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Sample records for aerobic oxidation reactions

  1. Highly diastereoselective and regioselective copper-catalyzed nitrosoformate dearomatization reaction under aerobic-oxidation conditions.

    PubMed

    Yang, Weibo; Huang, Long; Yu, Yang; Pflästerer, Daniel; Rominger, Frank; Hashmi, A Stephen K

    2014-04-01

    An unprecedented copper-catalyzed acylnitroso dearomatization reaction, which expands the traditional acylnitroso ene reaction and acylnitroso Diels-Alder reaction to a new type of transformation, has been developed under aerobic oxidation. Intermolecular and intra-/intermolecular reaction modes demonstrate an entirely different N- or O-acylnitroso selectivity. Hence, we can utilize this reaction as a highly diastereoselective access to a series of new pyrroloindoline derivatives, which are important structural motifs for natural-product synthesis.

  2. Reaction-driven surface restructuring and selectivity control in allylic alcohol catalytic aerobic oxidation over Pd.

    PubMed

    Lee, Adam F; Ellis, Christine V; Naughton, James N; Newton, Mark A; Parlett, Christopher M A; Wilson, Karen

    2011-04-20

    Synchronous, time-resolved DRIFTS/MS/XAS cycling studies of the vapor-phase selective aerobic oxidation of crotyl alcohol over nanoparticulate Pd have revealed surface oxide as the desired catalytically active phase, with dynamic, reaction-induced Pd redox processes controlling selective versus combustion pathways.

  3. Catalyst-Controlled Regioselectivity in the Synthesis of Branched Conjugated Dienes via Aerobic Oxidative Heck Reactions

    PubMed Central

    Zheng, Changwu; Wang, Dian; Stahl, Shannon S.

    2012-01-01

    Pd-catalyzed aerobic oxidative coupling of vinylboronic acids and electronically unbiased alkyl olefins provides regioselective access to 1,3-disubstituted conjugated dienes. Catalyst-controlled regioselectivity is achieved by using 2,9-dimethylphenanthroline as a ligand. The observed regioselectivity is opposite to that observed from a traditional (non-oxidative) Heck reaction between a vinyl bromide and an alkene. DFT computational studies reveal that steric effects of the 2,9-dimethylphenanthroline ligand promote C–C bond-formation at the internal position of the alkene. PMID:22998540

  4. Aerobic oxidation of methanol to formic acid on Au20-: a theoretical study on the reaction mechanism.

    PubMed

    Bobuatong, Karan; Karanjit, Sangita; Fukuda, Ryoichi; Ehara, Masahiro; Sakurai, Hidehiro

    2012-03-07

    The aerobic oxidation of methanol to formic acid catalyzed by Au(20)(-) has been investigated quantum chemically using density functional theory with the M06 functional. Possible reaction pathways are examined taking account of full structure relaxation of the Au(20)(-) cluster. The proposed reaction mechanism consists of three elementary steps: (1) formation of formaldehyde from methoxy species activated by a superoxo-like anion on the gold cluster; (2) nucleophilic addition by the hydroxyl group of a hydroperoxyl-like complex to formaldehyde resulting in a hemiacetal intermediate; and (3) formation of formic acid by hydrogen transfer from the hemiacetal intermediate to atomic oxygen attached to the gold cluster. A comparison of the computed energetics of various elementary steps indicates that C-H bond dissociation of the methoxy species leading to formation of formaldehyde is the rate-determining step. A possible reaction pathway involving single-step hydrogen abstraction, a concerted mechanism, is also discussed. The stabilities of reactants, intermediates and transition state structures are governed by the coordination number of the gold atoms, charge distribution, cooperative effect and structural distortion, which are the key parameters for understanding the relationship between the structure of the gold cluster and catalytic activity in the aerobic oxidation of alcohols.

  5. Metallic Sn spheres and SnO2@C core-shells by anaerobic and aerobic catalytic ethanol and CO oxidation reactions over SnO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Won Joo; Lee, Sung Woo; Sohn, Youngku

    2015-08-01

    SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications.

  6. Metallic Sn spheres and SnO2@C core-shells by anaerobic and aerobic catalytic ethanol and CO oxidation reactions over SnO2 nanoparticles.

    PubMed

    Kim, Won Joo; Lee, Sung Woo; Sohn, Youngku

    2015-08-24

    SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications.

  7. Metallic Sn spheres and SnO2@C core-shells by anaerobic and aerobic catalytic ethanol and CO oxidation reactions over SnO2 nanoparticles

    PubMed Central

    Kim, Won Joo; Lee, Sung Woo; Sohn, Youngku

    2015-01-01

    SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications. PMID:26300041

  8. Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

    USGS Publications Warehouse

    Amos, R.T.; Bekins, B.A.; Delin, G.N.; Cozzarelli, I.M.; Blowes, D.W.; Kirshtein, J.D.

    2011-01-01

    High resolution direct-push profiling over short vertical distances was used to investigate CH4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH4 and CO2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in ??13CCH4 from an average of - 57.6??? (?? 1.7???) in the methanogenic zone to - 39.6??? (?? 8.7???) at 105 m downgradient, strongly suggest CH4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O2 across the water table is leading to aerobic degradation of CH4 at this interface. Dissolved N2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O2 through aerobic degradation of CH4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O2 transport mechanisms. ?? 2011 Elsevier B.V. All rights reserved.

  9. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DTIC Science & Technology

    2014-10-27

    distribution is unlimited. Surface Structure of Aerobically Oxidized Diamond Nanocrystals The views, opinions and/or findings contained in this report...2211 diamond nanocrystals, REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR/MONITOR’S ACRONYM(S) ARO 8. PERFORMING...Room 254, Mail Code 8725 New York, NY 10027 -7922 ABSTRACT Surface Structure of Aerobically Oxidized Diamond Nanocrystals Report Title We investigate

  10. Aerobic Alcohol Oxidation Using a Copper(I)/TEMPO Catalyst System: A Green, Catalytic Oxidation Reaction for the Undergraduate Organic Chemistry Laboratory

    ERIC Educational Resources Information Center

    Hill, Nicholas J.; Hoover, Jessica M.; Stahl, Shannon S.

    2013-01-01

    Modern undergraduate organic chemistry textbooks provide detailed discussion of stoichiometric Cr- and Mn-based reagents for the oxidation of alcohols, yet the use of such oxidants in instructional and research laboratories, as well as industrial chemistry, is increasingly avoided. This work describes a laboratory exercise that uses ambient air as…

  11. Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon.

    PubMed

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

    Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

  12. Click on silica: systematic immobilization of Co(II) Schiff bases to the mesoporous silica via click reaction and their catalytic activity for aerobic oxidation of alcohols.

    PubMed

    Rana, Bharat S; Jain, Suman L; Singh, Bhawan; Bhaumik, Asim; Sain, Bir; Sinha, Anil K

    2010-09-07

    The systematic immobilization of cobalt(II) Schiff base complexes on SBA-15 mesoporous silica via copper catalyzed [3 + 2] azide-alkyne cycloaddition (CuAAC) "click reaction" involving either step-wise synthesis of silica-bound Schiff base ligand followed by its subsequent complexation with cobalt ions, or by the direct immobilization of preformed Co(II) Schiff base complex to the silica support is described. The catalytic activity of the prepared complexes was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were recycled for several runs without loss in catalytic activity and no leaching was observed during this course.

  13. Surface Structure of Aerobically Oxidized Diamond Nanocrystals.

    PubMed

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E; Chen, Edward H; Nordlund, Dennis; Diaz, Rosa E; Gaathon, Ophir; Englund, Dirk; Owen, Jonathan S

    2014-11-20

    We investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5-50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core-hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. The importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications is discussed.

  14. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    PubMed Central

    2015-01-01

    We investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. The importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications is discussed. PMID:25436035

  15. Co(salophen)-Catalyzed Aerobic Oxidation of p-Hydroquinone: Mechanism and Implications for Aerobic Oxidation Catalysis

    SciTech Connect

    Anson, Colin W.; Ghosh, Soumya; Hammes-Schiffer, Sharon; Stahl, Shannon S.

    2016-03-30

    Macrocyclic metal complexes and p-benzoquinones are commonly used as co-catalytic redox mediators in aerobic oxidation reactions. In an effort to gain insight into the mechanism and energetic efficiency of these reactions, we investigated Co(salophen)-catalyzed aerobic oxidation of p-hydroquinone. Kinetic and spectroscopic data suggest that the catalyst resting-state consists of an equilibrium between a CoII(salophen) complex, a CoIII-superoxide adduct, and a hydrogen-bonded adduct between the hydroquinone and the CoIII–O2 species. The kinetic data, together with density functional theory data, suggest that the turnover-limiting step features proton-coupled electron transfer from a semi-hydroquinone species and a CoIII-hydroperoxide intermediate. Additional experimental and computational data suggest that a coordinated H2O2 intermediate oxidizes a second equivalent of hydroquinone. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. The NSF provided partial support for the EPR instrumentation (NSF CHE-0741901).

  16. Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

    PubMed

    Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

    2012-11-16

    An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

  17. Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-02-13

    Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols.

  18. A mild oxidative aryl radical addition into alkenes by aerobic oxidation of arylhydrazines.

    PubMed

    Taniguchi, Tsuyoshi; Zaimoku, Hisaaki; Ishibashi, Hiroyuki

    2011-04-04

    A mild and practical oxyarylation of alkenes by oxidative radical addition has been developed by using aerobic oxidation of hydrazine compounds. The use of a catalytic amount of potassium ferrocyanide trihydrate (K(4)[Fe(CN)(6)]⋅3H(2)O) and water accelerated this radical reaction to give peroxides or alcohols from simple alkenes in good yields. The environmentally friendly and economical radical reactions were achieved at room temperature in the presence of iron catalyst, oxygen gas, and water. A method involving aniline as a radical precursor is also described.

  19. Development of Safe and Scalable Continuous-Flow Methods for Palladium-Catalyzed Aerobic Oxidation Reactions†

    PubMed Central

    Ye, Xuan; Diao, Tianning

    2010-01-01

    Summary The synthetic scope and utility of Pd-catalyzed aerobic oxidation reactions has advanced significantly over the past decade, and these reactions have potential to address important green-chemistry challenges in the pharmaceutical industry. This potential has been unrealized, however, because safety concerns and process constraints hinder large-scale applications of this chemistry. These limitations are addressed by the development of a continuous-flow tube reactor, which has been demonstrated on several scales in the aerobic oxidation of alcohols. Use of a dilute oxygen gas source (8% O2 in N2) ensures that the oxygen/organic mixture never enters the explosive regime, and efficient gas-liquid mixing in the reactor minimizes decomposition of the homogeneous catalyst into inactive Pd metal. These results provide the basis for large-scale implementation of palladium-catalyzed (and other) aerobic oxidation reactions for pharmaceutical synthesis. PMID:20694169

  20. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    SciTech Connect

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; Chen, Edward H.; Nordlund, Dennis; Diaz, Rosa E.; Gaaton, Ophir; Englund, Dirk; Owen, Jonathan S.

    2014-10-27

    Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.

  1. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DOE PAGES

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; ...

    2014-10-27

    Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed.more » Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.« less

  2. Growth of nitrite-oxidizing bacteria by aerobic hydrogen oxidation.

    PubMed

    Koch, Hanna; Galushko, Alexander; Albertsen, Mads; Schintlmeister, Arno; Gruber-Dorninger, Christiane; Lücker, Sebastian; Pelletier, Eric; Le Paslier, Denis; Spieck, Eva; Richter, Andreas; Nielsen, Per H; Wagner, Michael; Daims, Holger

    2014-08-29

    The bacterial oxidation of nitrite to nitrate is a key process of the biogeochemical nitrogen cycle. Nitrite-oxidizing bacteria are considered a highly specialized functional group, which depends on the supply of nitrite from other microorganisms and whose distribution strictly correlates with nitrification in the environment and in wastewater treatment plants. On the basis of genomics, physiological experiments, and single-cell analyses, we show that Nitrospira moscoviensis, which represents a widely distributed lineage of nitrite-oxidizing bacteria, has the genetic inventory to utilize hydrogen (H2) as an alternative energy source for aerobic respiration and grows on H2 without nitrite. CO2 fixation occurred with H2 as the sole electron donor. Our results demonstrate a chemolithoautotrophic lifestyle of nitrite-oxidizing bacteria outside the nitrogen cycle, suggesting greater ecological flexibility than previously assumed.

  3. Bioinspired Aerobic Oxidation of Secondary Amines and Nitrogen Heterocycles with a Bifunctional Quinone Catalyst

    PubMed Central

    Wendlandt, Alison E.; Stahl, Shannon S.

    2014-01-01

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here, we report a novel bioinspired quinone catalyst system, consisting of 1,10-phenanthroline-5,6-dione/ZnI2, that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts. PMID:24328193

  4. Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

    PubMed Central

    Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

    2015-01-01

    Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

  5. Challenges in polyoxometalate-mediated aerobic oxidation catalysis: catalyst development meets reactor design.

    PubMed

    Lechner, Manuel; Güttel, Robert; Streb, Carsten

    2016-11-14

    Selective catalytic oxidation is one of the most widely used chemical processes. Ideally, highly active and selective catalysts are used in combination with molecular oxygen as oxidant, leading to clean, environmentally friendly process conditions. For homogeneous oxidation catalysis, molecular metal oxide anions, so-called polyoxometalates (POMs) are ideal prototypes which combine high reactivity and stability with chemical tunability on the molecular level. Typically, POM-mediated aerobic oxidations are biphasic, using gaseous O2 and liquid reaction mixtures. Therefore, the overall efficiency of the reaction is not only dependent on the chemical components, but requires chemical engineering insight to design reactors with optimized productivity. This Perspective shows that POM-mediated aerobic liquid-phase oxidations are ideal reactions to be carried out in microstructured flow reactors as they enable facile mass and energy transfer, provide large gas-liquid interfaces and can be easily upscaled. Recent advances in POM-mediated aerobic catalytic oxidations are therefore summarized with a focus on technological importance and mechanistic insight. The principles of reactor design are discussed from a chemical engineering point of view with a focus on homogeneous oxidation catalysis using O2 in microfluidic systems. Further, current limitations to catalytic activity are identified and future directions based on combined chemistry and chemical engineering approaches are discussed to show that this approach could lead to sustainable production methods in industrial chemistry based on alternative energy sources and chemical feedstocks.

  6. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    PubMed Central

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  7. Reactions Catalysed by a Binuclear Copper Complex: Relay Aerobic Oxidation of N-Aryl Tetrahydroisoquinolines to Dihydroisoquinolones with a Vitamin B1 Analogue.

    PubMed

    Liu, Yuxia; Wang, Chao; Xue, Dong; Xiao, Miao; Liu, Jiao; Li, Chaoqun; Xiao, Jianliang

    2017-03-02

    N-Aryl tetrahydroisoquinolines were oxidised to dihydroisoquinolones through the relay catalysis of a binuclear paddle-wheel copper complex and a vitamin B1 analogue with oxygen as oxidant. Mechanistic studies revealed that the copper catalyst oxidises amines to the corresponding iminium salts, which are then oxygenated to lactam products by catalysis of the vitamin B1 analogue.

  8. Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

    NASA Technical Reports Server (NTRS)

    Caldwell, D.

    1985-01-01

    Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

  9. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    PubMed Central

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-01-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal. PMID:27687877

  10. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions.

  11. Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

    PubMed

    Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

    2014-02-15

    The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes.

  12. The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

    SciTech Connect

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng

    2014-06-01

    A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. The reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.

  13. Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

    SciTech Connect

    Deng, Yi; Zhang, Guanghui; Qi, Xiaotian; Liu, Chao; Miller, Jeffrey T.; Kropf, A. Jeremy; Bunel, Emilio E.; Lan, Yu; Lei, Aiwen

    2015-01-01

    In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(I) to Cu(II) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI–TMEDA involves a side-on transition state, while oxidation of CuCl–TMEDA involves an end-on transition state which has a lower activation energy.

  14. Respirometric characterization of aerobic sulfide, thiosulfate and elemental sulfur oxidation by S-oxidizing biomass.

    PubMed

    Mora, Mabel; López, Luis R; Lafuente, Javier; Pérez, Julio; Kleerebezem, Robbert; van Loosdrecht, Mark C M; Gamisans, Xavier; Gabriel, David

    2016-02-01

    Respirometry was used to reveal the mechanisms involved in aerobic biological sulfide oxidation and to characterize the kinetics and stoichiometry of a microbial culture obtained from a desulfurizing biotrickling filter. Physical-chemical processes such as stripping and chemical oxidation of hydrogen sulfide were characterized since they contributed significantly to the conversions observed in respirometric tests. Mass transfer coefficient for hydrogen sulfide and the kinetic parameters for chemical oxidation of sulfide with oxygen were estimated. The stoichiometry of the process was determined and the different steps in the sulfide oxidation process were identified. The conversion scheme proposed includes intermediate production of elemental sulfur and thiosulfate and the subsequent oxidation of both compounds to sulfate. A kinetic model describing each of the reactions observed during sulfide oxidation was calibrated and validated. The product selectivity was found to be independent of the dissolved oxygen to hydrogen sulfide concentration ratio in the medium at sulfide concentrations ranging from 3 to 30 mg S L(-1). Sulfide was preferentially consumed (SOURmax = 49.2 mg DO g(-1) VSS min(-1)) and oxidized to elemental sulfur at dissolved oxygen concentrations above 0.8 mg DO L(-1). Substrate inhibition of sulfide oxidation was observed (K(i,S(2-))= 42.4 mg S L(-1)). Intracellular sulfur accumulation also affected negatively the sulfide oxidation rate. The maximum fraction of elemental sulfur accumulated inside cells was estimated (25.6% w/w) and a shrinking particle equation was included in the kinetic model to describe elemental sulfur oxidation. The microbial diversity obtained through pyrosequencing analysis revealed that Thiothrix sp. was the main species present in the culture (>95%).

  15. Palladium nanoparticles in ionic liquids: reusable catalysts for aerobic oxidation of alcohols

    NASA Astrophysics Data System (ADS)

    Mondal, Arijit; Das, Amit; Adhikary, Bibhutosh; Mukherjee, Deb Kumar

    2014-04-01

    The search for more efficient catalytic systems that might combine the advantages of both homogenous (catalyst modulation) and heterogenous catalysis (catalyst recycling) is still the challenge of modern chemistry. With the advent of nanochemistry, it has been possible to prepare soluble analogues of heterogenous catalysts. These nanoparticles are generally stabilized against aggregation into larger less active particles by electrostatic or steric protection. In the present case, we demonstrate the use of room temperature ionic liquids (ILs) as effective agents of dispersion of palladium nanoparticles (prepared from palladium chloride with 5 ± 0.5 nm size distribution) that are recyclable catalysts for aerobic oxidation of alcohols under mild conditions. The particles suspended in ILs show no metal agglomeration or loss of catalytic activity even on prolonged use. An attempt has been made to elucidate the reaction mechanism of aerobic alcohol oxidation using a soluble palladium catalyst.

