was measured using the oxygen radical absorbance capacity (ORAC) assay. The scavenging of H(2)O(2), HOCl, and (1)O(2) was evaluated using colorimetric methods. The results were expressed as micromoles of ferulic acid equivalents (FAE) per gram of grain on a dry weight basis. In addition, major hydroxycinnamic acids were identified and quantified using high-performance liquid chromatography (HPLC) and HPLC-mass spectrometry (MS). All millet varieties displayed effective radical and ROS inhibition activities, which generally positively correlated with phenolic contents, except for hydroxyl radical. HPLC analysis revealed the presence of ferulic and p-coumaric acids as major hydroxycinnamic acids in phenolic extract and responsible for the observed effects. Bound extracts of millet contributed 38-99% to ROS scavenging, depending on the variety and the test system employed. Hence, bound phenolics must be included in the evaluation of the antioxidant activity of millets and other cereals. PMID:21133411

  17. Oxygen activation in NO synthases: evidence for a direct role of the substrate.

    PubMed

    Brunel, Albane; Lang, Jérôme; Couture, Manon; Boucher, Jean-Luc; Dorlet, Pierre; Santolini, Jérôme

    2016-05-01

    Nitric oxide (NO) and the other reactive nitrogen species (RNOS) play crucial patho-physiological roles at the interface of oxidative stress and signalling processes. In mammals, the NO synthases (NOSs) are the source of these reactive nitrogen species, and so to understand the precise biological role of RNOS and NO requires elucidation of the molecular functioning of NOS. Oxygen activation, which is at the core of NOS catalysis, involves a sophisticated sequence of electron and proton transfers. While electron transfer in NOS has received much attention, the proton transfer processes has been scarcely investigated. Here, we report an original approach that combines fast-kinetic techniques coupled to resonance Raman spectroscopy with the use of synthetic analogues of NOS substrate. We characterise Fe(II)-O2 reaction intermediates in the presence of L-arginine (Arg), alkyl- and aryl-guanidines. The presence of new reaction intermediates, such as ferric haem-peroxide, that was formerly postulated, was tracked by analysing the oxygen activation reaction at different times and with different excitation wavelengths. Our results suggest that Arg is not a proton donor, but indirectly intervenes in oxygen activation mechanism by modulating the distal H-bond network and, in particular, by tuning the position and the role of the distal water molecule. This report supports a catalytic model with two proton transfers in step 1 (Arg hydroxylation) but only one proton transfer in step 2 (N(ω)-hydroxy-L-arginine oxidation). PMID:27419044

  18. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  19. 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.

  20. A mathematical model relating cortical oxygenated and deoxygenated hemoglobin flows and volumes to neural activity

    NASA Astrophysics Data System (ADS)

    Cornelius, Nathan R.; Nishimura, Nozomi; Suh, Minah; Schwartz, Theodore H.; Doerschuk, Peter C.

    2015-08-01

    Objective. To describe a toolkit of components for mathematical models of the relationship between cortical neural activity and space-resolved and time-resolved flows and volumes of oxygenated and deoxygenated hemoglobin motivated by optical intrinsic signal imaging (OISI). Approach. Both blood flow and blood volume and both oxygenated and deoxygenated hemoglobin and their interconversion are accounted for. Flow and volume are described by including analogies to both resistive and capacitive electrical circuit elements. Oxygenated and deoxygenated hemoglobin and their interconversion are described by generalization of Kirchhoff's laws based on well-mixed compartments. Main results. Mathematical models built from this toolkit are able to reproduce experimental single-stimulus OISI results that are described in papers from other research groups and are able to describe the response to multiple-stimuli experiments as a sublinear superposition of responses to the individual stimuli. Significance. The same assembly of tools from the toolkit but with different parameter values is able to describe effects that are considered distinctive, such as the presence or absence of an initial decrease in oxygenated hemoglobin concentration, indicating that the differences might be due to unique parameter values in a subject rather than different fundamental mechanisms.

  1. 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

  2. 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. PMID:21667986

  3. 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.

  4. Reactive oxygen species scavenging activity of Jixueteng evaluated by electron spin resonance (ESR) and photon emission.

    PubMed

    Toyama, Toshizo; Wada-Takahashi, Satoko; Takamichi, Maomi; Watanabe, Kiyoko; Yoshida, Ayaka; Yoshino, Fumihiko; Miyamoto, Chihiro; Maehata, Yojiro; Sugiyama, Shuta; Takahashi, Shun-Suke; Todoki, Kazuo; Lee, Masaichi-Chang-Il; Hamada, Nobushiro

    2014-12-01

    Jixueteng, the dried stem of Spatholobus suberectus Dunn (Leguminosae), is a traditional Chinese herbal medicine that is commonly classified as a herb that promotes blood circulation and can be used to treat blood stasis. The aim of this study was to examine the reactive oxygen species (ROS) scavenging activity of Jixueteng and other herbal medicines. The ROS scavenging activities of the water extracts of Jixueteng, Cnidium officinale and Salvia miltiorrhiza were examined using an electron spin resonance (ESR) technique and faint luminescence measurement. The ESR signal intensities of the superoxide anion (O2·) and hydroxyl radical (HO·) were reduced more by Jixueteng than the other herbal medicines we tested. High photon emission intensity to hydrogen peroxide (H202) and HO· was observed in Jixueteng using the XYZ chemiluminescence system that was used as faint luminescence measurement and analysis. The results of the present study revealed that the ROS scavenging activity of 8% Jixueteng was the strongest among the herbal medicines we tested. It has been reported that Jixueteng includes various polyphenols. In the ROS scavenging activity by Jixueteng, it is supposed that the antioxidant activity caused by these polyphenols would contribute greatly. In conclusion, a water extract component of Jixueteng had potent free radical scavenging activity and an antioxidative effect that inhibited the oxidative actions of O2·⁻, H2O2 and HO·. Therefore, Jixueteng represents a promising therapeutic drug for reactive oxygen-associated pathologies. PMID:25632478

  5. 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

  6. 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

  7. 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

  8. A Strategy to Promote the Electrocatalytic Activity of Spinels for Oxygen Reduction by Structure Reversal.

    PubMed

    Wu, Guangping; Wang, Jun; Ding, Wei; Nie, Yao; Li, Li; Qi, Xueqiang; Chen, Siguo; Wei, Zidong

    2016-01-22

    The electrocatalytic performance of a spinel for the oxygen reduction reaction (ORR) can be significantly promoted by reversing its crystalline structure from the normal to the inverse. As the spinel structure reversed, the activation and cleavage of O-O bonds are accelerated owing to a dissimilarity effect of the distinct metal atoms co-occupying octahedral sites. The Co(II)Fe(III)Co(III)O4 spinel with the Fe and Co co-occupying inverse structure exhibits an excellent ORR activity, which even exceeds that of the state-of-the-art commercial Pt/C by 42 mV in alkaline medium. PMID:26663768

  9. Structure-activity relationship in high-performance iron-based electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Song, Ping; Wang, Ying; Pan, Jing; Xu, Weilin; Zhuang, Lin

    2015-12-01

    A sustainable Iron (Fe), Nitrogen (N) co-doped high performance Fe-Nx/C electrocatalyst for oxygen reduction reaction (ORR) is synthesized simply based on nitric acid oxidation of cheap carbon black. The obtained optimal nonprecious metal electrocatalyst shows high ORR performance in both alkaline and acidic conditions and possesses appreciable performance/price ratio due to its low cost. Furthermore, the structure-activity relationship of different active sites on Fe-Nx/C is revealed systematically: Fe-N4/2-C > Fe4-N-C > N-C >> Fe4-C ≥ C, from both experimental and theoretical points of view.

  10. 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, ...

  11. 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.

  12. Khat (Catha edulis) generates reactive oxygen species and promotes hepatic cell apoptosis via MAPK activation.

    PubMed

    Abid, Morad Dirhem Naji; Chen, Juan; Xiang, Min; Zhou, Jie; Chen, Xiaoping; Gong, Feili

    2013-08-01

    A number of studies have suggested an association between khat (Catha edulis) chewing and acute liver lesions or chronic liver disease. However, little is known about the effects of khat on hepatic cells. In the current study, we investigated the mechanism behind khat-induced apoptosis in the L02 human hepatic cell line. We used cell growth inhibition assay, flow cytometry and Hoechst 33258 staining to measure hepatocyte apoptosis induced by khat. Western blot analysis was used to detect the expression levels of caspase-8 and -9, as well as those of Bax and Bcl-2. We also measured reactive oxygen species production. The results indicated that khat induced significant hepatocyte apoptosis in L02 cells. We found that khat activated caspase-8 and -9, upregulated Bax protein expression and downregulated Bcl-2 expression levels, which resulted in the coordination of apoptotic signals. Khat-induced hepatocyte apoptosis is primarily regulated through the sustained activation of the c-Jun NH2-terminal kinase (JNK) pathway and only partially via the extracellular signal-regulated kinase (ERK) cascade. Furthermore, the khat-induced reactive oxygen species (ROS) production and the activation of the ROS scavenger, N-acetyl-L-cysteine (NAC), attenuated the khat-induced activation of JNK and ERK. Our results demonstrate that khat triggers the generation of intracellular ROS and sequentially induces the sustainable activation of JNK, which in turn results in a decrease in cell viability and an increase in cell apoptosis. PMID:23708648

  13. 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.

  14. 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

  15. 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

  16. 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. PMID:24392654

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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...

  2. 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

  3. 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

  4. 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

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

    PubMed

    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 Co(3+/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

  6. 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

  7. Involvement of Activated Oxygen in Nitrate-Induced Senescence of Pea Root Nodules.

    PubMed Central

    Escuredo, P. R.; Minchin, F. R.; Gogorcena, Y.; Iturbe-Ormaetxe, I.; Klucas, R. V.; Becana, M.