  16. Copper(II)-Catalyzed Benzylic C(sp(3))-H Aerobic Oxidation of (Hetero)Aryl Acetimidates: Synthesis of Aryl-α-ketoesters.

    PubMed

    Kumar, Yogesh; Jaiswal, Yogesh; Kumar, Amit

    2016-12-16

    A straightforward method is developed in this paper for the synthesis of α-ketoesters through copper-catalyzed aerobic oxidation of (hetero)aryl acetimidates using molecular oxygen as a sustainable oxidant. The reaction represents the first example of the direct synthesis of aryl-α-ketoesters from arylacetimidates through the aerobic oxidation of a benzylic C(sp3)-H (C═O) bond in moderate to good yield. This transformation occurs under mild reaction conditions with a wide range of substrates and utilizes a readily available oxidant and catalyst. The synthetic utility of this transformation is demonstrated through scaled-up synthesis. A plausible reaction mechanism is also proposed.

  17. Approach to construct polysubstituted 1,2-dihydronaphtho[2,1-b]furans and their aerobic oxidative aromatization.

    PubMed

    Huo, Congde; Xu, Xiaolan; An, Jinzhu; Jia, Xiaodong; Wang, Xicun; Wang, Cheng

    2012-09-21

    Triarylaminium salt was disclosed as an efficient initiator for the novel Friedel-Crafts alkylation/annulation cascade reaction between chalcone epoxides and 2-naphthols to construct polysubstituted 1,2-dihydronaphtho[2,1-b]furans. The DDQ/NaNO(2)/O(2) catalytic system was first applied to the aerobic oxidative aromatization of heterocycles, and a simple and efficient one-pot tandem FC alkylation/annulation/aerobic oxidative aromatization procedure was also developed for the synthesis of complex naphtho[2,1-b]furans.

  18. Cu-catalyzed aerobic oxidative three-component coupling route to N-sulfonyl amidines via an ynamine intermediate.

    PubMed

    Kim, Jinho; Stahl, Shannon S

    2015-02-20

    Cu-catalyzed aerobic oxidative three-component coupling of a terminal alkyne, secondary amine, and sulfonamide enables efficient synthesis of amidines. The use of Cu(OTf)2 (5 mol %) produces amidines selectively without Glaser-Hay alkyne homocoupling products. Preliminary studies suggest that the reaction pathway involves initial oxidative coupling of the terminal alkyne with the secondary amine, followed by hydroamidation of the ynamine intermediate with the sulfonamide.

  19. Long-term aerobic exercise increases redox-active iron through nitric oxide in rat hippocampus.

    PubMed

    Chen, Qian; Xiao, De-Sheng

    2014-01-30

    Adult hippocampus is highly vulnerable to iron-induced oxidative stress. Aerobic exercise has been proposed to reduce oxidative stress but the findings in the hippocampus are conflicting. This study aimed to observe the changes of redox-active iron and concomitant regulation of cellular iron homeostasis in the hippocampus by aerobic exercise, and possible regulatory effect of nitric oxide (NO). A randomized controlled study was designed in the rats with swimming exercise treatment (for 3 months) and/or an unselective inhibitor of NO synthase (NOS) (L-NAME) treatment. The results from the bleomycin-detectable iron assay showed additional redox-active iron in the hippocampus by exercise treatment. The results from nonheme iron content assay, combined with the redox-active iron content, showed increased storage iron content by exercise treatment. NOx (nitrate plus nitrite) assay showed increased NOx content by exercise treatment. The results from the Western blot assay showed decreased ferroportin expression, no changes of TfR1 and DMT1 expressions, increased IRP1 and IRP2 expression, increased expressions of eNOS and nNOS rather than iNOS. In these effects of exercise treatment, the increased redox-active iron content, storage iron content, IRP1 and IRP2 expressions were completely reversed by L-NAME treatment, and decreased ferroportin expression was in part reversed by L-NAME. L-NAME treatment completely inhibited increased NOx and both eNOS and nNOS expression in the hippocampus. Our findings suggest that aerobic exercise could increase the redox-active iron in the hippocampus, indicating an increase in the capacity to generate hydroxyl radicals through the Fenton reactions, and aerobic exercise-induced iron accumulation in the hippocampus might mainly result from the role of the endogenous NO.

  20. Toxic effects of butyl elastomers on aerobic methane oxidation

    NASA Astrophysics Data System (ADS)

    Niemann, Helge; Steinle, Lea I.; Blees, Jan H.; Krause, Stefan; Bussmann, Ingeborg; Lehmann, Moritz F.; Treude, Tina

    2013-04-01

    Large quantities of the potent greenhouse gas methane are liberated into the water column of marine and lacustrine environments where it may be consumed by aerobic methane oxidising bacteria before reaching the atmosphere.The reliable quantification of aerobic methane oxidation (MOx) rates is consequently of paramount importance for estimating methane budgets and to understand the controls on water column methane cycling. A widely used set of methods for measuring MOx rates is based on the incubation of water samples during which the consumption of methane is monitored, for instance with radio-tracer assays. Typically, incubation vessels are sealed with butyl rubber stoppers because these elastomers are essentially impermeable for gases at the relevant time scales. We tested the effect of different stopper materials (unmodified- and halogenated butyl rubber) on MOx activity in environmental samples and in cultures of methane oxidising bacteria. MOx rates in samples sealed with unmodified butyl rubber were > 75% lower compared to parallel incubations with halogenated butyl rubber seals, suggesting inhibiting/toxic effects associated with the use of unmodified butyl elastomers. To further explore the cause of these effects, we analysed aqueous extracts of the different stoppers. Halogenated butyl rubber stoppers appeared to bleed off comparably little amounts of organics. In stark contrast, extracts of unmodified butyl rubber were contaminated with various organic compounds including potential bactericides such as benzyltoluenes, phenylalkanes and benzuothiazoles. We also found tetramethylthiourea, a scavenger of active oxygen species, which may inhibit the MOx pathway.

  1. Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms

    PubMed Central

    Kühl, Michael; Jørgensen, Bo Barker

    1992-01-01

    The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 μm) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

  2. Silver(I) as a widely applicable, homogeneous catalyst for aerobic oxidation of aldehydes toward carboxylic acids in water—“silver mirror”: From stoichiometric to catalytic

    PubMed Central

    Liu, Mingxin; Wang, Haining; Zeng, Huiying; Li, Chao-Jun

    2015-01-01

    The first example of a homogeneous silver(I)-catalyzed aerobic oxidation of aldehydes in water is reported. More than 50 examples of different aliphatic and aromatic aldehydes, including natural products, were tested, and all of them successfully underwent aerobic oxidation to give the corresponding carboxylic acids in extremely high yields. The reaction conditions are very mild and greener, requiring only a very low silver(I) catalyst loading, using atmospheric oxygen as the oxidant and water as the solvent, and allowing gram-scale oxidation with only 2 mg of our catalyst. Chromatography is completely unnecessary for purification in most cases. PMID:26601150

  3. Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: alleviating steric and electronic constraints of Cu/TEMPO catalyst systems.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2013-10-23

    Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of ((MeO)bpy)Cu(I)(OTf) and ABNO ((MeO)bpy = 4,4'-dimethoxy-2,2'-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant.

  4. Environmental control on aerobic methane oxidation in coastal waters

    NASA Astrophysics Data System (ADS)

    Steinle, Lea; Maltby, Johanna; Engbersen, Nadine; Zopfi, Jakob; Bange, Hermann; Elvert, Marcus; Hinrichs, Kai-Uwe; Kock, Annette; Lehmann, Moritz; Treude, Tina; Niemann, Helge

    2016-04-01

    Large quantities of methane are produced in anoxic sediments of continental margins and may be liberated to the overlying water column, where some of it is consumed by aerobic methane oxidizing bacteria (MOB). Aerobic methane oxidation (MOx) in the water column is consequently the final sink for methane before its release to the atmosphere, where it acts as a potent greenhouse gas. In the context of the ocean's contribution to atmospheric methane, coastal seas are particularly important accounting >75% of global methane emission from marine systems. Coastal oceans are highly dynamic, in particular with regard to the variability of methane and oxygen concentrations as well as temperature and salinity, all of which are potential key environmental factors controlling MOx. To determine important environmental controls on the activity of MOBs in coastal seas, we conducted a two-year time-series study with measurements of physicochemical water column parameters, MOx activity and the composition of the MOB community in a coastal inlet in the Baltic Sea (Boknis Eck Time Series Station, Eckernförde Bay - E-Bay). In addition, we investigated the influence of temperature and oxygen on MOx during controlled laboratory experiments. In E-Bay, hypoxia developed in bottom waters towards the end of the stratification period. Constant methane liberation from sediments resulted in bottom water methane accumulations and supersaturation (with respect to the atmospheric equilibrium) in surface waters. Here, we will discuss the factors impacting MOx the most, which were (i) perturbations of the water column (ii) temperature and (iii) oxygen concentration. (i) Perturbations of the water column caused by storm events or seasonal mixing led to a decrease in MOx, probably caused by replacement of stagnant water with a high standing stock of MOB by 'new' waters with a lower abundance of methanotrophs. b) An increase in temperature generally led to higher MOx rates. c) Even though methane was

  5. High catalytic activity of palladium(II)-exchanged mesoporous sodalite and NaA zeolite for bulky aryl coupling reactions: reusability under aerobic conditions.

    PubMed

    Choi, Minkee; Lee, Dong-Hwan; Na, Kyungsu; Yu, Byung-Woo; Ryoo, Ryong

    2009-01-01

    Exchange for the better: Mesoporous sodalite and NaA zeolite exchanged with Pd(2+) exhibit remarkably high activity and reusability in C-C coupling reactions under aerobic atmosphere. It is proposed that the catalytic reactions are mediated by a molecular Pd(0) species generated in situ within the pores (see picture), which is oxidized back to Pd(2+) by O(2), preventing the formation of catalytically inactive Pd(0) agglomerates.

  6. Selective aerobic oxidation mediated by TiO(2) photocatalysis.

    PubMed

    Lang, Xianjun; Ma, Wanhong; Chen, Chuncheng; Ji, Hongwei; Zhao, Jincai

    2014-02-18

    TiO2 is one of the most studied metal oxide photocatalysts and has unparal-leled efficiency and stability. This cheap, abundant, and non-toxic material has the potential to address future environmental and energy concerns. Understanding about the photoinduced interfacial redox events on TiO2 could have profound effect on the degradation of organic pollutants, splitting of H2O into H2 and O2, and selective redox organic transformations. Scientists traditionally accept that for a semiconductor photocatalyst such as TiO2 under the illumination of light with energy larger than its band gap, two photocarriers will be created to carry out their independent reduction and oxidation processes. However, our recent discoveries indicate that it is the concerted rather than independent effect of both photocarriers of valence band hole (hvb(+)) and conduction band electron (ecb(-)) that dictate the product formation during interfacial oxidation event mediated by TiO2 photocatalysis. In this Account, we describe our recent findings on the selective oxidation of organic substrates with O2 mediated by TiO2 photocatalysis. The transfer of O-atoms from O2 to the corresponding products dominates the selective oxidation of alcohols, amines, and alkanes mediated by TiO2 photocatalysis. We ascribe this to the concerted effect of both hvb(+) and ecb(-) of TiO2 in contribution to the oxidation products. These findings imply that O2 plays a unique role in its transfer into the products rather than independent role of ecb(-) scavenger. More importantly, ecb(-) plays a crucial role to ensure the high selectivity for the oxygenation of organic substrates. We can also use the half reactions such as those of the conduction band electron of TiO2 for efficient oxidation reactions with O2. To this end, efficient selective oxidation of organic substrates such as alcohols, amines, and aromatic alkanes with O2 mediated by TiO2 photocatalysis under visible light irradiation has been achieved. In

  7. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    PubMed Central

    2015-01-01

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

  8. Unexpected ring-opening reactions of aziridines with aldehydes catalyzed by nucleophilic carbenes under aerobic conditions.

    PubMed

    Liu, Yan-Kai; Li, Rui; Yue, Lei; Li, Bang-Jing; Chen, Ying-Chun; Wu, Yong; Ding, Li-Sheng

    2006-04-13

    [reaction: see text] The chemoselective ring opening of N-tosyl aziridines with aldehydes catalyzed by an N-heterocyclic carbene was investigated under aerobic conditions. Unexpected carboxylates of 1,2-amino alcohols from the corresponding aldehydes, rather than the acyl anion ring-opened beta-amino ketones, were exclusively obtained. A plausible mechanism for this unprecedented carbene-mediated reaction was also proposed.

  9. Initial reductive reactions in aerobic microbial metabolism of 2,4,6-trinitrotoluene.

    PubMed

    Vorbeck, C; Lenke, H; Fischer, P; Spain, J C; Knackmuss, H J

    1998-01-01

    Because of its high electron deficiency, initial microbial transformations of 2,4,6-trinitrotoluene (TNT) are characterized by reductive rather than oxidation reactions. The reduction of the nitro groups seems to be the dominating mechanism, whereas hydrogenation of the aromatic ring, as described for picric acid, appears to be of minor importance. Thus, two bacterial strains enriched with TNT as a sole source of nitrogen under aerobic conditions, a gram-negative strain called TNT-8 and a gram-positive strain called TNT-32, carried out nitro-group reduction. In contrast, both a picric acid-utilizing Rhodococcus erythropolis strain, HL PM-1, and a 4-nitrotoluene-utilizing Mycobacterium sp. strain, HL 4-NT-1, possessed reductive enzyme systems, which catalyze ring hydrogenation, i.e., the addition of a hydride ion to the aromatic ring of TNT. The hydride-Meisenheimer complex thus formed (H-TNT) was further converted to a yellow metabolite, which by electrospray mass and nuclear magnetic resonance spectral analyses was established as the protonated dihydride-Meisenheimer complex of TNT (2H-TNT). Formation of hydride complexes could not be identified with the TNT-enriched strains TNT-8 and TNT-32, or with Pseudomonas sp. clone A (2NT), for which such a mechanism has been proposed. Correspondingly, reductive denitration of TNT did not occur.

  10. Initial Reductive Reactions in Aerobic Microbial Metabolism of 2,4,6-Trinitrotoluene

    PubMed Central

    Vorbeck, Claudia; Lenke, Hiltrud; Fischer, Peter; Spain, Jim C.; Knackmuss, Hans-Joachim

    1998-01-01

    Because of its high electron deficiency, initial microbial transformations of 2,4,6-trinitrotoluene (TNT) are characterized by reductive rather than oxidation reactions. The reduction of the nitro groups seems to be the dominating mechanism, whereas hydrogenation of the aromatic ring, as described for picric acid, appears to be of minor importance. Thus, two bacterial strains enriched with TNT as a sole source of nitrogen under aerobic conditions, a gram-negative strain called TNT-8 and a gram-positive strain called TNT-32, carried out nitro-group reduction. In contrast, both a picric acid-utilizing Rhodococcus erythropolis strain, HL PM-1, and a 4-nitrotoluene-utilizing Mycobacterium sp. strain, HL 4-NT-1, possessed reductive enzyme systems, which catalyze ring hydrogenation, i.e., the addition of a hydride ion to the aromatic ring of TNT. The hydride-Meisenheimer complex thus formed (H−-TNT) was further converted to a yellow metabolite, which by electrospray mass and nuclear magnetic resonance spectral analyses was established as the protonated dihydride-Meisenheimer complex of TNT (2H−-TNT). Formation of hydride complexes could not be identified with the TNT-enriched strains TNT-8 and TNT-32, or with Pseudomonas sp. clone A (2NT−), for which such a mechanism has been proposed. Correspondingly, reductive denitration of TNT did not occur. PMID:16349484

  11. Photopromoted Ru-catalyzed asymmetric aerobic sulfide oxidation and epoxidation using water as a proton transfer mediator.

    PubMed

    Tanaka, Haruna; Nishikawa, Hiroaki; Uchida, Tatsuya; Katsuki, Tsutomu

    2010-09-01

    Ru(NO)-salen complexes were found to catalyze asymmetric aerobic oxygen atom transfer reactions such as sulfide oxidation and epoxidation in the presence of water under visible light irradiation at room temperature. Oxidation of sulfides including alkyl aryl sulfides and 2-substituted 1,3-dithianes using complex 2 as the catalyst proceeded with moderate to high enantioselectivity of up to 98% ee, and epoxidation of conjugated olefins using complex 3 as the catalyst proceeded with good to high enantioselectivity of 76-92% ee. Unlike biological oxygen atom transfer reactions that need a proton and electron transfer system, this aerobic oxygen atom transfer reaction requires neither such a system nor a sacrificial reductant. Although the mechanism of this oxidation has not been completely clarified, some experimental results support the notion that an aqua ligand coordinated with the ruthenium ion serves as a proton transfer agent for the oxygen activation process, and it is recycled and used as the proton transfer mediator during the process. Thus, we have achieved catalytic asymmetric oxygen atom transfer reaction using molecular oxygen that can be carried out under ambient conditions.

  12. Aerobic condition increases carotenoid production associated with oxidative stress tolerance in Enterococcus gilvus.

    PubMed

    Hagi, Tatsuro; Kobayashi, Miho; Nomura, Masaru

    2014-01-01

    Although it is known that a part of lactic acid bacteria can produce carotenoid, little is known about the regulation of carotenoid production. The objective of this study was to determine whether aerobic growth condition influences carotenoid production in carotenoid-producing Enterococcus gilvus. Enterococcus gilvus was grown under aerobic and anaerobic conditions. Its growth was slower under aerobic than under anaerobic conditions. The decrease in pH levels and production of lactic acid were also lower under aerobic than under anaerobic conditions. In contrast, the amount of carotenoid pigments produced by E. gilvus was significantly higher under aerobic than under anaerobic conditions. Further, real-time quantitative reverse transcription PCR revealed that the expression level of carotenoid biosynthesis genes crtN and crtM when E. gilvus was grown under aerobic conditions was 2.55-5.86-fold higher than when it was grown under anaerobic conditions. Moreover, after exposure to 16- and 32-mM H2O2, the survival rate of E. gilvus grown under aerobic conditions was 61.5- and 72.5-fold higher, respectively, than when it was grown under anaerobic conditions. Aerobic growth conditions significantly induced carotenoid production and the expression of carotenoid biosynthesis genes in E. gilvus, resulting in increased oxidative stress tolerance.