    1996-01-01

    The effect of short-term nitrate application (10 mM, 0-4 d) on nitrogenase (N2ase) activity, antioxidant defenses, and related parameters was investigated in pea (Pisum sativum L. cv Frilene) nodules. The response of nodules to nitrate comprised two stages. In the first stage (0-2 d), there were major decreases in N2ase activity and N2ase-linked respiration and concomitant increases in carbon cost of N2ase and oxygen diffusion resistance of nodules. There was no apparent oxidative damage, and the decline in N2ase activity was, to a certain extent, reversible. The second stage (>2 d) was typical of a senescent, essentially irreversible process. It was characterized by moderate increases in oxidized proteins and catalytic Fe and by major decreases in antioxidant enzymes and metabolites. The restriction in oxygen supply to bacteroids may explain the initial decline in N2ase activity. The decrease in antioxidant protection is not involved in this process and is not specifically caused by nitrate, since it also occurs with drought stress. However, comparison of nitrate- and drought-induced senescence shows an important difference: there is no lipid degradation or lipid peroxide accumulation with nitrate, indicating that lipid peroxidation is not necessarily involved in nodule senescence. PMID:12226252

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

    PubMed Central

    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

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  11. 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

  12. 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

  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. PMID:25817808

  14. 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

  15. 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

  16. 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

  17. In situ x-ray, electrochemical, and modeling investigation of the oxygen electrode activation.

    SciTech Connect

    Yildiz, B.; Chang, K.-C.; Meyers, D.; Carter, J. D.; You, H.

    2006-01-01

    Oxygen electrodes of solid oxide electrochemical cells have been shown to improve under strong cathodic and anodic polarization. Our study investigates the mechanism causing such improvement, using in situ x-ray and electrochemical characterization and electrochemical impedance modeling of the oxygen electrodes. Several porous and dense thin-film model electrodes of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSM) and La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LCM) on single crystal yttria-stabilized zirconia (YSZ) electrolytes have been analyzed in situ at the Advanced Photon Source (APS) using x-ray reflectivity and x-ray absorption near edge spectroscopy (XANES) at the Mn K-edge and La LII-edge. In situ x-ray reflectivity analysis show that no clear correlation between the polarization of the electrode and any further changes in the roughness of the LSM/YSZ interface exist. XANES measurements illustrate that the cathodic or anodic dc polarization at high temperature induces no detectable changes in Mn chemical state either in the bulk or at the surface of the LCM and LSM electrodes on YSZ, while the La chemical state changes reversibly at the electrode surface. This field-induced chemical change of La at the surface of electrodes is assumed to be a cause of the electrochemical activation through enhanced surface exchange of oxygen on the doped lanthanum manganite electrodes.

  18. 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

  19. 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

  20. 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.

  1. 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

  2. Activity-stability relationship in the surface electrochemistry of the oxygen evolution reaction.

    PubMed

    Chang, Seo Hyoung; Connell, Justin G; Danilovic, Nemanja; Subbaraman, Ram; Chang, Kee-Chul; Stamenkovic, Vojislav R; Markovic, Nenad M

    2014-01-01

    Understanding the functional links between the stability and reactivity of oxide materials during the oxygen evolution reaction (OER) is one key to enabling a vibrant hydrogen economy capable of competing with fossil fuel-based technologies. In this work, by focusing on the surface chemistry of monometallic Ru oxide in acidic and alkaline environments, we found that the kinetics of the OER are almost entirely controlled by the stability of the Ru surface atoms. The same activity-stability relationship was found for more complex, polycrystalline and single-crystalline SrRuO(3) thin films in alkaline solutions. We propose that the electrochemical transformation of either water (acidic solutions) or hydroxyl ions (alkaline solutions) to di-oxygen molecules takes place at defect sites that are inherently present on every electrode surface. During the OER, surface defects are also created by the corrosion of the Ru ions. The dissolution is triggered by the potential-dependent change in the valence state (n) of Ru: from stable but inactive Ru(4+) to unstable but active Ru(n>4+). We conclude that if the oxide is stable then it is completely inactive for the OER. A practical consequence is that the best materials for the OER should balance stability and activity in such a way that the dissolution rate of the oxide is neither too fast nor too slow. PMID:25490237

  3. 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.

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

    DOE PAGESBeta

    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

  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. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    NASA Astrophysics Data System (ADS)

    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

    2015-07-01

    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.

  11. 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. PMID:26952757

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. Oxygenator Is the Main Responsible for Leukocyte Activation in Experimental Model of Extracorporeal Circulation: A Cautionary Tale

    PubMed Central

    Rungatscher, Alessio; Tessari, Maddalena; Stranieri, Chiara; Solani, Erika; Linardi, Daniele; Milani, Elisabetta; Montresor, Alessio; Merigo, Flavia; Salvetti, Beatrice; Menon, Tiziano

    2015-01-01

    In order to assess mechanisms underlying inflammatory activation during extracorporeal circulation (ECC), several small animal models of ECC have been proposed recently. The majority of them are based on home-made, nonstandardized, and hardly reproducible oxygenators. The present study has generated fundamental information on the role of oxygenator of ECC in activating inflammatory signaling pathways on leukocytes, leading to systemic inflammatory response, and organ dysfunction. The present results suggest that experimental animal models of ECC used in translational research on inflammatory response should be based on standardized, reproducible oxygenators with clinical characteristics. PMID:26063972

  17. 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.

  18. Inhibition of histone deacetylase activity in reduced oxygen environment enhances the osteogenesis of mouse adipose-derived stromal cells.