  13. Aerobic organocatalytic oxidation of aryl aldehydes: flavin catalyst turnover by Hantzsch's ester.

    PubMed

    Chen, Shuai; Foss, Frank W

    2012-10-05

    The first Dakin oxidation fueled by molecular oxygen as the terminal oxidant is reported. Flavin and NAD(P)H coenzymes, from natural enzymatic redox systems, inspired the use of flavin organocatalysts and a Hantzsch ester to perform transition-metal-free, aerobic oxidations. Catechols and electron-rich phenols are achieved with as low as a 0.1 mol % catalyst loading, 1 equiv of Hantzsch ester, and O(2) or air as the stoichiometric oxidant source.

  14. Environmental Controls on Aerobic Methane Oxidation in Coastal Waters

    NASA Astrophysics Data System (ADS)

    Steinle, L.; Maltby, J.; Engbersen, N.; Zopfi, J.; Bange, H. W.; Elvert, M.; Hinrichs, K. U.; Kock, A.; Lehmann, M. F.; Treude, T.; Niemann, H.

    2015-12-01

    Large quantities of the greenhouse gas CH4 are produced in anoxic sediments of continental margins and may be liberated to the overlying water column, and later into the atmosphere. Indeed, coastal seas account for more than 75% of global oceanic CH4 emissions. Yet, aerobic CH4 oxidizing bacteria (MOB) consume an important part of CH4 in the water column, thus mitigating CH4 release to the atmosphere. Coastal oceans are highly dynamic systems, in particular with regard to the variability of temperature, salinity and oxygen concentrations, all of which are potential key environmental factors controlling MOx. To determine the most important controlling factors, we conducted a two-year time-series study with measurements of CH4, MOx, the composition of the MOB community, and physicochemical water column parameters in a coastal inlet in the Baltic Sea (Eckernförde(E-) Bay, Boknis Eck Time Series Station). In addition, we investigated the influence of temperature and oxygen on MOx during controlled laboratory experiments. In E-Bay, seasonal stratification leads to hypoxia in bottom waters towards the end of the stratification period. Methane is produced year-round in the sediments, resulting in accumulation of methane in bottom waters, and supersaturation (with respect to the atmospheric equilibrium) in surface waters. Here, we will discuss the factors impacting MOx the most, which were a) perturbations of the water column caused by storm events, currents or seasonal mixing, b) temperature and c) oxygen concentration. a) Perturbations of the water column led to a sharp decrease in MOx within hours, probably caused by replacement of 'old' water with a high standing stock of MOB by 'new' waters with a lower abundance of MOB. b) An increase in temperature generally led to higher MOx rates. c) Even though CH4 was abundant at all depths, MOx was highest in bottom waters (1-5 nM/d), which usually contain the lowest O2 concentrations. Lab-based experiments with adjusted O2

  15. Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2015-06-16

    Selective oxidation reactions have extraordinary value in organic chemistry, ranging from the conversion of petrochemical feedstocks into industrial chemicals and polymer precursors to the introduction of heteroatom functional groups into pharmaceutical and agrochemical intermediates. Molecular oxygen (O2) would be the ideal oxidant for these transformations. Whereas many commodity-scale oxidations of simple hydrocarbon feedstocks employ O2 as an oxidant, methods for selective oxidation of more complex molecules bearing diverse functional groups are often incompatible with existing aerobic oxidation methods. The latter limitation provides the basis for our interest in the development of new catalytic transformations and the elucidation of mechanistic principles that underlie selective aerobic oxidation reactions. One challenge inherent in such methods is the incommensurate redox stoichiometry associated with the use of O2, a four-electron oxidant, in reactions that achieve two-electron oxidation of organic molecules. This issue is further complicated by the use of first-row transition-metal catalysts, which tend to undergo facile one-electron redox steps. In recent years, we have been investigating Cu-catalyzed aerobic oxidation reactions wherein the complexities just noted are clearly evident. This Account surveys our work in this area, which has emphasized three general classes of reactions: (1) single-electron-transfer reactions for oxidative functionalization of electron-rich substrates, such as arenes and heterocycles; (2) oxidative carbon-heteroatom bond-forming reactions, including C-H oxidations, that proceed via organocopper(III) intermediates; and (3) methods for aerobic oxidation of alcohols and amines that use Cu(II) in combination with an organic redox-active cocatalyst to dehydrogenate the carbon-heteroatom bond. These reaction classes demonstrate three different pathways to achieve two-electron oxidation of organic molecules via the cooperative

  16. Analysis of Reaction Times and Aerobic Capacities of Soccer Players According to Their Playing Positions

    ERIC Educational Resources Information Center

    Taskin, Cengiz; Karakoc, Onder; Taskin, Mine; Dural, Murat

    2016-01-01

    70 soccer players in Gaziantep amateur league voluntarily participated in this study, (average of their ages 19,17±1,34years, average of their heights 181,28±5,06 cm, average of their body weights 76,75±4,43 kg and average of their sports experiences 3,78±0,95 years) to analyze visual and auditory reaction times and aerobic capacities of amateur…

  17. High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    SciTech Connect

    Gerken, James B.; Stahl, Shannon S.

    2015-07-15

    Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  18. Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions

    PubMed Central

    Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

    2014-01-01

    Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD. PMID:24245852

  19. Metabolic engineering of Escherichia coli for 1-butanol biosynthesis through the inverted aerobic fatty acid β-oxidation pathway.

    PubMed

    Gulevich, Andrey Yu; Skorokhodova, Alexandra Yu; Sukhozhenko, Alexey V; Shakulov, Rustem S; Debabov, Vladimir G

    2012-03-01

    The basic reactions of the clostridial 1-butanol biosynthesis pathway can be regarded to be the inverted reactions of the fatty acid β-oxidation pathway. A pathway for the biosynthesis of fuels and chemicals was recently engineered by combining enzymes from both aerobic and anaerobic fatty acid β-oxidation as well as enzymes from other metabolic pathways. In the current study, we demonstrate the inversion of the entire aerobic fatty acid β-oxidation cycle for 1-butanol biosynthesis. The constructed markerless and plasmidless Escherichia coli strain BOX-3 (MG1655 lacI(Q) attB-P(trc-ideal-4)-SD(φ10)-adhE(Glu568Lys) attB-P(trc-ideal-4)-SD(φ10)-atoB attB-P(trc-ideal-4)-SD(φ10)-fadB attB-P(trc-ideal-4)-SD(φ10)-fadE) synthesises 0.3-1 mg 1-butanol/l in the presence of the specific inducer. No 1-butanol production was detected in the absence of the inducer.

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

    SciTech Connect

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

    2006-07-01

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

  1. Combination of ozonation with conventional aerobic oxidation for distillery wastewater treatment.

    PubMed

    Sangave, Preeti C; Gogate, Parag R; Pandit, Aniruddha B

    2007-05-01

    Laboratory-scale experiments were conducted in order to investigate the effect of ozone as pre-aerobic treatment and post-aerobic treatment for the treatment of the distillery wastewater. The degradation of the pollutants present in distillery spent wash was carried out by ozonation, aerobic biological degradation processes alone and by using the combinations of these two processes to investigate the synergism between the two modes of wastewater treatment and with the aim of reducing the overall treatment costs. Pollutant removal efficiency was followed by means of global parameters directly related to the concentration of organic compounds in those effluents: chemical oxygen demand (COD) and the color removal efficiency in terms of absorbance of the sample at 254 nm. Ozone was found to be effective in bringing down the COD (up to 27%) during the pretreatment step itself. In the combined process, pretreatment of the effluent led to enhanced rates of subsequent biological oxidation step, almost 2.5 times increase in the initial oxidation rate has been observed. Post-aerobic treatment with ozone led to further removal of COD along with the complete discoloration of the effluent. The integrated process (ozone-aerobic oxidation-ozone) achieved approximately 79% COD reduction along with discoloration of the effluent sample as compared to 34.9% COD reduction for non-ozonated sample, over a similar treatment period.

  2. A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

    PubMed

    Xu, Boran; Lumb, Jean-Philip; Arndtsen, Bruce A

    2015-03-27

    The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols.

  3. Isolation of an aerobic sulfur oxidizer from the SUP05/Arctic96BD-19 clade.

    PubMed

    Marshall, Katharine T; Morris, Robert M

    2013-02-01

    Bacteria from the uncultured SUP05/Arctic96BD-19 clade of gamma proteobacterial sulfur oxidizers (GSOs) have the genetic potential to oxidize reduced sulfur and fix carbon in the tissues of clams and mussels, in oxygen minimum zones and throughout the deep ocean (>200 m). Here, we report isolation of the first cultured representative from this GSO clade. Closely related cultures were obtained from surface waters in Puget Sound and from the deep chlorophyll maximum in the North Pacific gyre. Pure cultures grow aerobically on natural seawater media, oxidize sulfur, and reach higher final cell densities when glucose and thiosulfate are added to the media. This suggests that aerobic sulfur oxidation enhances organic carbon utilization in the oceans. The first isolate from the SUP05/Arctic96BD-19 clade was given the provisional taxonomic assignment 'Candidatus: Thioglobus singularis', alluding to the clade's known role in sulfur oxidation and the isolate's planktonic lifestyle.

  4. Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

    PubMed Central

    Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

    2015-01-01

    Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

  5. Large-scale synthesis of ultrathin tungsten oxide nanowire networks: an efficient catalyst for aerobic oxidation of toluene to benzaldehyde under visible light

    NASA Astrophysics Data System (ADS)

    Bai, Hua; Yi, Wencai; Liu, Jingyao; Lv, Qing; Zhang, Qing; Ma, Qiang; Yang, Haifeng; Xi, Guangcheng

    2016-07-01

    As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%.As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%. Electronic supplementary information (ESI) available: Experimental procedure, XRD patterns, TEM and HRTEM images, energy-dispersive X-ray spectra, UV-vis spectra, X-ray photoelectron spectroscopy (XPS), and EDS. See DOI: 10.1039/c6nr02949c

  6. Treatment of real industrial wastewater using the combined approach of advanced oxidation followed by aerobic oxidation.

    PubMed

    Ramteke, Lokeshkumar P; Gogate, Parag R

    2016-05-01

    Fenton oxidation and ultrasound-based pretreatment have been applied to improve the treatment of real industrial wastewater based on the use of biological oxidation. The effect of operating parameters such as Fe(2+) loading, contact time, initial pH, and hydrogen peroxide loading on the extent of chemical oxygen demand (COD) reduction and change in biochemical oxygen demand (BOD5)/COD ratio has been investigated. The optimum operating conditions established for the pretreatment were initial pH of 3.0, Fe(2+) loading of 2.0, and 2.5 g L(-1) for the US/Fenton/stirring and Fenton approach, respectively, and temperature of 25 °C with initial H2O2 loading of 1.5 g L(-1). The use of pretreatment resulted in a significant increase in the BOD5/COD ratio confirming the production of easily digestible intermediates. The effect of the type of sludge in the aerobic biodegradation was also investigated based on the use of primary activated sludge (PAS), modified activated sludge (MAS), and activated sludge (AS). Enhanced removal of the pollutants as well as higher biomass yield was observed for MAS as compared to PAS and AS. The use of US/Fenton/stirring pretreatment under the optimized conditions followed by biological oxidation using MAS resulted in maximum COD removal at 97.9 %. The required hydraulic retention time for the combined oxidation system was also significantly lower as compared to only biological oxidation operation. Kinetic studies revealed that the reduction in the COD followed a first-order kinetic model for advanced oxidation and pseudo first-order model for biodegradation. The study clearly established the utility of the combined technology for the effective treatment of real industrial wastewater.

  7. High resolution and comprehensive techniques to analyze aerobic methane oxidation in mesocosm experiments

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Redmond, M. C.; Shiller, A. M.; Arrington, E. C.; Valentine, D. L.; Colombo, F.

    2015-12-01

    Many studies of microbially mediated aerobic methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on how quickly methane is oxidized once a microbial population is established and what factor(s) are limiting in these types of environments. These factors include the availability of CH4, O2, trace metals, nutrients, and the density of cell population. Limits to these factors can also control the temporal aspects of a methane oxidation event. In order to look at this process in its entirety and with higher temporal resolution, a mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) coupled with a set of analytical tools to monitor aerobic methane oxidation in real time. With the addition of newer laser spectroscopy techniques (cavity ringdown spectroscopy), stable isotope fractionation caused by microbial processes can also be examined on a real time and automated basis. Cell counting, trace metal, nutrient, and DNA community analyses have also been carried out in conjunction with these mesocosm samples to provide a clear understanding of the biology in methane oxidation dynamics. This poster will detail the techniques involved to provide insights into the chemical and isotopic kinetics controlling aerobic methane oxidation. Proof of concept applications will be presented from seep sites in the Hudson Canyon and the Sleeping Dragon seep field, Mississippi Canyon 118 (MC 118). This system was used to conduct mesocosm experiments to examine methane consumption, O2 consumption, nutrient consumption, and biomass production.

  8. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    PubMed

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts.

  9. Nitrous oxide production by Alcaligenes faecalis under transient and dynamic aerobic and anaerobic conditions

    SciTech Connect

    Otte, S.; Grobben, N.G.; Robertson, L.A.; Jetten, M.S.M.; Kuenen, J.G.

    1996-07-01

    Nitrous oxide production contributes to both greenhouse effect and ozone depletion in the stratosphere. A significant part of the global N2O emission can be attributed to microbial processes, especially nitrification and denitrification, used in biological wastewater treatment systems. This study looks at the efficiency of denitrification and the enzymes involved, with the emphasis on N2O production during the transient phase from aerobic to anaerobic conditions and vice versa. The effect of repetitive changing aerobic-anaerobic conditions on N2O was also studied. Alcaligenes faecalis was used as the model denitrofing organism. 35 refs., 3 figs., 1 tab.

  10. Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

    PubMed

    Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

    2015-05-13

    An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

  11. Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols.

    PubMed

    Qi, Yue; Luan, Yi; Yu, Jie; Peng, Xiong; Wang, Ge

    2015-01-19

    Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity.

  12. The nitric oxide producing reactions of hydroxyurea.

    PubMed

    King, S Bruce

    2003-03-01

    Hydroxyurea is used to treat a variety of cancers and sickle cell disease. Despite this widespread use, a complete mechanistic understanding of the beneficial actions of this compound remains to be understood. Hydroxyurea inhibits ribonucleotide reductase and increases the levels of fetal hemoglobin, which explains a portion of the effects of this drug. Administration of hydroxyurea to patients results in a significant increase in levels of iron nitrosyl hemoglobin, nitrite and nitrate suggesting the in vivo metabolism of hydroxyurea to nitric oxide. Formation of nitric oxide from hydroxyurea may explain a portion of the observed effects of hydroxyurea treatment. At the present, the mechanism or mechanisms of nitric oxide release, the identity of the in vivo oxidant and the site of metabolism remain to be identified. Chemical oxidation of hydroxyurea produces nitric oxide and nitroxyl, the one-electron reduced form of nitric oxide. These oxidative pathways generally proceed through the nitroxide radical (2) or C-nitrosoformamide (3). Biological oxidants, including both iron and copper containing enzymes and proteins, also convert hydroxyurea to nitric oxide or its decomposition products in vitro and these reactions also occur through these intermediates. A number of other reactions of hydroxyurea including the reaction with ribonucleotide reductase and irradiation demonstrate the potential to release nitric oxide and should be further investigated. Gaining an understanding of the metabolism of hydroxyurea to nitric oxide will provide valuable information towards the treatment of these disorders and may lead to the development of better therapeutic agents.

  13. Surface-active ionic liquids in catalysis: Impact of structure and concentration on the aerobic oxidation of octanol in water.

    PubMed

    Cognigni, Alice; Kampichler, Sebastian; Bica, Katharina

    2017-04-15

    We present design and synthesis of surface-active ionic liquids for the application in micellar catalysis. A series of 1-methyl-3-dodecylimidazolium based ionic liquids with variable core structures including dicationic and zwitterionic ones was synthesized and characterized. These surface-active ionic liquids where applied in the aerobic oxidation of aliphatic alcohols to carbonyl compounds. A strong dependence on the ionic liquid concentration and structure was identified, which is in accordance with the concepts of micellar catalysis. Optimum conditions for the oxidation of 1-octanol could be identified, and the use of surface-active ionic liquids strongly improved the reaction performance compared to pure water. Under optimized conditions, it was possible to isolate up to 75% of octanoic acid using only small amounts of surface-active ionic liquid in a 0.05mM solution in water without further ligands.

  14. Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2013-12-01

    accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

  15. Reactions of nitrogen oxides with polymers

    NASA Astrophysics Data System (ADS)

    Pariiskii, Georgii B.; Gaponova, I. S.; Davydov, Evgenii Ya

    2000-11-01

    The mechanisms of the reactions of nitrogen oxides and different classes of solid polymers are considered. Particular emphasis is given to the analysis of the mechanisms of the formation of stable nitroxyl radicals. Double bonds and amide groups of macromolecules, as well as hydroperoxides and peroxide macroradicals are shown to be involved in the reactions with nitrogen oxides. The application of nitrogen oxides for the preparation of spin-labelled polymers and the use of the ESR imaging technique (ESR tomography) for the investigation of the structure of the reaction front during nitration of solid polymers are considered. The bibliography includes 111 references.

  16. Combination of aerobic and vacuum packaging to control lipid oxidation and off-odor volatiles of irradiated raw turkey breast.

    PubMed

    Nam, K C; Ahn, D U

    2003-03-01

    Effects of the combination of aerobic and anaerobic packaging on color, lipid oxidation, and volatile production were determined to establish a modified packaging method to control quality changes in irradiated raw turkey meat. Lipid oxidation was the major problem with aerobically packaged irradiated turkey breast, while retaining characteristic irradiation off-odor volatiles such as dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide was the concern for vacuum-packaged breast during the 10-day refrigerated storage. Vacuum packaging of aerobically packaged irradiated turkey breast meat at 1 or 3 days of storage lowered the amounts of S-volatiles and lipid oxidation products compared with vacuum- and aerobically packaged meats, respectively. Irradiation increased the a-value of raw turkey breast, but exposing the irradiated meat to aerobic conditions alleviated the intensity of redness.

  17. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    PubMed

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency.

  18. Evaluation of methyl fluoride and dimethyl ether as inhibitors of aerobic methane oxidation

    USGS Publications Warehouse

    Oremland, R.S.; Culbertson, C.W.

    1992-01-01

    Methyl fluoride (MF) and dimethyl ether (DME) were effective inhibitors of aerobic methanotrophy in a variety of soils. MF and DME blocked consumption of CH4 as well as the oxidation of 14CH4 to 14CO2, but neither MF nor DME affected the oxidation of [14C]methanol or [14C]formate to 14CO2. Cooxidation of ethane and propane by methane-oxidizing soils was also inhibited by MF. Nitrification (ammonia oxidation) in soils was inhibited by both MF and DME. Production of N2O via nitrification was inhibited by MF; however, MF did not affect N2O production associated with denitrification. Methanogenesis was partially inhibited by MF but not by DME. Methane oxidation was ~100-fold more sensitive to MF than was methanogenesis, indicating that an optimum concentration could be employed to selectively block methanotrophy. MF inhibited methane oxidation by cell suspensions of Methylococcus capsulatus; however, DME was a much less effective inhibitor.

  19. Oxidative Reactions with Nonaqueous Enzymes

    SciTech Connect

    Jonathan S. Dordick; Douglas Clark; Brian H Davison; Alexander Klibanov

    2001-12-30

    The objective of this work is to demonstrate a proof-of-concept of enzymatic oxidative processing in nonaqueous media using alkene epoxidation and phenolic polymerization as relevant targets. This project will provide both the fundamental and applied investigations necessary to initiate the implementation of oxidative biocatalysts as commercially relevant alternatives to chemical processing in general, and to phenolic polymerizations and alkene epoxidation specifically. Thus, this work will address the Bioprocessing Solicitation Area to: (1) makes major improvements to phenolic polymerization and alkene epoxidation technologies; (2) is expected to be cost competitive with competing conventional processes; and (3) produces higher yields with less waste.

  20. An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes.

    PubMed

    Bortolini, O; Chiappe, C; Fogagnolo, M; Giovannini, P P; Massi, A; Pomelli, C S; Ragno, D

    2014-02-25

    N-Heterocyclic carbene catalysis for the aerobic oxidation and esterification of aromatic aldehydes was monitored by ESI-MS (MS/MS) and the key intermediates were intercepted and characterized using the charge-tag strategy.

  1. Supplementation with vitamin A enhances oxidative stress in the lungs of rats submitted to aerobic exercise.

    PubMed

    Gasparotto, Juciano; Petiz, Lyvia Lintzmaier; Girardi, Carolina Saibro; Bortolin, Rafael Calixto; de Vargas, Amanda Rodrigues; Henkin, Bernardo Saldanha; Chaves, Paloma Rodrigues; Roncato, Sabrina; Matté, Cristiane; Zanotto-Filho, Alfeu; Moreira, José Cláudio Fonseca; Gelain, Daniel Pens

    2015-12-01

    Exercise training induces reactive oxygen species production and low levels of oxidative damage, which are required for induction of antioxidant defenses and tissue adaptation. This process is physiological and essential to improve physical conditioning and performance. During exercise, endogenous antioxidants are recruited to prevent excessive oxidative stress, demanding appropriate intake of antioxidants from diet or supplements; in this context, the search for vitamin supplements that enhance the antioxidant defenses and improve exercise performance has been continuously increasing. On the other hand, excess of antioxidants may hinder the pro-oxidant signals necessary for this process of adaptation. The aim of this study was to investigate the effects of vitamin A supplementation (2000 IU/kg, oral) upon oxidative stress and parameters of pro-inflammatory signaling in lungs of rats submitted to aerobic exercise (swimming protocol). When combined with exercise, vitamin A inhibited biochemical parameters of adaptation/conditioning by attenuating exercise-induced antioxidant enzymes (superoxide dismutase and glutathione peroxidase) and decreasing the content of the receptor for advanced glycation end-products. Increased oxidative damage to proteins (carbonylation) and lipids (lipoperoxidation) was also observed in these animals. In sedentary animals, vitamin A decreased superoxide dismutase and increased lipoperoxidation. Vitamin A also enhanced the levels of tumor necrosis factor alpha and decreased interleukin-10, effects partially reversed by aerobic training. Taken together, the results presented herein point to negative effects associated with vitamin A supplementation at the specific dose here used upon oxidative stress and pro-inflammatory cytokines in lung tissues of rats submitted to aerobic exercise.

  2. Dissolution of Fe(III)(hydr)oxides by an Aerobic Bacterium

    SciTech Connect

    Maurice, P.

    2004-12-13

    This project investigated the effects of an aerobic Pseudomonas mendocina bacterium on the dissolution of Fe(III)(hydr)oxides. The research is important because metals and radionuclides that adsorb to Fe(III)(hydr)oxides could potentially be remobilized by dissolving bacteria. We showed that P. mendocina is capable of dissolving Fe-bearing minerals by a variety of mechanisms, including production of siderophores, pH changes, and formation of reductants. The production of siderophores by P. mendocina was quantified under a variety of growth conditions. Finally, we demonstrated that microbial siderophores may adsorb to and enhance dissolution of clay minerals.

  3. A new intra-aerobic metabolism in the nitrite-dependent anaerobic methane-oxidizing bacterium Candidatus 'Methylomirabilis oxyfera'.

    PubMed

    Wu, Ming L; Ettwig, Katharina F; Jetten, Mike S M; Strous, Marc; Keltjens, Jan T; van Niftrik, Laura

    2011-01-01

    Biological methane oxidation proceeds either through aerobic or anaerobic pathways. The newly discovered bacterium Candidatus 'Methylomirabilis oxyfera' challenges this dichotomy. This bacterium performs anaerobic methane oxidation coupled to denitrification, but does so in a peculiar way. Instead of scavenging oxygen from the environment, like the aerobic methanotrophs, or driving methane oxidation by reverse methanogenesis, like the methanogenic archaea in sulfate-reducing systems, it produces its own supply of oxygen by metabolizing nitrite via nitric oxide into oxygen and dinitrogen gas. The intracellularly produced oxygen is then used for the oxidation of methane by the classical aerobic methane oxidation pathway involving methane mono-oxygenase. The present mini-review summarizes the current knowledge about this process and the micro-organism responsible for it.

  4. Aerobic and anaerobic methane oxidation in terrestrial mud volcanoes in the Northern Apennines

    NASA Astrophysics Data System (ADS)

    Wrede, C.; Brady, S.; Rockstroh, S.; Dreier, A.; Kokoschka, S.; Heinzelmann, S. M.; Heller, C.; Reitner, J.; Taviani, M.; Daniel, R.; Hoppert, M.

    2012-07-01

    Methane oxidizing prokaryotes are ubiquitous in oxic and anoxic habitats wherever C1-compounds are present. Thus, methane saturated mud volcano fluids should be a preferred habitat of methane consuming prokaryotes, using the readily available electron donors. In order to understand the relevance of methane as a carbon and energy source in mud volcano communities, we investigate the diversity of prokaryotic organisms involved in oxidation of methane in fluid samples from the Salse di Nirano mud volcano field situated in the Northern Apennines. Cell counts were at approximately 0.7 × 106 microbial cells/ml. A fraction of the microbial biomass was identified as ANME (anaerobic methanotroph) archaea by fluorescence in situ hybridization (FISH) analysis. They are associated in densely colonized flakes, of some tens of μm in diameter, embedded in a hyaline matrix. Diversity analysis based on the 16S rDNA genes, retrieved from amplified and cloned environmental DNA, revealed a high proportion of archaea, involved in anaerobic oxidation of methane (AOM). Aerobic methane-oxidizing proteobacteria could be highly enriched from mud volcano fluids, indicating the presence of aerobic methanotrophic bacteria, which may contribute to methane oxidation, whenever oxygen is readily available. The results imply that biofilms, dominated by ANME archaea, colonize parts of the mud volcano venting system.

  5. Nickel-Catalyzed Aerobic Oxidative Isocyanide Insertion: Access to Benzimidazoquinazoline Derivatives via a Sequential Double Annulation Cascade (SDAC) Strategy.

    PubMed

    Shinde, Anand H; Arepally, Sagar; Baravkar, Mayur D; Sharada, Duddu S

    2017-01-06

    An efficient protocol for the synthesis of quinazoline derivatives through nickel-catalyzed ligand-/base-free oxidative isocyanide insertion under aerobic conditions with intramolecular bis-amine nucleophiles has been developed. A one-pot sequential double annulation cascade (SDAC) strategy involving an opening of isatoic anhydride and annulation to benzimidazole and further nickel-catalyzed intramolecular isocyanide insertion has also been demonstrated. The method is operationally simple to implement with a wide variety of substrates and represents a new approach for multiple C-N bond formations. The methodology has been successfully applied to the syntheses of hitherto unreported imidazo-fused benzimidazoquinazolines via a deprotection-GBB reaction sequence. Further, a florescence study reveals the potential of the present strategy for the discovery of highly fluorescent probes.

  6. Selective inhibition of nitrite oxidation by chlorate dosing in aerobic granules.

    PubMed

    Xu, Guangjing; Xu, Xiaochen; Yang, Fenglin; Liu, Sitong

    2011-01-15

    Partial nitrification was successfully achieved with addition of 5mM KClO(3) in the aerobic granules system. Batch tests demonstrated that KClO(3) selectively inhibited nitrite-oxidizing bacteria (NOB) but not ammonia-oxidizing bacteria (AOB). During stable partial nitrification, the influent pH was kept at 7.8-8.2, while the DO and temperature were not controlled in the SBR. When the NH(4)-N and COD levels were kept at 100mg/l and 400mg/l in the influent, the NH(4)-N and COD removal efficiencies reached 98.93% and 78.65%, respectively. The NO(2)-N accounted for 92.95% of the NO(χ)-N (NO(2)-N+NO(3)-N) in the effluent. Furthermore, about 90% of the chlorate was reduced to nontoxic chloride, thus it would not cause environmental problem. SEM showed that the main composition of the aerobic granules was bacilli and coccus bacteria. FISH analysis revealed that AOB became the dominant nitrifying bacteria, whereas NOB were detected only in low abundance. Chlorate could be used to control the development and maintenance of aerobic granules sludge for partial nitrification.

  7. Production of pesticide metabolites by oxidative reactions.

    PubMed

    Hodgson, E

    1982-08-01

    The cytochrome P-450-dependent monooxygenase system catalyzes a wide variety of oxidations of pesticide chemicals and related compounds. These reactions include epoxidation and aromatic hydroxylation, aliphatic hydroxylation, O-, N- and S-dealkylation, N-oxidation, oxidative deamination, S-oxidation, P-oxidation, desulfuration and ester cleavage and may result in either detoxication or activation of the pesticide. The current status of such reactions, relative to the production, in vivo, of biologically active intermediates in pesticide metabolism is summarized. More recently we have shown that the FAD-containing monooxygenase of mammalian liver (E.C.1.14.13.8), a xenobiotic metabolizing enzyme of broad specificity formerly known as an amine oxidase, is involved in a variety of pesticide oxidations. These include sulfoxidation of organophosphorus insecticides such as phorate and disulfoton, oxidative desulfuration of phosphonate insecticides such as fonofos and oxidation at the phosphorus atom in such compounds as the cotton defoliant, folex. The relative importance of the FAD-containing monooxygenase vis-a-vis the cytochrome P-450-dependent monooxygenase system is discussed, based on in vitro studies on purified enzymes.

  8. Induction of E. coli oh8Gua endonuclease by oxidative stress: its significance in aerobic life.

    PubMed

    Kim, H S; Park, Y W; Kasai, H; Nishimura, S; Park, C W; Choi, K H; Chung, M H

    1996-06-12

    The induction of 8-hydroxyguanine (oh8Gua) endonuclease, a DNA repair enzyme for an oxidatively modified guanine, oh8Gua was studied in various growth conditions in Escherichia coli (AB1157). Anaerobically grown E. coli were found to have a very low activity of this enzyme while aerobically grown cells showed activity about 20 times that of the anaerobic level. Under the same condition, superoxide dismutase (SOD) showed about 6-fold increase in activity. A shift in growth conditions from anaerobic to aerobic resulted in rapid induction of this enzyme, and this induction was blocked (but not completely) by chloramphenicol. It is indicated that molecular oxygen is an effective stimulator to the induction of this enzyme and its induction depends partly on protein synthesis. Superoxide-producing compounds such as paraquat and menadione also increased the activity of endonuclease as well as SOD, but H2O2 showed no effect. Thus, superoxides are also implied as a stimulator. In contrast, hyperoxia induced only SOD not the endonuclease. This induction of the endonuclease by hyperoxia was only observed in a SOD-deficient strain (QC774). The aerobic activity of the endonuclease in QC774 was the same as that of wild types (AB1157, GC4468). It is implied that the responsiveness of oh8Gua endonuclease to superoxides is less sensitive than that of SOD. The endonuclease was also induced by a temperature shift from 30 to 43 degrees C and treatment with nalidixic acid. Among the stimuli used, molecular oxygen seems to be most effective for its induction. The inducible nature of this enzyme will serve as an important mechanism for the protection of oxidative DNA damage in the aerobic environment.

  9. Nitrous oxide emissions from an aerobic granular sludge system treating low-strength ammonium wastewater.

    PubMed

    Gao, Mingming; Yang, Sen; Wang, Mingyu; Wang, Xin-Hua

    2016-11-01

    Aerobic granular sludge is a promising technology in wastewater treatment process. Its special microorganism structure could make the emissions of greenhouse gas nitrous oxide (N2O) more complicated. This study investigated the N2O emissions from a batch-fed aerobic granular sludge system during nitrification of low-strength synthetic ammonium wastewater. The N2O emission was 2.72 ± 0.52% of the oxidized ammonium during the whole anoxic-oxic sequencing batch reactor (SBR) cycle. Under nitrification batch test with sole ammonium substrate (50 mg N/L), N2O emission factor was 1.82% (N2ON/NH4(+)-Nox) and ammonia-oxidizing bacteria (AOB) was the responsible microorganism. The presence of high ammonium concentration (or high ammonium oxidation rate (AOR)) and accumulation of nitrite would lead to significant N2O emissions. AOB denitrification pathway was speculated to contribute more to the N2O emissions under nitrification conditions. While under simultaneous nitrification and denitrification condition with carbon source of 500 mg COD/L, the N2O emission factor increased to 2.76%. Both AOB and heterotrophic denitrifiers were responsible for N2O emission and heterotrophic denitrification enhances N2O emission. Step feeding of organic carbon source declined N2O emission factor to 1.60%, which underlined the role of storage substance consumption in N2O generation during denitrification.

  10. Effects of acute aerobic and anaerobic exercise on blood markers of oxidative stress.

    PubMed

    Bloomer, Richard J; Goldfarb, Allan H; Wideman, Laurie; McKenzie, Michael J; Consitt, Leslie A

    2005-05-01

    The purpose of this study was to compare oxidative modification of blood proteins, lipids, DNA, and glutathione in the 24 hours following aerobic and anaerobic exercise using similar muscle groups. Ten cross-trained men (24.3 +/- 3.8 years, [mean +/- SEM]) performed in random order 30 minutes of continuous cycling at 70% of Vo(2)max and intermittent dumbbell squatting at 70% of 1 repetition maximum (1RM), separated by 1-2 weeks, in a crossover design. Blood samples taken before, and immediately, 1, 6, and 24 hours postexercise were analyzed for plasma protein carbonyls (PC), plasma malondialdehyde (MDA), and whole-blood total (TGSH), oxidized (GSSG), and reduced (GSH) glutathione. Blood samples taken before and 24 hours postexercise were analyzed for serum 8-hydroxy-2'-deoxyguanosine (8-OHdG). PC values were greater at 6 and 24 hours postexercise compared with pre-exercise for squatting, with greater PC values at 24 hours postexercise for squatting compared with cycling (0.634 +/- 0.053 vs. 0.359 +/- 0.018 nM.mg protein(-1)). There was no significant interaction or main effects for MDA or 8-OHdG. GSSG experienced a short-lived increase and GSH a transient decrease immediately following both exercise modes. These data suggest that 30 minutes of aerobic and anaerobic exercise performed by young, cross-trained men (a) can increase certain biomarkers of oxidative stress in blood, (b) differentially affect oxidative stress biomarkers, and (c) result in a different magnitude of oxidation based on the macromolecule studied. Practical applications: While protein and glutathione oxidation was increased following acute exercise as performed in this study, future research may investigate methods of reducing macromolecule oxidation, possibly through the use of antioxidant therapy.

  11. Climatic thresholds for pedogenic iron oxides under aerobic conditions: Processes and their significance in paleoclimate reconstruction

    NASA Astrophysics Data System (ADS)

    Long, Xiaoyong; Ji, Junfeng; Barrón, Vidal; Torrent, José

    2016-10-01

    Iron oxides are widely distributed across the surface of the Earth as a result of the aerobic weathering of primary Fe-bearing minerals. Pedogenic iron oxides which consist mainly of hematite (Hm), goethite (Gt), maghemite (Mgh), are often concentrated synchronously in aerobic soils under low to moderate rainfall regimes. Magnetic susceptibility (χ) and redness, which respectively reflect the content of Mgh and Hm in soils, are considered reasonable pedogenic and climatic indicators in soil taxonomy and paleorainfall reconstruction. However, under high rainfall regimes, the grain growth of Mgh and transformation to Hm, combined with the prior formation of Gt under conditions of high relative humidity (RH), can result in magnetic reduction and dramatic yellowing of soils and sediments, which explains the existence of rainfall thresholds for Mgh and Hm at a large scale even before the pedogenic environment turns anaerobic. In order to capture the rainfall thresholds for Mgh and Hm occurring under aerobic conditions, we explored a tropical transect across a granitic region where the soil color turned from red to yellow under a wide rainfall range of 900-2200 mm/yr and a corresponding mean annual RH range of 77%-85%. We observed a lower rainfall threshold of ∼1500 mm/yr and a corresponding RH ∼80% for Mgh and Hm along this transect, as well as a higher rainfall threshold of ∼1700 mm/yr and a corresponding RH of ∼81% for Gt and total pedogenic iron oxides (citrate/bicarbonate/dithionite-extractable Fe, Fed). Cross-referencing with comparable studies in temperate and subtropical regions, we noted that the rainfall or RH thresholds for Fed and Hm or Mgh likewise increase with temperature. Moreover, the different thresholds for total and individual iron oxide phase indicates that a negative correlation between chemical weathering intensity and redness or χ in sediment sequences can occur under the prevalent climate regime just between their thresholds. Finally

  12. Effect of selected monoterpenes on methane oxidation, denitrification, and aerobic metabolism by bacteria in pure culture.