    PubMed

    Xu, Yue; Hammerick, Kyle E; James, Aaron W; Carre, Antoine L; Leucht, Philipp; Giaccia, Amato J; Longaker, Michael T

    2009-12-01

    Recent studies suggest that oxygen tension has a great impact on the osteogenic differentiation capacity of mesenchymal cells derived from adipose tissue: reduced oxygen impedes osteogenesis. We have found that expansion of mouse adipose-derived stromal cells (mASCs) in reduced oxygen tension (10%) results in increased cell proliferation along with induction of histone deacetylase (HDAC) activity. In this study, we utilized two HDAC inhibitors (HDACi), sodium butyrate (NaB) and valproic acid (VPA), and studied their effects on mASCs expanded in various oxygen tensions (21%, 10%, and 1% O(2)). Significant growth inhibition was observed with NaB or VPA treatment in each oxygen tension. Osteogenesis was enhanced by treatment with NaB or VPA, particularly in reduced oxygen tensions (10% and 1% O(2)). Conversely, adipogenesis was decreased with treatments of NaB or VPA at all oxygen tensions. Finally, NaB- or VPA-treated, reduced oxygen tension-exposed (1% O(2)) ASCs were grafted into surgically created mouse tibial defects and resulted in significantly increased bone regeneration. In conclusion, HDACi significantly promote the osteogenic differentiation of mASCs exposed to reduced oxygen tension; HDACi may hold promise for future clinical applications of ASCs for skeletal regeneration. PMID:19505250

  19. Inhibition of Histone Deacetylase Activity in Reduced Oxygen Environment Enhances the Osteogenesis of Mouse Adipose-Derived Stromal Cells

    PubMed Central

    Xu, Yue; Hammerick, Kyle E.; James, Aaron W.; Carre, Antoine L.; Leucht, Philipp; Giaccia, Amato J.

    2009-01-01

    Recent studies suggest that oxygen tension has a great impact on the osteogenic differentiation capacity of mesenchymal cells derived from adipose tissue: reduced oxygen impedes osteogenesis. We have found that expansion of mouse adipose-derived stromal cells (mASCs) in reduced oxygen tension (10%) results in increased cell proliferation along with induction of histone deacetylase (HDAC) activity. In this study, we utilized two HDAC inhibitors (HDACi), sodium butyrate (NaB) and valproic acid (VPA), and studied their effects on mASCs expanded in various oxygen tensions (21%, 10%, and 1% O2). Significant growth inhibition was observed with NaB or VPA treatment in each oxygen tension. Osteogenesis was enhanced by treatment with NaB or VPA, particularly in reduced oxygen tensions (10% and 1% O2). Conversely, adipogenesis was decreased with treatments of NaB or VPA at all oxygen tensions. Finally, NaB- or VPA-treated, reduced oxygen tension–exposed (1% O2) ASCs were grafted into surgically created mouse tibial defects and resulted in significantly increased bone regeneration. In conclusion, HDACi significantly promote the osteogenic differentiation of mASCs exposed to reduced oxygen tension; HDACi may hold promise for future clinical applications of ASCs for skeletal regeneration. PMID:19505250

  20. 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. PMID:20605188

  1. 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…

  2. Non-hypoxic activation of the negative regulatory feedback loop of prolyl-hydroxylase oxygen sensors.

    PubMed

    Tug, Suzan; Delos Reyes, Buena; Fandrey, Joachim; Berchner-Pfannschmidt, Utta

    2009-07-10

    Hypoxia inducible factors (HIF) coordinate cellular responses towards hypoxia. HIFs are mainly regulated by a group of prolyl-hydroxylases (PHDs) that in the presence of oxygen, target the HIFalpha subunit for degradation. Herein, we studied the role of nitric oxide (NO) in regulating PHD activities under normoxic conditions. In the present study we show that different NO-donors initially inhibited endogenous PHD2 activity which led to accumulation of HIF-1alpha subsequently to enhance HIF-1 dependent increased PHD2 promoter activity. Consequently PHD2 abundance and activity were strongly induced which caused downregulation of HIF-1alpha. Interestingly, upregulation of endogenous PHD2 activity by NO was not found in cells that lack an intact pVHL dependent degradation pathway. Recovery of PHD activity required intact cells and was not observed in cell extracts or recombinant PHD2. In conclusion induction of endogenous PHD2 activity by NO is dependent on a feedback loop initiated despite normoxic conditions. PMID:19427832

  3. Oxygenation, EMG and position sense during computer mouse work. Impact of active versus passive pauses.

    PubMed

    Crenshaw, A G; Djupsjöbacka, M; Svedmark, A

    2006-05-01

    We investigated the effects of active versus passive pauses implemented during computer mouse work on muscle oxygenation and EMG of the forearm extensor carpi radialis muscle, and on wrist position sense. Fifteen healthy female subjects (age: 19-24 years) performed a 60-min mouse-operated computer task, divided into three 20 min periods, on two occasions separated by 3-6 days. On one occasion a passive pause (subjects resting) was implemented at the end of each 20-min period, and on another occasion an active pause (subjects performed a number of high intensity extensions of the forearm) was implemented. Also at the end of each 20-min period, test contractions were conducted and subjective ratings of fatigue and stress were obtained. Another parameter of interest was total haemoglobin calculated as the summation of oxy-and deoxy-haemoglobin, since it reflects blood volume changes. The most interesting findings were an overall increasing trend in total haemoglobin throughout the mouse work (P<0.001), and that this trend was greater for the active pause as compared to the passive pause (P<0.01). These data were accompanied by an overall increase in oxygen saturation (P<0.001), with a tendency, albeit not significant, toward a higher increase for the active pause (P=0.13). EMG amplitude and median frequency tended to decrease (P=0.08 and 0.05, respectively) during the mouse work but was not different between pause types. Borg ratings of forearm fatigue showed an overall increase during the activity (P<0.001), but the perceptions of stress did not change. Position sense did not change due to the mouse work for either pause type. While increasing trends were found for both pause types, the present study lends support to the hypothesis of an enhancement in oxygenation and blood volume for computer mouse work implemented with active pauses. However, a presumption of an association between this enhancement and attenuated fatigue during the mouse work was not supported