    PubMed

    Amaral, J A; Ekins, A; Richards, S R; Knowles, R

    1998-02-01

    Selected monoterpenes inhibited methane oxidation by methanotrophs (Methylosinus trichosporium OB3b, Methylobacter luteus), denitrification by environmental isolates, and aerobic metabolism by several heterotrophic pure cultures. Inhibition occurred to various extents and was transient. Complete inhibition of methane oxidation by Methylosinus trichosporium OB3b with 1.1 mM (-)-alpha-pinene lasted for more than 2 days with a culture of optical density of 0.05 before activity resumed. Inhibition was greater under conditions under which particulate methane monooxygenase was expressed. No apparent consumption or conversion of monoterpenes by methanotrophs was detected by gas chromatography, and the reason that transient inhibition occurs is not clear. Aerobic metabolism by several heterotrophs was much less sensitive than methanotrophy was; Escherichia coli (optical density, 0.01), for example, was not affected by up to 7.3 mM (-)-alpha-pinene. The degree of inhibition was monoterpene and species dependent. Denitrification by isolates from a polluted sediment was not inhibited by 3.7 mM (-)-alpha-pinene, gamma-terpinene, or beta-myrcene, whereas 50 to 100% inhibition was observed for isolates from a temperate swamp soil. The inhibitory effect of monoterpenes on methane oxidation was greatest with unsaturated, cyclic hydrocarbon forms [e.g., (-)-alpha-pinene, (S)-(-)-limonene, (R)-(+)-limonene, and gamma-terpinene]. Lower levels of inhibition occurred with oxide and alcohol derivatives [(R)-(+)-limonene oxide, alpha-pinene oxide, linalool, alpha-terpineol] and a noncyclic hydrocarbon (beta-myrcene). Isomers of pinene inhibited activity to different extents. Given their natural sources, monoterpenes may be significant factors affecting bacterial activities in nature.

  13. The effect of widespread early aerobic marine ecosystems on methane cycling and the Great Oxidation

    NASA Astrophysics Data System (ADS)

    Daines, Stuart J.; Lenton, Timothy M.

    2016-01-01

    The balance of evidence suggests that oxygenic photosynthesis had evolved by 3.0-2.7 Ga, several hundred million years prior to the Great Oxidation ≈2.4 Ga. Previous work has shown that if oxygenic photosynthesis spread globally prior to the Great Oxidation, this could have supported widespread aerobic ecosystems in the surface ocean, without oxidising the atmosphere. Here we use a suite of models to explore the implications for carbon cycling and the Great Oxidation. We find that recycling of oxygen and carbon within early aerobic marine ecosystems would have restricted the balanced fluxes of methane and oxygen escaping from the ocean, lowering the atmospheric concentration of methane in the Great Oxidation transition and its aftermath. This in turn would have minimised any bi-stability of atmospheric oxygen, by weakening a stabilising feedback on oxygen from hydrogen escape to space. The result would have been a more reversible and probably episodic rise of oxygen at the Great Oxidation transition, consistent with existing geochemical evidence. The resulting drop in methane levels to ≈10 ppm is consistent with climate cooling at the time but adds to the puzzle of what kept the rest of the Proterozoic warm. A key test of the scenario of abundant methanotrophy in oxygen oases before the Great Oxidation is its predicted effects on the organic carbon isotope (δ13Corg) record. Our open ocean general circulation model predicts δC13org ≈ - 30 to -45‰ consistent with most data from 2.65 to 2.45 Ga. However, values of δC13org ≈ - 50 ‰ require an extreme scenario such as concentrated methanotroph production where shelf-slope upwelling of methane-rich water met oxic shelf water.

  14. Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Anthony, K. Walter; Thalasso, F.

    2015-08-01

    Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH4) produced in lakes. Aerobic CH4 oxidation depends mainly on lake CH4 and oxygen (O2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcely reported in the literature. In the present study, we measured CH4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH4 and O2 concentrations. We found that in the winter, aerobic CH4 oxidation was mainly controlled by the dissolved O2 concentration, while in the summer it was controlled primarily by the CH4 concentration, which was scarce compared to dissolved O2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH4 cycling.

  15. Modeling of simultaneous denitrification--anaerobic digestion--organic matter aerobic oxidation and nitrification in an anoxic-anaerobic-aerobic compact filter reactor.

    PubMed

    Moya, Jaime; Huiliñir, César; Peredo, Karol; Aspé, Estrella; Roeckel, Marlene

    2012-08-31

    A mathematical model was developed for a compact anoxic-anaerobic-aerobic filter reactor with liquid recirculation for the treatment of fishing effluents. The model includes denitrification, anaerobic digestion, aerobic carbon oxidation and nitrification steps, as well as an evaluation of the liquid gas mass transfer and pH. The model was calibrated using one experimental condition at a recycling ratio (R)=10, and was validated with R equal to 2 and 0, with an organic concentration of 554±24 mg TOCL(-1), salinity of 24 g L(-1) and hydraulic retention time (HRT) of 2 d. Carbon total removal is higher than 98%, while maximum nitrogen removal is 62% using total nitrification in the aerobic zone, due to a higher quantity of NO(x) produced which were recirculated to the anoxic zone. In the aerobic zone, simultaneous nitrification and denitrification processes occur, because the diffusion limitations cause a low oxygen penetration in the biofilm. In the anoxic-anaerobic zone, denitrification or methanogenesis inhibition by DO (caused by the recycled oxygen) is not observed.

  16. Copper(II) complexes as catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine

    NASA Astrophysics Data System (ADS)

    Khattar, Raghvi; Yadav, Anjana; Mathur, Pavan

    2015-05-01

    Two new mononuclear copper(II) complexes [Cu (L) (NO3)2] (1) and [Cu (L) Br2] (2) where (L = bis(1-(pyridin-2-ylmethyl)-benzimidazol-2-ylmethyl)ether) are synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, UV-Visible, IR spectroscopy, EPR and cyclic voltammetry. The complexes exhibit different coordination structures; the E1/2 value of the complex (1) is found to be relatively more cathodic than that of complex (2). X-band EPR spectra at low temperature in DMF supports a tetragonally distorted complex (1) while complex (2) shows three different g values suggesting a rhombic geometry. These complexes were utilized as a catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine assisted by molecular oxygen. The initial rate of reaction is dependent on the concentration of Cu(II) complex as well as substrate, and was found to be higher for the nitrate bound complex, while presence of acetate anion acts as a mild inhibitor of the reaction, as it is likely to pick up protons generated during the course of reaction. The inhibition suggests that the generated protons are further required in another important catalytic step.

  17. Copper(II) complexes as catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine.

    PubMed

    Khattar, Raghvi; Yadav, Anjana; Mathur, Pavan

    2015-05-05

    Two new mononuclear copper(II) complexes [Cu (L) (NO3)2] (1) and [Cu (L) Br2] (2) where (L=bis(1-(pyridin-2-ylmethyl)-benzimidazol-2-ylmethyl)ether) are synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, UV-Visible, IR spectroscopy, EPR and cyclic voltammetry. The complexes exhibit different coordination structures; the E1/2 value of the complex (1) is found to be relatively more cathodic than that of complex (2). X-band EPR spectra at low temperature in DMF supports a tetragonally distorted complex (1) while complex (2) shows three different g values suggesting a rhombic geometry. These complexes were utilized as a catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine assisted by molecular oxygen. The initial rate of reaction is dependent on the concentration of Cu(II) complex as well as substrate, and was found to be higher for the nitrate bound complex, while presence of acetate anion acts as a mild inhibitor of the reaction, as it is likely to pick up protons generated during the course of reaction. The inhibition suggests that the generated protons are further required in another important catalytic step.

  18. Free radicals: how do we stand them? Anaerobic and aerobic free radical (chain) reactions involved in the use of fluorogenic probes and in biological systems.

    PubMed

    Liochev, Stefan I

    2014-01-01

    Biologically significant conclusions have been based on the use of fluorogenic and luminogenic probes for the detection of reactive species. The basic mechanisms of the processes involved have not been satisfactorily elucidated. In the present work, the mechanism of the enzyme and photosensitized oxidation of NAD(P)H by resorufin is analyzed and appears to involve both aerobic and anaerobic free radical chain reactions. There are two major fallouts of this analysis. Many of the conclusions about the participation of radicals based on the use of probes such as resorufin and Amplex red need reevaluation. It is also concluded that anaerobic free radical reactions may be biologically significant, and the possible existence of enzymatic systems to eliminate certain free radicals is discussed.

  19. Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?

    PubMed

    Zhang, Guoqi; Proni, Gloria; Zhao, Sherry; Constable, Edwin C; Housecroft, Catherine E; Neuburger, Markus; Zampese, Jennifer A

    2014-08-28

    The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1 : 1 : 1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)- in high yield. The single crystal structure of (R)- reveals a tetranuclear copper(ii) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)- and (S,R)- have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)- selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (770) in the air, while (S,R)- exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)- and (S,R)- in controlling the reactivity towards aerobic oxidation reactions is discussed.

  20. Oxidation state of BZ reaction mixtures.

    PubMed

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

    2006-01-12

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

  1. Aerobic methane oxidation and methanotroph community composition during seasonal stratification in Mono Lake, California (USA).

    PubMed

    Carini, Stephen; Bano, Nasreen; LeCleir, Gary; Joye, Samantha B

    2005-08-01

    Patterns of aerobic methane (CH4) oxidation and associated methanotroph community composition were investigated during the development of seasonal stratification in Mono Lake, California (USA). CH4 oxidation rates were measured using a tritiated CH4 radiotracer technique. Fluorescence in situ hybridization (FISH), denaturing gradient gel electrophoresis (DGGE) and sequence analysis were used to characterize methanotroph community composition. A temporally shifting zone of elevated CH4 oxidation (59-123 nM day(-1)) was consistently associated with a suboxycline, microaerophilic zone that migrated upwards in the water column as stratification progressed. FISH analysis revealed stable numbers of type I (4.1-9.3 x 10(5) cells ml(-1)) and type II (1.4-3.4 x 10(5) cells ml(-1)) methanotrophs over depth and over time. Denaturing gradient gel electrophoresis and sequence analysis indicated slight shifts in methanotroph community composition despite stable absolute cell numbers. Variable CH4 oxidation rates in the presence of a relatively stable methanotroph population suggested that zones of high CH4 oxidation resulted from an increase in activity of a subset of the existing methanotroph population. These results challenge existing paradigms suggesting that zones of elevated CH4 oxidation activity result from the accumulation of methanotrophic biomass and illustrate that type II methanotrophs may be an important component of the methanotroph population in saline and/or alkaline pelagic environments.

  2. Evaluation of Methyl Fluoride and Dimethyl Ether as Inhibitors of Aerobic Methane Oxidation

    PubMed Central

    Oremland, Ronald S.; Culbertson, Charles W.

    1992-01-01

    Methyl fluoride (MF) and dimethyl ether (DME) were effective inhibitors of aerobic methanotrophy in a variety of soils. MF and DME blocked consumption of CH4 as well as the oxidation of 14CH4 to 14CO2, but neither MF nor DME affected the oxidation of [14C]methanol or [14C]formate to 14CO2. Cooxidation of ethane and propane by methane-oxidizing soils was also inhibited by MF. Nitrification (ammonia oxidation) in soils was inhibited by both MF and DME. Production of N2O via nitrification was inhibited by MF; however, MF did not affect N2O production associated with denitrification. Methanogenesis was partially inhibited by MF but not by DME. Methane oxidation was ∼100-fold more sensitive to MF than was methanogenesis, indicating that an optimum concentration could be employed to selectively block methanotrophy. MF inhibited methane oxidation by cell suspensions of Methylococcus capsulatus; however, DME was a much less effective inhibitor. PMID:16348771

  3. Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

    NASA Astrophysics Data System (ADS)

    Mondal, Arijit; Mukherjee, Debkumar; Adhikary, Bibhutosh; Ahmed, Md Azharuddin

    2016-05-01

    Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4-6 nm) can also be prepared from PdCl2 and K2PtCl4, respectively, using the same surfactant but require high temperature ( 120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90-95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.

  4. Effect of Eight Weekly Aerobic Training Program on Auditory Reaction Time and MaxVO[subscript 2] in Visual Impairments

    ERIC Educational Resources Information Center

    Taskin, Cengiz

    2016-01-01

    The aim of study was to examine the effect of eight weekly aerobic exercises on auditory reaction time and MaxVO[subscript 2] in visual impairments. Forty visual impairment children that have blind 3 classification from the Turkey, experimental group; (age = 15.60 ± 1.10 years; height = 164.15 ± 4.88 cm; weight = 66.60 ± 4.77 kg) for twenty…

  5. Antibacterial Action of Nitric Oxide-Releasing Chitosan Oligosaccharides against Pseudomonas aeruginosa under Aerobic and Anaerobic Conditions

    PubMed Central

    Reighard, Katelyn P.

    2015-01-01

    Chitosan oligosaccharides were modified with N-diazeniumdiolates to yield biocompatible nitric oxide (NO) donor scaffolds. The minimum bactericidal concentrations and MICs of the NO donors against Pseudomonas aeruginosa were compared under aerobic and anaerobic conditions. Differential antibacterial activities were primarily the result of NO scavenging by oxygen under aerobic environments and not changes in bacterial physiology. Bacterial killing was also tested against nonmucoid and mucoid biofilms and compared to that of tobramycin. Smaller NO payloads were required to eradicate P. aeruginosa biofilms under anaerobic versus aerobic conditions. Under oxygen-free environments, the NO treatment was 10-fold more effective at killing biofilms than tobramycin. These results demonstrate the potential utility of NO-releasing chitosan oligosaccharides under both aerobic and anaerobic environments. PMID:26239983

  6. Combined Fenton oxidation and aerobic biological processes for treating a surfactant wastewater containing abundant sulfate.

    PubMed

    Wang, Xiao-Jun; Song, Yang; Mai, Jun-Sheng

    2008-12-30

    The present study is to investigate the treatment of a surfactant wastewater containing abundant sulfate by Fenton oxidation and aerobic biological processes. The operating conditions have been optimized. Working at an initial pH value of 8, a Fe2+ dosage of 600mgL(-1) and a H2O2 dosage of 120mgL(-1), the chemical oxidation demand (COD) and linear alkylbenzene sulfonate (LAS) were decreased from 1500 and 490mgL(-1) to 230 and 23mgL(-1) after 40min of Fenton oxidation, respectively. Advanced oxidation pretreatment using Fenton reagent was very effective at enhancing the biodegradability of this kind of wastewater. The wastewater was further treated by a bio-chemical treatment process based on an immobilized biomass reactor with a hydraulic detention time (HRT) of 20h after Fenton oxidation pretreatment under the optimal operating conditions. It was found that the COD and LAS of the final effluent were less than 100 and 5mgL(-1), corresponding to a removal efficiencies of over 94% and 99%, respectively.

  7. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    PubMed Central

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  8. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters.

    PubMed

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the "structure-activity" relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au(3+) ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  9. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  10. Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

    PubMed

    Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

    2017-03-06

    Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW11O39](7-) (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O2) oxidation of CO to CO2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O2 + H2O = CO2 + H2O2. After control experiments verified that the H2O2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H2O2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K(+) salts): 1, the Wells-Dawson ion [α-P2W18O62](6-) (2) and the monodefect Keggin anion [α-SiW11O39](8-) (3) revealed that binding energies of electrons in the Au 4f7/2 and 4f5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O2. Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

  11. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation.

    PubMed

    Könneke, Martin; Schubert, Daniel M; Brown, Philip C; Hügler, Michael; Standfest, Sonja; Schwander, Thomas; Schada von Borzyskowski, Lennart; Erb, Tobias J; Stahl, David A; Berg, Ivan A

    2014-06-03

    Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments.

  12. Oxidative stress and inflammation response following aerobic exercise: role of ethnicity.

    PubMed

    McKenzie, M J; Goldfarb, A; Garten, R S; Vervaecke, L

    2014-09-01

    African-Americans are at a significantly greater risk for developing several diseases and conditions. These conditions often have underlying oxidative stress mechanisms. Therefore the purpose of this investigation was to ascertain the post-exercise oxidative response to a single bout of aerobic exercise in African-American and Caucasian college-age females. A total of 10 African-American and 10 Caucasian females completed the study. Each subject had her VO2 max measured while exercising on a treadmill. A week later, each subject returned to the laboratory and performed a 30-min run at 70% of her VO2max. Blood samples were taken immediately prior to and following exercise for analysis. Lipid hydroperoxides, protein carbonyls, malondialdehyde, xanthine oxidase, glutathione in the reduced (GSH) and oxidized (GSSG) forms, TNFα and interleukin 6 were measured from blood taken before and after exercise. Significance was set at p≤0.05 a priori. Xanthine oxidase was the only measure that did not significantly increase following exercise. All other markers showed a significant elevation in response to the exercise bout with no difference between groups except that the Caucasian group had significantly higher malondialdehyde post-exercise compared to the African-American group. This cohort of college-age African-American and Caucasian females showed little difference in their response to a single 30-min run at 70% of their max in the markers of oxidative stress within the blood.

  13. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation

    PubMed Central

    Könneke, Martin; Schubert, Daniel M.; Brown, Philip C.; Hügler, Michael; Standfest, Sonja; Schwander, Thomas; Schada von Borzyskowski, Lennart; Erb, Tobias J.; Stahl, David A.; Berg, Ivan A.

    2014-01-01

    Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments. PMID:24843170

  14. Metabolic reprogramming during neuronal differentiation from aerobic glycolysis to neuronal oxidative phosphorylation

    PubMed Central

    Zheng, Xinde; Boyer, Leah; Jin, Mingji; Mertens, Jerome; Kim, Yongsung; Ma, Li; Ma, Li; Hamm, Michael; Gage, Fred H; Hunter, Tony

    2016-01-01

    How metabolism is reprogrammed during neuronal differentiation is unknown. We found that the loss of hexokinase (HK2) and lactate dehydrogenase (LDHA) expression, together with a switch in pyruvate kinase gene splicing from PKM2 to PKM1, marks the transition from aerobic glycolysis in neural progenitor cells (NPC) to neuronal oxidative phosphorylation. The protein levels of c-MYC and N-MYC, transcriptional activators of the HK2 and LDHA genes, decrease dramatically. Constitutive expression of HK2 and LDHA during differentiation leads to neuronal cell death, indicating that the shut-off aerobic glycolysis is essential for neuronal survival. The metabolic regulators PGC-1α and ERRγ increase significantly upon neuronal differentiation to sustain the transcription of metabolic and mitochondrial genes, whose levels are unchanged compared to NPCs, revealing distinct transcriptional regulation of metabolic genes in the proliferation and post-mitotic differentiation states. Mitochondrial mass increases proportionally with neuronal mass growth, indicating an unknown mechanism linking mitochondrial biogenesis to cell size. DOI: http://dx.doi.org/10.7554/eLife.13374.001 PMID:27282387

  15. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph

    PubMed Central

    Harrold, Zoë R.; Skidmore, Mark L.; Hamilton, Trinity L.; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E.