  4. Atomic Ordering Enhanced Electrocatalytic Activity of Nanoalloys for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Shan, Shiyao; Petkov, Valeri; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

    2013-10-01

    For oxygen reduction reaction (ORR) over alloy electrocatalysts, the understanding of how the atomic arrangement of the metal species in the nanocatalysts is responsible for the catalytic enhancement is challenging for achieving better design and tailoring of nanoalloy catalysts. This paper reports results of an investigation of the atomic structures and the electrocatalytic activities of ternary and binary nanoalloys, aiming at revealing a fundamental insight into the unique atomic-scale structure-electrocatalytic activity relationship. PtIrCo catalyst and its binary counterparts (PtCo and PtIr) are chosen as a model system for this study. The effect of thermochemical treatment temperature on the atomic-scale structure of the catalysts was examined as a useful probe to the structure-activity correlation. The structural characterization of the binary and ternary nanoalloy catalysts was performed by combining surface sensitive techniques such as XPS and 3D atomic ordering sensitive techniques such as high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis (HE-XRD/PDFs) and computer simulations. The results show that the thermal treatment temperature tunes the nanoalloy’s atomic and chemical ordering in a different way depending on the chemical composition, leading to differences in the nanoalloy’s mass and specific activities. A unique structural tunability of the atomic ordering in a platinum-iridium-cobalt nanoalloy has been revealed for enhancing greatly the electrocatalytic activity toward oxygen reduction reaction, which has significant implication for rational design and nanoengineering of advanced catalysts for electrochemical energy conversion and storage.

  5. Biomass Oxidation: Formyl C-H Bond Activation by the Surface Lattice Oxygen of Regenerative CuO Nanoleaves.

    PubMed

    Amaniampong, Prince N; Trinh, Quang Thang; Wang, Bo; Borgna, Armando; Yang, Yanhui; Mushrif, Samir H

    2015-07-27

    An integrated experimental and computational investigation reveals that surface lattice oxygen of copper oxide (CuO) nanoleaves activates the formyl C-H bond in glucose and incorporates itself into the glucose molecule to oxidize it to gluconic acid. The reduced CuO catalyst regains its structure, morphology, and activity upon reoxidation. The activity of lattice oxygen is shown to be superior to that of the chemisorbed oxygen on the metal surface and the hydrogen abstraction ability of the catalyst is correlated with the adsorption energy. Based on the present investigation, it is suggested that surface lattice oxygen is critical for the oxidation of glucose to gluconic acid, without further breaking down the glucose molecule into smaller fragments, because of C-C cleavage. Using CuO nanoleaves as catalyst, an excellent yield of gluconic acid is also obtained for the direct oxidation of cellobiose and polymeric cellulose, as biomass substrates. PMID:26119659

  6. 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

  7. Metal-Oxygen Bond Ionicity as an Efficient Descriptor for Doped NiOOH Photocatalytic Activity.

    PubMed

    Zaffran, Jeremie; Toroker, Maytal Caspary

    2016-06-01

    The computational design of solid catalysts has become a very "hot" field during the last decades, especially with the recent increase in computational tool performance. However, theoretical techniques are still very time demanding because they require the consideration of many adsorption configurations of the reaction intermediates on the surface. Herein, we propose to use the metal-oxygen (M-O) bond ionicity as a descriptor for the photocatalytic activity of one of the best catalysts for the oxygen evolution reaction (OER). Ionicity is a bulk property and thus carries the advantage of being easily obtainable from a simple Bader charge analysis by using density functional theory (DFT). We will show that this criterion can be used successfully to design efficient dopants for NiOOH material. This catalyst is known to exhibit interesting photoelectrochemical properties for OER if it is doped with specific transition metals. Finally, we demonstrate that other electronic properties that relate to bulk calculation, such as oxidation states and density of states, are not alone sufficient to explain the photocatalytic activity of the material. Thus, M-O bond ionicity attracts significant interest compared with other bulk observables obtained by using DFT computations. PMID:26945687

  8. Ni- and Mn-Promoted Mesoporous Co3O4: A Stable Bifunctional Catalyst with Surface-Structure-Dependent Activity for Oxygen Reduction Reaction and Oxygen Evolution Reaction.