    2015-01-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O32−), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O32− that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO42−) several orders of magnitude higher than those of S2O32−. Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O32−, CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O32− as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O32−-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O32− by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  16. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2015-12-28

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment.

  17. A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

    PubMed

    Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

    2016-01-04

    Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance.

  18. Complete genome sequence of Methylocystis sp. strain SC2, an aerobic methanotroph with high-affinity methane oxidation potential.

    PubMed

    Dam, Bomba; Dam, Somasri; Kube, Michael; Reinhardt, Richard; Liesack, Werner

    2012-11-01

    Methylocystis sp. strain SC2 is an aerobic type II methanotroph isolated from a highly polluted aquifer in Germany. A specific trait of the SC2 strain is the expression of two isozymes of particulate methane monooxygenase with different methane oxidation kinetics. Here we report the complete genome sequence of this methanotroph that contains not only a circular chromosome but also two large plasmids.

  19. Heterogeneous reaction of ozone with aluminum oxide

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.

    1976-01-01

    Rates and collision efficiencies for ozone decomposition on aluminum oxide surfaces were determined. Samples were characterized by BET surface area, X-ray diffraction, particle size, and chemical analysis. Collision efficiencies were found to be between 2 times 10 to the -10 power and 2 times 10 to the -9 power. This is many orders of magnitude below the value of 0.000001 to 0.00001 needed for appreciable long-term ozone loss in the stratosphere. An activation energy of 7.2 kcal/mole was found for the heterogeneous reaction between -40 C and 40 C. Effects of pore diffusion, outgassing and treatment of the aluminum oxide with several chemical species were also investigated.

  20. Aerobic nitric oxide-induced thiol nitrosation in the presence and absence of magnesium cations.

    PubMed

    Kolesnik, Bernd; Heine, Christian L; Schmidt, Renate; Schmidt, Kurt; Mayer, Bernd; Gorren, Antonius C F

    2014-11-01

    Although different routes for the S-nitrosation of cysteinyl residues have been proposed, the main in vivo pathway is unknown. We recently demonstrated that direct (as opposed to autoxidation-mediated) aerobic nitrosation of glutathione is surprisingly efficient, especially in the presence of Mg(2+). In the present study we investigated this reaction in greater detail. From the rates of NO decay and the yields of nitrosoglutathione (GSNO) we estimated values for the apparent rate constants of 8.9 ± 0.4 and 0.55 ± 0.06 M(-1)s(-1) in the presence and absence of Mg(2+). The maximum yield of GSNO was close to 100% in the presence of Mg(2+) but only about half as high in its absence. From this observation we conclude that, in the absence of Mg(2+), nitrosation starts by formation of a complex between NO and O2, which then reacts with the thiol. Omission of superoxide dismutase (SOD) reduced by half the GSNO yield in the absence of Mg(2+), demonstrating O2(-) formation. The reaction in the presence of Mg(2+) seems to involve formation of a Mg(2+)•glutathione (GSH) complex. SOD did not affect Mg(2+)-stimulated nitrosation, suggesting that no O2(-) is formed in that reaction. Replacing GSH with other thiols revealed that reaction rates increased with the pKa of the thiol, suggesting that the nucleophilicity of the thiol is crucial for the reaction, but that the thiol need not be deprotonated. We propose that in cells Mg(2+)-stimulated NO/O2-induced nitrosothiol formation may be a physiologically relevant reaction.

  1. Oxidative stability of pork emulsion containing tomato products and pink guava pulp during refrigerated aerobic storage.

    PubMed

    Joseph, Serlene; Chatli, Manish K; Biswas, Ashim K; Sahoo, Jhari

    2014-11-01

    Lipid oxidation-induced quality problems can be minimized with the use of natural antioxidants. Antioxidant potential of tomato puree (10 %; T-1), tomato pulp (12.5 %; T-2), lyophilized tomato peel (6 %; T-3), and pink guava pulp (10 %; T-4) was evaluated in raw pork emulsion during refrigerated storage for 9 days under aerobic packaging. The lycopene and β-carotene content varied in pork emulsion as T-3 > T-1 > T-2 > T-4 and decreased (P < 0.05) during storage. The surface redness (a* value) increased (P < 0.05) with the incorporation of tomato products and pink guava pulp. Furthermore, metmyoglobin formation and lipid oxidation were lower (P < 0.05) in tomato- and guava-treated emulsions than in control. Overall, incorporation of tomato products and pink guava pulp improved the visual colour and odour scores of raw pork emulsion. These results indicated that tomato products and guava pulp can be utilized as sources of natural antioxidants in raw pork products to minimize lipid oxidation, off-odour development, and surface discolouration.

  2. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    PubMed Central

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  3. Preparation and catalytic activity of poly(N-vinyl-2-pyrrolidone)-protected Au nanoparticles for the aerobic oxidation of glucose.

    PubMed

    Zhang, Haijun; Li, Wenqi; Gu, Yajun; Zhang, Shaowei

    2014-08-01

    PVP-protected Au nanoparticles (NPs) for the aerobic oxidation of glucose were prepared by using NaBH4 reduction method. The effects of processing parameters such as Au3+ ion concentration, reaction temperature, ratio of NaBH4 or PVP to Au3+, and solvent composition on their particle sizes and catalytic activities were studied in detail and the synthesis conditions optimized. As-prepared Au NPs possessed a FCC structure, with an average size varying from about 100 to 2.6 nm depending on their preparation conditions. The size changes affected their catalytic activities in the aerobic oxidation of glucose. The Au NPs with the average size of 2.6 nm prepared under the optimal conditions showed a high instantaneous catalytic activity as well as a high long-time stability. Based on the kinetic study on the glucose oxidation over the PVP-protected Au NPs, the corresponding apparent activation energy was determined as 82 kJ mol(-1).

  4. Microbiology and potential applications of aerobic methane oxidation coupled to denitrification (AME-D) process: A review.

    PubMed

    Zhu, Jing; Wang, Qian; Yuan, Mengdong; Tan, Giin-Yu Amy; Sun, Faqian; Wang, Cheng; Wu, Weixiang; Lee, Po-Heng

    2016-03-01

    Aerobic methane oxidation coupled to denitrification (AME-D) is an important link between the global methane and nitrogen cycles. This mini-review updates discoveries regarding aerobic methanotrophs and denitrifiers, as a prelude to spotlight the microbial mechanism and the potential applications of AME-D. Until recently, AME-D was thought to be accomplished by a microbial consortium where denitrifying bacteria utilize carbon intermediates, which are excreted by aerobic methanotrophs, as energy and carbon sources. Potential carbon intermediates include methanol, citrate and acetate. This mini-review presents microbial thermodynamic estimations and postulates that methanol is the ideal electron donor for denitrification, and may serve as a trophic link between methanotrophic bacteria and denitrifiers. More excitingly, new discoveries have revealed that AME-D is not only confined to the conventional synergism between methanotrophic bacteria and denitrifiers. Specifically, an obligate aerobic methanotrophic bacterium, Methylomonas denitrificans FJG1, has been demonstrated to couple partial denitrification with methane oxidation, under hypoxia conditions, releasing nitrous oxide as a terminal product. This finding not only substantially advances the understanding of AME-D mechanism, but also implies an important but unknown role of aerobic methanotrophs in global climate change through their influence on both the methane and nitrogen cycles in ecosystems. Hence, further investigation on AME-D microbiology and mechanism is essential to better understand global climate issues and to develop niche biotechnological solutions. This mini-review also presents traditional microbial techniques, such as pure cultivation and stable isotope probing, and powerful microbial techniques, such as (meta-) genomics and (meta-) transcriptomics, for deciphering linked methane oxidation and denitrification. Although AME-D has immense potential for nitrogen removal from wastewater, drinking

  5. Release of ANP and fat oxidation in overweight persons during aerobic exercise in water.

    PubMed

    Fenzl, M; Schnizer, W; Aebli, N; Schlegel, C; Villiger, B; Disch, A; Gredig, J; Zaugg, T; Krebs, J

    2013-09-01

    Exercise in water compared to land-based exercise (LE) results in a higher release of natriuretic peptides, which are involved in the regulation of exercise-induced adipose tissue lipolysis. The present study was performed to compare the release of atrial natriuretic peptide (ANP) and free fatty acids (FFA) during prolonged aerobic water-based exercise (WE) with the release after an identical LE. 14 untrained overweight subjects performed 2 steady state workload tests on the same ergometer in water and on land. Before and after exercise, venous blood samples were collected for measuring ANP, FFA, epinephrine, norepinephrine, insulin and glucose. The respiratory exchange ratio (RER) was determined for fat oxidation.The exercises resulted in a significant increase in ANP in LE (61%) and in WE (177%), and FFA increased about 3-fold in LE and WE with no significant difference between the groups. Epinephrine increased, while insulin decreased similarly in both groups. The RER values decreased during the exercises, but there was no significant difference between LE and WE. In conclusion, the higher ANP concentrations in WE had no additional effect on lipid mobilization, FFA release and fat oxidation. Moderate-intensity exercises in water offer no benefit regarding adipose tissue lipolysis in comparison to LE.

  6. Treatment of leather industry wastewater by aerobic biological and Fenton oxidation process.

    PubMed

    Mandal, Tamal; Dasgupta, Dalia; Mandal, Subhasis; Datta, Siddhartha

    2010-08-15

    Degradation of leather industry wastewater by sole aerobic treatment incorporating Thiobacillus ferrooxidans, Fenton's reagents, and combined treatment was investigated in this study. The sole treatment by Fenton's oxidation involving the introduction of 6g FeSO(4) and 266 g H(2)O(2) in a liter of wastewater at pH of 3.5 and 30 degrees C for 30 min at batch conditions reduced COD, BOD(5), sulfide, total chromium and color up to 69%, 72%, 88%, 5%, 100% and T. ferrooxidans alone showed maximum reduction to an extent of 77, 80, 85, 52, 89, respectively, in 21 d treatment at pH 2.5, FeSO(4) 16 g/L and temperature of 30 degrees C. The combined treatment at batch conditions involving 30 min chemical treatment by Fenton's oxidation followed by 72 h biochemical treatment by T. ferrooxidans at batch conditions gave rise up to 93%, 98%, 72%, 62% and 100% removal efficiencies of COD, BOD, sulfide, chromium and color at pH of 2.5 and 30 degrees C. Decrease in photo absorption of the Fenton's reagent treated samples, as compared to the banks, at 280, 350 and 470 nm wave lengths was observed. This may be the key factor for stimulating the biodegradation by T. ferrooxidans.

  7. Onset of the aerobic nitrogen cycle during the Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Zerkle, Aubrey L.; Poulton, Simon W.; Newton, Robert J.; Mettam, Colin; Claire, Mark W.; Bekker, Andrey; Junium, Christopher K.

    2017-02-01

    The rise of oxygen on the early Earth (about 2.4 billion years ago) caused a reorganization of marine nutrient cycles, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event). Our data fill a gap of about 400 million years in the temporal 15N/14N record and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.

  8. Onset of the aerobic nitrogen cycle during the Great Oxidation Event.

    PubMed

    Zerkle, Aubrey L; Poulton, Simon W; Newton, Robert J; Mettam, Colin; Claire, Mark W; Bekker, Andrey; Junium, Christopher K

    2017-02-23

    The rise of oxygen on the early Earth (about 2.4 billion years ago) caused a reorganization of marine nutrient cycles, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope ((15)N/(14)N) values from approximately 2.31-billion-year-old shales of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event). Our data fill a gap of about 400 million years in the temporal (15)N/(14)N record and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.

  9. The aerobic oxidation of a Pd(II) dimethyl complex leads to selective ethane elimination from a Pd(III) intermediate.

    PubMed

    Khusnutdinova, Julia R; Rath, Nigam P; Mirica, Liviu M

    2012-02-01

    Oxidation of the Pd(II) complex (N4)Pd(II)Me(2) (N4 = N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane) with O(2) or ROOH (R = H, tert-butyl, cumyl) produces the Pd(III) species [(N4)Pd(III)Me(2)](+), followed by selective formation of ethane and the monomethyl complex (N4)Pd(II)Me(OH). Cyclic voltammetry studies and use of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap suggest an inner-sphere mechanism for (N4)Pd(II)Me(2) oxidation by O(2) to generate a Pd(III)-superoxide intermediate. In addition, reaction of (N4)Pd(II)Me(2) with cumene hydroperoxide involves a heterolytic O-O bond cleavage, implying a two-electron oxidation of the Pd(II) precursor and formation of a transient Pd(IV) intermediate. Mechanistic studies of the C-C bond formation steps and crossover experiments are consistent with a nonradical mechanism that involves methyl group transfer and transient formation of a Pd(IV) species. Moreover, the (N4)Pd(II)Me(OH) complex formed upon ethane elimination reacts with weakly acidic C-H bonds of acetone and terminal alkynes, leading to formation of a new Pd(II)-C bond. Overall, this study represents the first example of C-C bond formation upon aerobic oxidation of a Pd(II) dimethyl complex, with implications in the development of Pd catalysts for aerobic oxidative coupling of C-H bonds.

  10. Variable carbon isotope fractionation expressed by aerobic CH 4-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Templeton, Alexis S.; Chu, Kung-Hui; Alvarez-Cohen, Lisa; Conrad, Mark E.

    2006-04-01

    Carbon isotope fractionation factors reported for aerobic bacterial oxidation of CH 4(α) range from 1.003 to 1.039. In a series of experiments designed to monitor changes in the carbon isotopic fractionation of CH 4 by Type I and Type II methanotrophic bacteria, we found that the magnitude of fractionation was largely due to the first oxidation step catalyzed by methane monooxygenase (MMO). The most important factor that modulates the (α) is the fraction of the total CH 4 oxidized per unit time, which strongly correlates to the cell density of the growth cultures under constant flow conditions. At cell densities of less than 0.1 g/L, fractionation factors greater than 1.03 were observed, whereas at cell densities greater than 0.5 g/L the fractionation factors decreased to as low as 1.002. At low cell densities, low concentrations of MMO limit the amount of CH 4 oxidized, while at higher cell densities, the overall rates of CH 4 oxidation increase sufficiently that diffusion of CH 4 from the gaseous to dissolved state and into the cells is likely the rate-determining step. Thus, the residual CH 4 is more fractionated at low cell densities, when only a small fraction of the total CH 4 has been oxidized, than at high cell densities, when up to 40% of the influent CH 4 has been utilized. Therefore, since Rayleigh distillation behavior is not observed, δ 13C values of the residual CH 4 cannot be used to infer the amount oxidized in either laboratory or field-studies. The measured (α) was the same for both Type I and Type II methanotrophs expressing particulate or soluble MMO. However, large differences in the δ 13C values of biomass produced by the two types of methanotrophs were observed. Methylosinus trichosporium OB3b (Type II) produced biomass with δ 13C values about 15‰ higher than the dissimilated CO 2, whereas Methylomonas methanica (Type I) produced biomass with δ 13C values only about 6‰ higher than the CO 2. These effects were independent of the

  11. Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

    SciTech Connect

    Xie, Jiahan; Yin, Kehua; Serov, Alexey; Artyushkova, Kateryna; Pham, Hien N.; Sang, Xiahan; Unocic, Raymond R.; Atanassov, Plamen; Datye, Abhaya K.; Davis, Robert J.

    2016-12-15

    Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.

  12. Oxygen-transfer reactions of methylrhenium oxides

    SciTech Connect

    Abu-Omar, M.M.; Espenson, J.H.; Appelman, E.H.

    1996-12-18

    Methylrhenium dioxide, CH{sub 3}ReO{sub 2} (or MDO), is produced from methylrhenium trioxide, CH{sub 3}ReO{sub 3} (or MTO), and hypophosphorous acid in acidic aqueous medium. Its mechanism is discussed in light of MTO`s coordination ability and the inverse kinetic isotope effect (kie): H{sub 2}P(O)OH, k = 0.028 L mol{sup -1} s{sup -1}; D{sub 2}P(O)OH, k = 0.039 L mol{sup -1} s{sup -1}. The Re(V) complex, MDO, reduces perchlorate and other inorganic oxoanions (XO{sub n}{sup -}, where X = Cl, Br, or I and N = 4 or 3). The rate is controlled by the first oxygen abstraction from perchlorate to give chlorate, with a second-order rate constant at pH 0 and 25 {degrees}C of 7.3 L mol{sup -1} s{sup -1}. Organic oxygen-donors such as sulfoxides and pyridine N-oxides oxidize MDO to MTO as do metal oxo complexes: VO{sup 2+}{sub (aq)}, VO{sub 2}{sup +}{sub (aq)}, HOMoO{sub 2}{sup +}{sub (aq)}, and MnO{sub 4}{sup -}. The reaction between V{sup 2+}{sub (aq)} with MTO and the reduction of VO{sup 2+} with MDO made it possible to determine the free energy for MDO/MTO. Oxygen-atom transfer from oxygen-donors to MDO involves nucleophilic attack of X-O on the electrophilic Re(V) center of MDO; the reaction proceeds via an [MDO{center_dot}XO] adduct, which is supported by the saturation kinetics observed for some. The parameters that control and facilitate the kinetics of such oxygen-transfer processes are suggested and include the force constant for the asymmetric stretching of the element-oxygen bond.

  13. Techno-economic evaluation of the application of ozone-oxidation in a full-scale aerobic digestion plant.

    PubMed

    Chiavola, Agostina; D'Amato, Emilio; Gori, Riccardo; Lubello, Claudio; Sirini, Piero

    2013-04-01

    This paper deals with the application of the ozone-oxidation in a full scale aerobic sludge digester. Ozonation was applied continuously to a fraction of the biological sludge extracted from the digestion unit; the ozonated sludge was then recirculated to the same digester. Three different ozone flow rates were tested (60,500 and 670g O3 h(-1)) and their effects evaluated in terms of variation of the total and soluble fractions of COD, nitrogen and phosphorous, of total and volatile suspended solids concentrations and Sludge Volume Index in the aerobic digestion unit. During the 7-month operation of the ozonation process, it was observed an appreciable improvement of the aerobic digestion efficiency (up to about 20% under the optimal conditions) and of the sludge settleability properties. These results determined an average reduction of about 60% in the biological sludge extracted from the plant and delivered to final disposal. A thorough economic analysis showed that this reduction allowed to achieve a significant cost saving for the plant with respect to the previous years operated without ozonation. Furthermore, it was determined the threshold disposal cost above which implementation of the ozone oxidation in the aerobic digestion units of similar WWTPs becomes economically convenient (about 60€t(-1) of sludge).

  14. N-Heterocyclic Carbene Complexes in Oxidation Reactions

    NASA Astrophysics Data System (ADS)

    Jurčík, Václav; Cazin, Catherine S. J.

    This chapter describes applications of N-heterocyclic carbenes (NHCs) in oxidation chemistry. The strong σ-donation capabilities of the NHCs allow an efficient stabilisation of metal centres in high oxidation states, while high metal-NHC bond dissociation energies suppress their oxidative decomposition. These properties make NHCs ideal ligands for oxidation processes. The first part of this chapter is dedicated to the reactivity of NHC-metal complexes towards molecular oxygen whilst the second half highlights all oxidation reactions catalysed by such complexes. These include oxidation of alcohols and olefins, oxidative cyclisations, hydrations of alkynes and nitriles, oxidative cleavage of alkenes and the oxidation of methane.

  15. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  16. C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

    PubMed Central

    Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

    2014-01-01

    Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway. PMID:24413448

  17. Treatment of high salt oxidized modified starch waste water using micro-electrolysis, two-phase anaerobic aerobic and electrolysis for reuse

    NASA Astrophysics Data System (ADS)

    Yi, Xuenong; Wang, Yulin

    2016-08-01

    A combined process of micro-electrolysis, two-phase anaerobic, aerobic and electrolysis was investigated for the treatment of oxidized modified starch wastewater (OMSW). Optimum ranges for important operating variables were experimentally determined and the treated water was tested for reuse in the production process of corn starch. The optimum hydraulic retention time (HRT) of micro-electrolysis, methanation reactor, aerobic process and electrolysis process were 5, 24, 12 and 3 h, respectively. The addition of iron-carbon fillers to the acidification reactor was 200 mg/L while the best current density of electrolysis was 300 A/m2. The biodegradability was improved from 0.12 to 0.34 by micro-electrolysis. The whole treatment was found to be effective with removal of 96 % of the chemical oxygen demand (COD), 0.71 L/day of methane energy recovery. In addition, active chlorine production (15,720 mg/L) was obtained by electrolysis. The advantage of this hybrid process is that, through appropriate control of reaction conditions, effect from high concentration of salt on the treatment was avoided. Moreover, the process also produced the material needed in the production of oxidized starch while remaining emission-free and solved the problem of high process cost.

  18. C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

    NASA Astrophysics Data System (ADS)

    Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

    2014-01-01

    Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

  19. C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol.

    PubMed

    Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

    2014-01-13

    Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C(3)N(4)) and Keggin-type polyoxometalate H(5)PMo(10)V(2)O(40) (PMoV(2)) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C(3)N(4) and O2 by the V-O-V structure of PMoV(2). This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

  20. 40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic). 721.10375... Substances § 721.10375 Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (PMN P-10-200)...

  1. 40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic). 721.10375... Substances § 721.10375 Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (PMN P-10-200)...

  2. 40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic). 721.10375... Substances § 721.10375 Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (PMN P-10-200)...

  3. [Enhanced Resistance of Pea Plants to Oxidative: Stress Caused by Paraquat during Colonization by Aerobic Methylobacteria].

    PubMed

    Agafonova, N V; Doronina, N Y; Trotsenko, Yu A

    2016-01-01

    The influence of colonization of the pea (Pisum sativum L.) by aerobic methylobacteria of five different species (Methylophilus flavus Ship, Methylobacterium extorquens G10, Methylobacillus arboreus Iva, Methylopila musalis MUSA, Methylopila turkiensis Sidel) on plant resistance to paraquat-induced stresses has been studied. The normal conditions of pea colonization by methylobacteria were characterized by a decrease in the activity of antioxidant enzymes (superoxide dismutase, catalase, and peroxidases) and in the concentrations of endogenous H2O2, proline, and malonic dialdehyde, which is a product of lipid peroxidation and indicator of damage to plant cell membranes, and an increase in the activity of the photosynthetic apparatus (the content of chlorophylls a, b and carotenoids). In the presence of paraquat, the colonized plants had higher activities of antioxidant enzymes, stable photosynthetic indices, and a less intensive accumulation of the products of lipid peroxidation as compared to noncolonized plants. Thus, colonization by methylobacteria considerably increased the adaptive protection of pea plants to the paraquat-induced oxidative stress.

  4. Praseodymium incorporated AIPO-5 molecular sieves for aerobic oxidation of ethylbenzene.

    PubMed

    Sundaravel, B; Babu, C M; Palanisamy, B; Palanichamy, M; Shanthi, K; Murugesan, V

    2013-04-01

    PrAlPO-5 with (Al + P)/Pr ratios of 25, 50, 75 and 100 molecular sieves were successfully synthesized by hydrothermal method. These molecular sieves were characterised using XPS, TPD-NH3, ex-situ pyridine adsorbed IR, TPR, TGA, 27Al and 31P MAS-NMR and ESR studies. The incorporation of praseodymium in the framework of AlPO-5 was confirmed by XRD, DRS UV-vis and 27Al and 31P MAS-NMR analysis. ESR spectrum showed the presence of adsorbed oxygen. The nature and strength of acid sites were identified by ex-situ pyridine adsorbed IR and TPD-NH3. The BET surface area was found to be in the range of 238-272 m2 g(-1). The catalytic activity of the molecular sieves was tested for the liquid phase aerobic oxidation of ethylbenzene. Acetophenone was found to be the major product with more than 90% ethylbenzene conversion. ICP-OES analysis revealed the presence of praseodymium intact in the framework of AlPO-5 up to five cycles.

  5. Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

    DOE PAGES

    Xie, Jiahan; Yin, Kehua; Serov, Alexey; ...

    2016-12-15

    Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidationmore » catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.« less

  6. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

    DOE PAGES

    Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; ...

    2016-09-23

    Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) andmore » 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.« less

  7. Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

    SciTech Connect

    Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; Angelici, Robert J.; Woo, L. Keith

    2016-09-23

    Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.

  8. Investigating the chemical and isotopic kinetics of aerobic methane oxidation in the Northern US Atlantic Margin, Hudson Canyon

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Shiller, A. M.; Redmond, M. C.; Arrington, E. C.; Valentine, D. L.

    2015-12-01

    Recent discoveries of methane seepage along the US Atlantic margin have led to speculation on the fate of the released methane. Here we examine the kinetics of aerobic methane oxidation to gain a fundamental understanding of this methane sink. In order to look at this process in its entirety, a unique mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) to monitor in real time the chemical and isotopic changes involved with aerobic methane oxidation. This system measures changes in methane, carbon dioxide, and oxygen concentrations as well as the stable carbon isotopes of methane and carbon dioxide with time. In addition samples are strategically removed to characterize trace metals, nutrients, cell counts, and microbial community genetics. This presentation will detail the results obtained from samples collected inside the Hudson Canyon at the edge of the methane clathrate stability zone and outside the Hudson Canyon, not influenced by the methane seepage. These results show that in both environments along the Atlantic margin, methane was consumed aggressively but the timing of consumption varied based on location. In addition, these results are leading to insights into the chemical requirements needed for aerobic methane oxidation and the resulting isotopic fractionation.

  9. Flexible bacterial strains that oxidize arsenite in anoxic or aerobic conditions and utilize hydrogen or acetate as alternative electron donors.

    PubMed

    Rodríguez-Freire, Lucía; Sun, Wenjie; Sierra-Alvarez, Reyes; Field, Jim A

    2012-02-01

    Arsenic is a carcinogenic compound widely distributed in the groundwater around the world. The fate of arsenic in groundwater depends on the activity of microorganisms either by oxidizing arsenite (As(III)), or by reducing arsenate (As(V)). Because of the higher toxicity and mobility of As(III) compared to As(V), microbial-catalyzed oxidation of As(III) to As(V) can lower the environmental impact of arsenic. Although aerobic As(III)-oxidizing bacteria are well known, anoxic oxidation of As(III) with nitrate as electron acceptor has also been shown to occur. In this study, three As(III)-oxidizing bacterial strains, Azoarcus sp. strain EC1-pb1, Azoarcus sp. strain EC3-pb1 and Diaphorobacter sp. strain MC-pb1, have been characterized. Each strain was tested for its ability to oxidize As(III) with four different electron acceptors, nitrate, nitrite, chlorate and oxygen. Complete As(III) oxidation was achieved with both nitrate and oxygen, demonstrating the novel ability of these bacterial strains to oxidize As(III) in either anoxic or aerobic conditions. Nitrate was only reduced to nitrite. Different electron donors were used to study their suitability in supporting nitrate reduction. Hydrogen and acetate were readily utilized by all the cultures. The flexibility of these As(III)-oxidizing bacteria to use oxygen and nitrate to oxidize As(III) as well as organic and inorganic substrates as alternative electron donors explains their presence in non-arsenic-contaminated environments. The findings suggest that at least some As(III)-oxidizing bacteria are flexible with respect to electron-acceptors and electron-donors and that they are potentially widespread in low arsenic concentration environments.

  10. Tunable porosity of crosslinked-polyhedral oligomeric silsesquioxane (POSS) supports for palladium-catalyzed aerobic alcohol oxidation in water.

    PubMed

    Sangtrirutnugul, Preeyanuch; Chaiprasert, Thanawat; Hunsiri, Warodom; Jitjaroendee, Thanudkit; Songkhum, Patsaya; Laohhasurayotin, Kritapas; Osotchan, Tanakorn; Ervithayasuporn, Vuthichai

    2017-03-24

    Polyhedral oligomeric silsesquioxane (POSS)-based materials, poly-POSS-Tn [n = 8 (1), 10 (2), 12 (3), and mix (4)], were prepared in high yields via free radical polymerization of corresponding pure forms of methacrylate-functionalized POSS monomers, MMA-POSS-Tn (n = 8, 10, 12), and the mixture form, MMA-POSS-Tmix. Powder X-ray diffraction (XRD) spectra and BET analysis indicate that 1-4 are amorphous materials with high surface areas (683-839 m2•g-1). The surface areas and total pore volumes follow the trend: poly-POSS-T12 > poly-POSS-T10 > poly-POSS-Tmix > poly-POSS-T8. In addition, based on Barrett-Joyner-Halenda (BJH) analysis, poly-POSS-T12 contains the highest amount of mesopores. The Pd nanoparticles immobilized on poly-POSS-Tn [n = 8 (5), 10 (6), 12 (7), and mix (8)] are well dispersed with 4-6 wt% Pd content and similar average particle size of 6.2-6.5 nm, according to transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) and microwave plasma-atomic emission spectroscopy (MP-AES). At 90 oC, the stabilized Pd nanoparticles in 5-8 catalyzed aerobic oxidation of benzyl alcohol to benzaldehyde in 72-100% yields at 6 h using a mixture of a H2O/Pluronic (P123) solution. The PdNp@poly-POSS-T8 catalyst (5) exhibited the lowest catalytic activity, as a result of its lowest surface areas, total pore volumes, and amounts of mesopores. With the catalyst 8, various benzyl alcohol derivatives were converted to the corresponding aldehydes in good to excellent yields. However, with alcoholic substrates featuring electron-withdrawing substituents, high conversions were achieved with one equivalent of K2CO3 additive and longer reaction times.

  11. Methane Emission From the Congo Deep Sea Fan and Subsequent Aerobic Oxidation in the Quaternary Tropical Atlantic

    NASA Astrophysics Data System (ADS)

    Handley, L.; Cooke, M. P.; Talbot, H. M.; Wagner, T.

    2008-12-01

    The Congo Fan is a well-documented region of important methane (CH4) storage and gas seepage: gas hydrates abound at and just below the sediment surface as do large deeply-buried reservoirs of thermogenic methane linked with hydrocarbon source rocks. In the Congo Fan, both sources of methane are intimately connected through a complex network of faults, structuring this massive sediment wedge in a unique way. Methane release from both reservoirs has the potential to drive or respond to changes in local and global climate, thus causing changes in ocean chemical properties and biotic responses. Understanding these poorly-constrained mechanisms of methane emission and reconstructing the history of past emissions in the ocean is the main focus of our study. The ultimate fate of CH4 is, typically, its oxidation to CO2; this process can occur aerobically and anaerobically. Compared to anaerobic processes, aerobic methane oxidation, and its underlying mechanisms and possible feedbacks for the ocean-climate system, has received little attention. Here we present molecular evidence from Congo Fan sediments for aerobic methane oxidation and highlight how the process may play a previously unrecognised role in carbon cycling and oxygen availability in the water column. Bacteriohopanepolyols (BHPs) are lipid membrane constituents and occur with a wide range of structural and functional variability in many bacteria. Amino-BHPs are produced in large abundances by methane-oxidising bacteria and the 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) is a highly specific biomarker for aerobic methane oxidation. The Congo Fan record (ODP Leg 175, Site 1075; 2996 m depth) spans the last 1 Myr and reveals remarkable organic biomarker preservation, with a suite of 13 different BHPs identified in most sediment horizons, including aminopentol. Aminopentol abundance varies widely throughout the section and appears to do so cyclically, with markedly greater concentrations between ca

  12. QuadraPure-Supported Palladium Nanocatalysts for Microwave-Promoted Suzuki Cross-Coupling Reaction under Aerobic Condition

    PubMed Central

    Loh, Poh Lee; Juan, Joon Ching; Yarmo, Mohd Ambar; Yusop, Rahimi M.

    2014-01-01

    Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4–10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity. PMID:25054185

  13. QuadraPure-supported palladium nanocatalysts for microwave-promoted Suzuki cross-coupling reaction under aerobic condition.

    PubMed

    Liew, Kin Hong; Loh, Poh Lee; Juan, Joon Ching; Yarmo, Mohd Ambar; Yusop, Rahimi M

    2014-01-01

    Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4-10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity.

  14. Six weeks of aerobic dance exercise improves blood oxidative stress status and increases interleukin-2 in previously sedentary women.

    PubMed

    Leelarungrayub, Donrawee; Saidee, Kunteera; Pothongsunun, Prapas; Pratanaphon, Sainetee; YanKai, Araya; Bloomer, Richard J

    2011-07-01

    This study evaluated the change in blood oxidative stress, blood interleukin-2, and physical performance following 6 weeks of moderate intensity and duration aerobic dance exercise in 24 sedentary women. Blood samples were collected at rest twice before (baseline) and after the 6-week intervention for analysis of protein hydroperoxide (PrOOH), malondialdehyde (MDA), total anti-oxidant capacity (TAC), and interleukin-2 (IL-2) levels. Maximal treadmill run time (Time(max)) and maximal oxygen consumption (VO(2max)) were also measured. All variables were statistically analyzed with a repeated measurement ANOVA and Tukey post hoc. No differences were noted in any variable during the baseline period (p > 0.05). After aerobic dance exercise, VO(2max), Time(max), TAC and IL-2 were significantly increased, whereas MDA levels were decreased significantly (p < 0.05). PrOOH did not change either between baseline measures or after exercise. It can be concluded that aerobic dance exercise at a moderate intensity and duration can improve physical fitness, decrease MDA, and increase TAC and IL-2 in previously sedentary women.

  15. Aerobic cometabolic degradation of trichloroethene by methane and ammonia oxidizing microorganisms naturally associated with Carex comosa roots.

    PubMed

    Powell, C L; Nogaro, G; Agrawal, A

    2011-06-01

    The degradation potential of trichloroethene by the aerobic methane- and ammonia-oxidizing microorganisms naturally associated with wetland plant (Carex comosa) roots was examined in this study. In bench-scale microcosm experiments with washed (soil free) Carex comosa roots, the activity of root-associated methane- and ammonia-oxidizing microorganisms, which were naturally present on the root surface and/or embedded within the roots, was investigated. Significant methane and ammonia oxidation were observed reproducibly in batch reactors with washed roots incubated in growth media, where methane oxidation developed faster (2 weeks) compared to ammonia oxidation (4 weeks) in live microcosms. After enrichment, the methane oxidizers demonstrated their ability to degrade 150 μg l(-1) TCE effectively at 1.9 mg l(-1) of aqueous CH(4). In contrast, ammonia oxidizers showed a rapid and complete inhibition of ammonia oxidation with 150 μg l(-1) TCE at 20 mg l(-1) of NH(4)(+)-N, which may be attributed to greater sensitivity of ammonia oxidizers to TCE or its degradation product. No such inhibitory effect of TCE degradation was detected on methane oxidation at the above experimental conditions. The results presented here suggest that microorganisms associated with wetland plant roots can assist in the natural attenuation of TCE in contaminated aquatic environments.

  16. Synthesis of indazoles and azaindazoles by intramolecular aerobic oxidative C-N coupling under transition-metal-free conditions.

    PubMed

    Hu, Jiantao; Xu, Huacheng; Nie, Pengju; Xie, Xiaobo; Nie, Zongxiu; Rao, Yu

    2014-04-01

    A transition-metal-free oxidative C-N coupling method has been developed for the synthesis of 1H-azaindazoles and 1H-indazoles from easily accessible hydrazones. The procedure uses TEMPO, a basic additive, and dioxygen gas as the terminal oxidant. This reaction demonstrates better reactivity, functional group tolerance, and broader scope than comparable metal catalyzed reactions.

  17. Oxidation and Reduction Reactions in Organic Chemistry

    ERIC Educational Resources Information Center

    Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

    2010-01-01

    A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

  18. Catalytic Amine Oxidation under Ambient Aerobic Conditions: Mimicry of Monoamine Oxidase B**

    PubMed Central

    Murray, Alexander T; Dowley, Myles J H; Pradaux-Caggiano, Fabienne; Baldansuren, Amgalanbaatar; Fielding, Alistair J; Tuna, Floriana; Hendon, Christopher H; Walsh, Aron; Lloyd-Jones, Guy C; John, Matthew P; Carbery, David R

    2015-01-01

    The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase B activity. PMID:26087676

  19. Catalytic Amine Oxidation under Ambient Aerobic Conditions: Mimicry of Monoamine Oxidase B.

    PubMed

    Murray, Alexander T; Dowley, Myles J H; Pradaux-Caggiano, Fabienne; Baldansuren, Amgalanbaatar; Fielding, Alistair J; Tuna, Floriana; Hendon, Christopher H; Walsh, Aron; Lloyd-Jones, Guy C; John, Matthew P; Carbery, David R

    2015-07-27

    The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase B activity.