    PubMed

    Song, Wenqiao; Ren, Zheng; Chen, Sheng-Yu; Meng, Yongtao; Biswas, Sourav; Nandi, Partha; Elsen, Heather A; Gao, Pu-Xian; Suib, Steven L

    2016-08-17

    Efficient bifunctional catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable due to their wide applications in fuel cells and rechargeable metal air batteries. However, the development of nonprecious metal catalysts with comparable activities to noble metals is still challenging. Here we report a one-step wet-chemical synthesis of Ni-/Mn-promoted mesoporous cobalt oxides through an inverse micelle process. Various characterization techniques including powder X-ray diffraction (PXRD), N2 sorption, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) confirm the successful incorporation of Ni and Mn leading to the formation of Co-Ni(Mn)-O solid solutions with retained mesoporosity. Among these catalysts, cobalt oxide with 5% Ni doping demonstrates promising activities for both ORR and OER, with an overpotential of 399 mV for ORR (at -3 mA/cm(2)) and 381 mV (at 10 mA/cm(2)) for OER. Furthermore, it shows better durability than precious metals featuring little activity decay throughout 24 h continuous operation. Analyses of cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), Raman, and O2-temperature-programmed desorption (O2-TPD) reveal that redox activity of Co(3+) to Co(4+) is crucial for OER performance, while the population of surface oxygen vacancies and surface area determine ORR activities. The comprehensive investigation of the intrinsic active sites for ORR and OER by correlating different physicochemical properties to the electrochemical activities is believed to provide important insight toward the rational design of high-performance electrocatalysts for ORR and OER reactions. PMID:27458646

  9. NQO1-induced activation of AMPK contributes to cancer cell death by oxygen-glucose deprivation

    PubMed Central

    Lee, Hyemi; Oh, Eun-Taex; Choi, Bo-Hwa; Park, Moon-Taek; Lee, Ja-Kyeong; Lee, Jae-Seon; Park, Heon Joo

    2015-01-01

    Oxygen and glucose deprivation (OGD) due to insufficient blood circulation can decrease cancer cell survival and proliferation in solid tumors. OGD increases the intracellular [AMP]/[ATP] ratio, thereby activating the AMPK. In this study, we have investigated the involvement of NQO1 in OGD-mediated AMPK activation and cancer cell death. We found that OGD activates AMPK in an NQO1-dependent manner, suppressing the mTOR/S6K/4E-BP1 pathway, which is known to control cell survival. Thus, the depletion of NQO1 prevents AMPK-induced cancer cell death in OGD. When we blocked OGD-induced Ca2+/CaMKII signaling, the NQO1-induced activation of AMPK was attenuated. In addition, when we blocked the RyR signaling, the accumulation of intracellular Ca2+ and subsequent activation of CaMKII/AMPK signaling was decreased in NQO1-expressing cells under OGD. Finally, siRNA-mediated knockdown of CD38 abrogated the OGD-induced activation of Ca2+/CaMKII/AMPK signaling. Taken together, we conclude that NQO1 plays a key role in the AMPK-induced cancer cell death in OGD through the CD38/cADPR/RyR/Ca2+/CaMKII signaling pathway. PMID:25586669

  10. 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

  11. 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

  12. 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).

  13. 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. PMID:25686380

  14. Porous Dendritic Platinum Nanotubes with Extremely High Activity and Stability for Oxygen Reduction Reaction

    PubMed Central

    Zhang, Gaixia; Sun, Shuhui; Cai, Mei; Zhang, Yong; Li, Ruying; Sun, Xueliang

    2013-01-01

    Controlling the morphology of Pt nanostructures can provide opportunities to greatly increase their activity and stability. Porous dendritic Pt nanotubes were successfully synthesized by a facile, cost-effective aqueous solution method at room temperature in large scale. These unique structures are porous, hollow, hierarchical, and single crystalline, which not only gives them a large surface area with high catalyst utilization, but also improves mass transport and gas diffusion. These novel Pt structures exhibited significantly improved catalytic activity (4.4 fold) for oxygen reduction reaction (ORR) and greatly enhanced durability (6.1 fold) over that of the state-of-the-art commercial Pt/C catalyst. This work provides a promising approach to the design of highly efficient next-generation electrocatalysts. PMID:23524665

  15. 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. PMID:26704530

  16. 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. PMID:27499058

  17. 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

  18. Molecular mimicry of substrate oxygen atoms by water molecules in the beta-amylase active site.

    PubMed

    Pujadas, G; Palau, J

    2001-08-01

    Soybean beta-amylase (EC 3.2.1.2) has been crystallized both free and complexed with a variety of ligands. Four water molecules in the free-enzyme catalytic cleft form a multihydrogen-bond network with eight strategic residues involved in enzyme-ligand hydrogen bonds. We show here that the positions of these four water molecules are coincident with the positions of four potential oxygen atoms of the ligands within the complex. Some of these waters are displaced from the active site when the ligands bind to the enzyme. How many are displaced depends on the shape of the ligand. This means that when one of the four positions is not occupied by a ligand oxygen atom, the corresponding water remains. We studied the functional/structural role of these four waters and conclude that their presence means that the conformation of the eight side chains is fixed in all situations (free or complexed enzyme) and preserved from unwanted or forbidden conformational changes that could hamper the catalytic mechanism. The water structure at the active pocket of beta-amylase is therefore essential for providing the ligand recognition process with plasticity. It does not affect the protein active-site geometry and preserves the overall hydrogen-bonding network, irrespective of which ligand is bound to the enzyme. We also investigated whether other enzymes showed a similar role for water. Finally, we discuss the potential use of these results for predicting whether water molecules can mimic ligand atoms in the active center. PMID:11468361

  19. Oxidative DNA adducts after Cu(2+)-mediated activation of dihydroxy PCBs: role of reactive oxygen species.

    PubMed

    Spencer, Wendy A; Lehmler, Hans-Joachim; Robertson, Larry W; Gupta, Ramesh C

    2009-05-15

    Polychlorinated biphenyls (PCBs) are toxic industrial chemicals, complete carcinogens, and efficacious tumor promoters. However, the mechanism(s) of PCB-mediated carcinogenicity remains largely undefined. One likely pathway by which these agents may play a role in carcinogenesis is the generation of oxidative DNA damage by redox cycling of dihydroxylated PCB metabolites. We have now employed a new (32)P-postlabeling system to examine novel oxidative DNA lesions induced by Cu(2+)-mediated activation of PCB metabolites. (32)P postlabeling of DNA incubated with various PCB metabolites resulted in over a dozen novel polar oxidative DNA adducts that were chromatographically similar for all active agents. The most potent metabolites tested were the hydroquinones (hydroxyl groups arranged para to each other), yielding polar oxidative adduct levels ranging from 55 to 142 adducts/10(6) nucleotides. PCB catechols, or ortho-dihydroxy metabolites, were up to 40% less active than their corresponding hydroquinone congeners, whereas monohydroxylated and quinone metabolites did not produce detectable oxidative damage over that of vehicle. With the exception of 2,4,5-Cl-2',5'-dihydroxybiphenyl, this oxidative DNA damage seemed to be inversely related to chlorine content: no chlorine approximately mono->di->trichlorinated metabolites. Importantly, copper, but not iron, was essential for activation of the PCB metabolites to these polar oxidative DNA adducts, because in its absence or in the presence of the Cu(+)-specific scavenger bathocuproine, no adducts were detected. Intervention studies with known reactive oxygen species (ROS) modifiers suggested that H(2)O(2), singlet oxygen, hydroxyl radical, and superoxide may also be involved in this PCB-mediated oxidative DNA damage. These data indicate a mechanistic role for several ROS, in addition to copper, in PCB-induced DNA damage and provide further support for oxidative DNA damage in PCB-mediated carcinogenesis. PMID:19233261

  20. Intensity of daily physical activity is associated with central hemodynamic and leg muscle oxygen availability in COPD.

    PubMed

    Louvaris, Zafeiris; Kortianou, Eleni A; Spetsioti, Stavroula; Vasilopoulou, Maroula; Nasis, Ioannis; Asimakos, Andreas; Zakynthinos, Spyros; Vogiatzis, Ioannis

    2013-09-01

    In chronic obstructive pulmonary disease (COPD), daily physical activity is reported to be adversely associated with the magnitude of exercise-induced dynamic hyperinflation and peripheral muscle weakness. There is limited evidence whether central hemodynamic, oxygen transport, and peripheral muscle oxygenation capacities also contribute to reduced daily physical activity. Nineteen patients with COPD (FEV1, 48 ± 14% predicted) underwent a treadmill walking test at a speed corresponding to the individual patient's mean walking intensity, captured by a triaxial accelerometer during a preceding 7-day period. During the indoor treadmill test, the individual patient mean walking intensity (range, 1.5 to 2.3 m/s2) was significantly correlated with changes from baseline in cardiac output recorded by impedance cardiography (range, 1.2 to 4.2 L/min; r = 0.73), systemic vascular conductance (range, 7.9 to 33.7 ml·min(-1)·mmHg(-1); r = 0.77), systemic oxygen delivery estimated from cardiac output and arterial pulse-oxymetry saturation (range, 0.15 to 0.99 L/min; r = 0.70), arterio-venous oxygen content difference calculated from oxygen uptake and cardiac output (range, 3.7 to 11.8 mlO2/100 ml; r = -0.73), and quadriceps muscle fractional oxygen saturation assessed by near-infrared spectrometry (range, -6 to 23%; r = 0.77). In addition, mean walking intensity significantly correlated with the quadriceps muscle force adjusted for body weight (range, 0.28 to 0.60; r = 0.74) and the ratio of minute ventilation over maximal voluntary ventilation (range, 38 to 89%, r = -0.58). In COPD, in addition to ventilatory limitations and peripheral muscle weakness, intensity of daily physical activity is associated with both central hemodynamic and peripheral muscle oxygenation capacities regulating the adequacy of matching peripheral muscle oxygen availability by systemic oxygen transport. PMID:23845982

  1. Metal Ion Adsorption by Activated Carbons Made from Pecan Shells: Effect of Oxygen Level During Activation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Agricultural by-products represent a considerable quantity of harvested commodity crops. The use of by-products as precursors for the production of widely used adsorbents, such as activated carbons, may impart a value-added component of the overall biomass harvested. Our objective in this presenta...

  2. 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

  3. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGESBeta

    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

  4. Mitochondria are required for antigen-specific T cell activation through reactive oxygen species signaling

    PubMed Central

    Sena, Laura A.; Li, Sha; Jairaman, Amit; Prakriya, Murali; Ezponda, Teresa; Hildeman, David A.; Wang, Chyung-Ru; Schumacker, Paul T.; Licht, Jonathan D.; Perlman, Harris; Bryce, Paul J.; Chandel, Navdeep S.

    2013-01-01

    SUMMARY It is widely appreciated that T cells increase glycolytic flux during activation, however the role of mitochondrial flux is unclear. Here we have shown that mitochondrial metabolism, in the absence of glucose metabolism, was sufficient to support interleukin-2 (IL-2) induction. Furthermore, we used mice with reduced mitochondrial reactive oxygen species (mROS) production in T cells (T-Uqcrfs−/− mice) to show that mitochondria are required for T cell activation to produce mROS for activation of nuclear factor of activated T cells (NFAT) and subsequent IL-2 induction. These mice could not induce antigen-specific expansion of T cells in vivo, however Uqcrfs1−/− T cells retained the ability to proliferate in vivo under lymphopenic conditions. This suggests that Uqcrfs1−/− T cells were not lacking bioenergetically, but rather lacked specific ROS-dependent signaling events needed for antigen-specific expansion. Thus, mitochondrial metabolism is a critical component of T cell activation through production of complex III ROS. PMID:23415911

  5. 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.

  6. A Clark-type oxygen chip for in situ estimation of the respiratory activity of adhering cells.

    PubMed

    Wu, Ching-Chou; Luk, Hsiang-Ning; Lin, Yen-Ting Tsai; Yuan, Chia-Yin

    2010-04-15

    A Clark-type oxygen chip consisting of a polydimethylsiloxane (PDMS) reservoir containing an amino group-modified PDMS oxygen-permeable membrane (OPM) and a glass substrate containing a three-electrode detector has been constructed by using microfabrication techniques, and it is utilized for in situ measurement of the respiration activity of adhering cells. Use of the alginate sol electrolyte and the electroplating Ag/AgCl pseudo-reference electrode can effectively diminish the crosstalk between the electrochemical electrodes and supply a stable potential for the detection of dissolved oxygen, respectively. The Clark-type oxygen chips possess only 1.00% residual current, response time of 13.4s and good linearity with a correlation coefficient of 0.9933. The modification of amino groups for the OPM obviously facilitates the adhesion of HeLa cells onto the PDMS OPM surface and allows the cells to spread after 2h of incubation. The oxygen consumption of the cells in the cell-adhesion process increases with the adhesion time, and the increment of cellular oxygen consumption per minute reaches a maximum after 30 min of incubation. Moreover, the change in the respiration activity of adhering HeLa cells stimulated by the high concentration of glucose or propofol anaesthetic can be monitored in real time with the Clark-type oxygen chip. PMID:20188913

  7. 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. PMID:26232709

  8. Human autonomic activity and its response to acute oxygen supplement after high altitude acclimatization.

    PubMed

    Bao, Xuping; Kennedy, Brian P; Hopkins, Susan R; Bogaard, Harm J; Wagner, Peter D; Ziegler, Michael G

    2002-11-29

    It is well established that after acclimatization at high altitude, many sympathetic pathways are hyperactive yet heart rate (HR) remains unchanged. In this study, we attempted to determine if this unchanged heart rate is due to compensatory mechanisms such as changes in parasympathetic activity or levels of receptors for autonomic neurotransmitters. We also examined the role played by hypoxia in these autonomic adaptations to high altitude. Three experiments were carried out on five healthy lowlanders both at sea level (SL) and after 2 weeks of acclimatization at 3800 m (Post-Ac) with: (a) placebo (control); (b) acute beta-adrenergic receptor blockade by propranolol (PRO), or (c) acute parasympathetic receptor blockade by glycopyrrolate (GLY). Compared with SL control values, post-Ac venous norepinephrine (NE) and dopamine increased by 96% (p < 0.001) and 55% (p < 0.05), but epinephrine and HR did not change. PRO resulted in a smaller decrease in HR (bpm) Post-Ac than at SL (15 +/- 6 vs. 21 +/- 6, p < 0.05), while GLY caused a greater increase in HR Post-Ac than at SL (59 +/- 8 vs. 45 +/- 6, p < 0.05). Breathing oxygen at SL concentration while at altitude did not decrease NE, or alter the effect of PRO on HR, but reduced the chronotropic effect of GLY by 14% (p < 0.05). These results suggest that after acclimatization to altitude, increased parasympathetic neurotransmitter release and decreased beta-adenoreceptor activity account for the unchanged HR despite enhanced sympathetic activity. Acute oxygen replacement rapidly counteracted the parasympathetic, but not sympathetic hyperactivity that occurs at high altitude. PMID:12492136

  9. 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

  10. Asymmetric Enzymatic Synthesis of Allylic Amines: A Sigmatropic Rearrangement Strategy.

    PubMed

    Prier, Christopher K; Hyster, Todd K; Farwell, Christopher C; Huang, Audrey; Arnold, Frances H

    2016-04-01

    Sigmatropic rearrangements, while rare in biology, offer opportunities for the efficient and selective synthesis of complex chemical motifs. A "P411" serine-ligated variant of cytochrome P450BM3 has been engineered to initiate a sulfimidation/[2,3]-sigmatropic rearrangement sequence in whole E. coli cells, a non-natural function for any enzyme, providing access to enantioenriched, protected allylic amines. Five mutations in the enzyme substantially enhance its activity toward this new function, demonstrating the evolvability of the catalyst toward challenging nitrene transfer reactions. The evolved catalyst additionally performs the highly enantioselective imidation of non-allylic sulfides. PMID:26970325