  20. Oxidative reactions during early stages of beer brewing studied by electron spin resonance and spin trapping.

    PubMed

    Frederiksen, Anne M; Festersen, Rikke M; Andersen, Mogens L

    2008-09-24

    An electron spin resonance (ESR)-based method was used for evaluating the levels of radical formation during mashing and in sweet wort. The method included the addition of 5% (v/v) ethanol together with the spin trap alpha-4-pyridyl(1-oxide)- N- tert-butylnitrone (POBN) to wort, followed by monitoring the rate of formation of POBN spin adducts during aerobic heating of the wort. The presence of ethanol makes the spin trapping method more selective and sensitive for the detection of highly reactive radicals such as hydroxyl and alkoxyl radicals. Samples of wort that were collected during the early stages of the mashing process gave higher rates of spin adduct formation than wort samples collected during the later stages. The lower oxidative stability of the early wort samples was confirmed by measuring the rate of oxygen consumption during heating of the wort. The addition of Fe(II) to the wort samples increased the rate of spin adduct formation, whereas the addition of Fe(II) during the mashing had no effect on the oxidative stability of the wort samples. Analysis of the iron content in the sweet wort samples demonstrated that iron added during the mashing had no effect on the iron level in the wort. The moderate temperatures during the early steps of mashing allow the endogenous malt enzymes to be active. The potential antioxidative effects of different redox-active enzymes during mashing were tested by measuring the rate of spin adduct formation in samples of wort. Surprisingly, a high catalase dosage caused a significant, 20% reduction of the initial rate of radical formation, whereas superoxide dismutase had no effect on the oxidation rates. This suggests that hydrogen peroxide and superoxide are not the only intermediates that play a role in the oxidative reactions occurring during aerobic oxidation of sweet wort.

  1. Warburg Meets Autophagy: Cancer-Associated Fibroblasts Accelerate Tumor Growth and Metastasis via Oxidative Stress, Mitophagy, and Aerobic Glycolysis

    PubMed Central

    Pavlides, Stephanos; Vera, Iset; Gandara, Ricardo; Sneddon, Sharon; Pestell, Richard G.; Mercier, Isabelle; Martinez-Outschoorn, Ubaldo E.; Whitaker-Menezes, Diana; Howell, Anthony

    2012-01-01

    Abstract Significance: Here, we review certain recent advances in oxidative stress and tumor metabolism, which are related to understanding the contributions of the microenvironment in promoting tumor growth and metastasis. In the early 1920s, Otto Warburg, a Nobel Laureate, formulated a hypothesis to explain the “fundamental basis” of cancer, based on his observations that tumors displayed a metabolic shift toward glycolysis. In 1963, Christian de Duve, another Nobel Laureate, first coined the phrase auto-phagy, derived from the Greek words “auto” and “phagy,” meaning “self” and “eating.” Recent Advances: Now, we see that these two ideas (autophagy and aerobic glycolysis) physically converge in the tumor stroma. First, cancer cells secrete hydrogen peroxide. Then, as a consequence, oxidative stress in cancer-associated fibroblasts drives autophagy, mitophagy, and aerobic glycolysis. Critical Issues: This “parasitic” metabolic coupling converts the stroma into a “factory” for the local production of recycled and high-energy nutrients (such as L-lactate)—to fuel oxidative mitochondrial metabolism in cancer cells. We believe that Warburg and de Duve would be pleased with this new two-compartment model for understanding tumor metabolism. It adds a novel stromal twist to two very well-established cancer paradigms: aerobic glycolysis and autophagy. Future Directions: Undoubtedly, these new metabolic models will foster the development of novel biomarkers, and corresponding therapies, to achieve the goal of personalized cancer medicine. Given the central role that oxidative stress plays in this process, new powerful antioxidants should be developed in the fight against cancer. Antioxid. Redox Signal. 16, 1264–1284. PMID:21883043

  2. Whole-Genome Transcriptional Analysis of Chemolithoautotrophic Thiosulfate Oxidation by Thiobacillus denitrificans Under Aerobic vs. Denitrifying Conditions

    SciTech Connect

    Beller, H R; Letain, T E; Chakicherla, A; Kane, S R; Legler, T C; Coleman, M A

    2006-04-22

    Thiobacillus denitrificans is one of the few known obligate chemolithoautotrophic bacteria capable of energetically coupling thiosulfate oxidation to denitrification as well as aerobic respiration. As very little is known about the differential expression of genes associated with ke chemolithoautotrophic functions (such as sulfur-compound oxidation and CO2 fixation) under aerobic versus denitrifying conditions, we conducted whole-genome, cDNA microarray studies to explore this topic systematically. The microarrays identified 277 genes (approximately ten percent of the genome) as differentially expressed using Robust Multi-array Average statistical analysis and a 2-fold cutoff. Genes upregulated (ca. 6- to 150-fold) under aerobic conditions included a cluster of genes associated with iron acquisition (e.g., siderophore-related genes), a cluster of cytochrome cbb3 oxidase genes, cbbL and cbbS (encoding the large and small subunits of form I ribulose 1,5-bisphosphate carboxylase/oxygenase, or RubisCO), and multiple molecular chaperone genes. Genes upregulated (ca. 4- to 95-fold) under denitrifying conditions included nar, nir, and nor genes (associated respectively with nitrate reductase, nitrite reductase, and nitric oxide reductase, which catalyze successive steps of denitrification), cbbM (encoding form II RubisCO), and genes involved with sulfur-compound oxidation (including two physically separated but highly similar copies of sulfide:quinone oxidoreductase and of dsrC, associated with dissimilatory sulfite reductase). Among genes associated with denitrification, relative expression levels (i.e., degree of upregulation with nitrate) tended to decrease in the order nar > nir > nor > nos. Reverse transcription, quantitative PCR analysis was used to validate these trends.

  3. Dynamics of photoinduced reactions at oxide surfaces

    NASA Astrophysics Data System (ADS)

    Al-Shamery, K.

    1996-11-01

    This report summarizes our work on UV-laser induced desorption of small molecules and atoms from transition metal oxides. The systems presented serve as examples for a simple photochemical reaction, the fission of the molecule surface bond. State resolved detection methods were used to record the final state distributions of the desorbing neutral molecules. Detailed results on the systems NO/NiO(1 1 1) and CO/Cr2O3(0 0 0 1) are presented. The experiments include investigations on stereodynamic aspects like the angular distributions of the desorbing molecules and, in the case of CO desorption, the rotational alignment with respect to the surface normal. Large desorption cross sections of (6±1) ṡ 10-17 cm2 for NO and (3.5±1) ṡ 10-17 cm2 for CO have been found for the desorption at 6.4 eV. The wavelength dependence indicates that the primary excitation step is substrate induced. The final state distributions show a high degree of translational, rotational and vibrational excitation and are clearly nonthermal of origin. The results are consistent with the formation of a negative ion intermediate state of the adsorbate. This observation is supported from a comparison to former results on NO/NiO(1 0 0) for which extensive ab initio calculations including electronically excited states exist. A spin state dependence of the vibrational excitation of NO could only be observed for NO/NiO(1 1 1) and is absent for NO/NiO(1 0 0). We attribute this observation to a spin state dependent coupling of the desorbing molecule to the surface in case the spin lattice orientation of the surface shows a preferential orientation. In the (1 1 1) plane the spin orientation is parallel within neighbour nickel ions while it is alternating in the (1 0 0) plane. For both systems studied the velocity component parallel to the surface is constant leading to a strong peaking along the surface normal for the fast molecules. The change from a preferred helicopter rotation (angular momentum

  4. Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry

    PubMed Central

    2015-01-01

    Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. The data obtained from these studies help define safe operating conditions for the use of oxygen with organic solvents. PMID:26622165

  5. CONTAMINANT ADSORPTION AND OXIDATION VIA FENTON REACTION

    EPA Science Inventory

    A ground water treatment process is proposed involving two cgemical processes: adsorption and oxidation. Adsorption of an organic compound onto granulated activated carbon (GAC) containing iron conveniently results in immobilizing and concentrating contaminants from the ground w...

  6. Guanine oxidation: one- and two-electron reactions.

    PubMed

    Pratviel, Geneviève; Meunier, Bernard

    2006-08-07

    Guanine bases in DNA are the most sensitive to oxidation. A lot of effort has been devoted to the understanding of the chemical modifications of guanine under different oxidizing conditions, the final goal being to know which lesions in DNA can be expected in vivo and their biological consequences. This article analyses the mechanisms underlying guanine oxidation by the comparison between one- and two-electron transfer processes. The different oxidants used in vitro give complementary answers. This overview presents a choice of some key intermediates and the predictive description of G-oxidation products that can be generated from these intermediates depending on the reaction conditions.

  7. High temperature heterogeneous reaction kinetics and mechanisms of tungsten oxidation

    NASA Astrophysics Data System (ADS)

    Sabourin, Justin L.

    Tungsten, which is a material used in many high temperature applications, is limited by its susceptibility to oxidation at elevated temperatures. Although tungsten has the highest melting temperature of any metal, at much lower temperatures volatile oxides are formed during oxidation with oxygen containing species. This differs from many heterogeneous oxidation reactions involving metals since most reactions form very stable oxides that have higher melting or boiling points than the pure metal (e.g., aluminum, iron). Understanding heterogeneous oxidation and vaporization processes may allow for the expansion and improvement of high temperature tungsten applications. In order to increase understanding of the oxidation processes of tungsten, there is a need to develop reaction mechanisms and kinetics for oxidation processes involving oxidizers and environmental conditions of interest. Tungsten oxidation was thoroughly studied in the past, and today there is a good phenomenological understanding of these processes. However, as the design of large scale systems increasingly relies on computer modeling there becomes a need for improved descriptions of chemical reactions. With the increase in computing power over the last several decades, and the development of quantum chemistry and physics theories, heterogeneous systems can be modeled in detail at the molecular level. Thermochemical parameters that may not be measured experimentally may now be determined theoretically, a tool that was previously unavailable to scientists and engineers. Additionally, chemical kinetic modeling software is now available for both homogeneous and heterogeneous reactions. This study takes advantage of these new theoretical tools, as well as a thermogravimetric (TG) flow reactor developed as part of this study to learn about mechanisms and kinetics of tungsten oxidation. Oxidizers of interest are oxygen (O2), carbon dioxide (CO 2), water (H2O), and other oxidizers present in combustion and

  8. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    PubMed

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-06

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  9. The Effect of Metal Oxide on Nanoparticles from Thermite Reactions

    ERIC Educational Resources Information Center

    Moore, Lewis Ryan

    2006-01-01

    The purpose of this research was to determine how metal oxide used in a thermite reaction can impact the production of nanoparticles. The results showed the presence of nanoparticles (less than 1 micron in diameter) of at least one type produced by each metal oxide. The typical particles were metallic spheres, which ranged from 300 nanometers in…

  10. Cyclization Reactions through DDQ-Mediated Vinyl Oxazolidinone Oxidation

    PubMed Central

    Liu, Lei; Floreancig, Paul E.

    2009-01-01

    Vinyl oxazolidinones react with DDQ to form α,β-unsaturated acyliminium ions in a new method for forming electrophiles under oxidative conditions. Appended nucleophiles undergo 1,4-addition reactions with these intermediates to form cyclic vinyl oxazolidinones with good levels of diastereocontrol, highlighting a new approach to utilizing oxidative carbon–hydrogen bond functionalization to increase molecular complexity. PMID:19552390

  11. Isotopomeric characterization of nitrous oxide produced by reaction of enzymes extracted from nitrifying and denitrifying bacteria

    NASA Astrophysics Data System (ADS)

    Yamazaki, T.; Hozuki, T.; Arai, K.; Toyoda, S.; Koba, K.; Fujiwara, T.; Yoshida, N.

    2014-05-01

    Nitrous oxide (N2O) is a potent greenhouse gas and produced in denitrification and nitrification by various microorganisms. Site preference (SP) of 15N in N2O, which is defined as the difference in the natural abundance of isotopomers 14N15NO and 15N14NO relative to 14N14NO, has been reported to be a useful tool to quantitatively distinguish N2O production pathways. To determine representative SP values for each microbial process, we firstly measured SP of N2O produced in the enzyme reaction of hydroxylamine oxidoreductase (HAO) purified from two species of ammonia oxidizing bacteria (AOB), Nitrosomonas europaea and Nitrosococcus oceani, and that of nitric oxide reductase (NOR) from Paracoccus denitrificans. The SP value for NOR reaction (-5.9 ± 2.1‰) showed nearly the same value as that reported for N2O produced by P. denitrificans in pure culture. In contrast, SP value for HAO reaction (36.3 ± 2.3‰) was a little higher than the values reported for N2O produced by AOB in aerobic pure culture. Using the SP values obtained by HAO and NOR reactions, we calculated relative contribution of the nitrite (NO2-) reduction (which is followed by NO reduction) to N2O production by N. oceani incubated under different O2 availability. Our calculations revealed that previous in vivo studies might have underestimated the SP value for the NH2OH oxidation pathway possibly due to a small contribution of NO2- reduction pathway. Further evaluation of isotopomer signatures of N2O using common enzymes of other processes related to N2O would improve the isotopomer analysis of N2O in various environments.

  12. Isotopomeric characterization of nitrous oxide produced by reaction of enzymes extracted from nitrifying and denitrifying bacteria

    NASA Astrophysics Data System (ADS)

    Yamazaki, T.; Hozuki, T.; Arai, K.; Toyoda, S.; Koba, K.; Fujiwara, T.; Yoshida, N.

    2013-10-01

    Nitrous oxide (N2O) is a potent greenhouse gas and produced in denitrification and nitrification in environmental nitrogen cycle by various microorganism. Site preference (SP) of 15N in N2O, which is defined as the difference in the natural abundance of isotopomers 14N15NO and 15N14NO relative to 14N14NO, has been reported to be a useful tool to quantitatively distinguish N2O production pathway. To determine representative SP value for each microbial process, we firstly measured SP of N2O produced in the enzyme reaction of hydroxylamine oxidoreductase (HAO) purified from two species of ammonia oxidizing bacteria (AOB), Nitrosomonas europaea and Nitrosococcus oceani, and that of nitric oxide reductase (NOR) from Paracoccus denitrificans, respectively. The SP value for NOR reaction (-5.9 ± 2.1‰) showed nearly the same value as that reported for N2O produced by P. denitrificans in pure culture. In contrast, SP value for HAO reaction (36.3 ± 2.3‰) was a little higher than the values reported for N2O produced by AOB in aerobic pure culture. Using the SP values obtained by HAO and NOR reactions, we calculated relative contribution of the nitrite (NO2-) reduction (which is followed by NO reduction) to N2O production by N. oceani incubated under different O2 availability. Our calculations revealed that previous in vivo studies might have underestimated the SP value for NH2OH oxidation pathway possibly due to a small contribution of NO2- reduction pathway. Further evaluation of isotopomer signatures of N2O using common enzymes of other processes related to N2O would improve the isotopomer analysis of N2O in various environments.

  13. Thermal oxidative degradation reactions of perfluoroalkylethers

    NASA Technical Reports Server (NTRS)

    Paciorek, K. L.; Ito, T. I.; Kratzer, R. H.

    1981-01-01

    The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

  14. A method for on-line measurement of wastewater organic substrate oxidation level during aerobic heterotrophic respiration.

    PubMed

    Rudelle, E A; Vollertsen, J; Hvitved-Jacobsen, T; Nielsen, A H

    2013-01-01

    A method for on-line measurement of the organic carbon oxidation level (OXC) during aerobic heterotrophic respiration in domestic wastewater was developed and tested. The method is based on batch incubation of sewer wastewater in an intermittently aerated respirometric reactor. Between aeration cycles, measured pH, dissolved oxygen (DO) and dissolved carbon dioxide (CO2) were used to calculate electron flow accepted by DO and the resulting production of dissolved inorganic carbon (DIC). The CO2 production was measured using a novel fiber-optic sensor based on luminescence quenching. The method was tested on domestic wastewater with a relatively high pH and alkalinity. From the DO and DIC measurements, it was possible to evaluate substrate oxidation levels with a temporal resolution of less than an hour. Addition of organic substrates during the experiments confirmed the method's applicability. The substrates tested included ethanol (OXC = -2), glucose (OXC = 0) and oxalic acid (OXC = 3).

  15. Isolation and characterization of homodimeric type-I reaction center complex from Candidatus Chloracidobacterium thermophilum, an aerobic chlorophototroph.

    PubMed

    Tsukatani, Yusuke; Romberger, Steven P; Golbeck, John H; Bryant, Donald A

    2012-02-17

    The recently discovered thermophilic acidobacterium Candidatus Chloracidobacterium thermophilum is the first aerobic chlorophototroph that has a type-I, homodimeric reaction center (RC). This organism and its type-I RCs were initially detected by the occurrence of pscA gene sequences, which encode the core subunit of the RC complex, in metagenomic sequence data derived from hot spring microbial mats. Here, we report the isolation and initial biochemical characterization of the type-I RC from Ca. C. thermophilum. After removal of chlorosomes, crude membranes were solubilized with 0.1% (w/v) n-dodecyl β-D-maltoside, and the RC complex was purified by ion-exchange chromatography. The RC complex comprised only two polypeptides: the reaction center core protein PscA and a 22-kDa carotenoid-binding protein denoted CbpC. The absorption spectrum showed a large, broad absorbance band centered at ∼483 nm from carotenoids as well as smaller Q(y) absorption bands at 672 and 812 nm from chlorophyll a and bacteriochlorophyll a, respectively. The light-induced difference spectra of whole cells, membranes, and the isolated RC showed maximal bleaching at 840 nm, which is attributed to the special pair and which we denote as P840. Making it unique among homodimeric type-I RCs, the isolated RC was photoactive in the presence of oxygen. Analyses by optical spectroscopy, chromatography, and mass spectrometry revealed that the RC complex contained 10.3 bacteriochlorophyll a(P), 6.4 chlorophyll a(PD), and 1.6 Zn-bacteriochlorophyll a(P)' molecules per P840 (12.8:8.0:2.0). The possible functions of the Zn-bacteriochlorophyll a(P)' molecules and the carotenoid-binding protein are discussed.

  16. Fractionation of the methane isotopologues 13CH4, 12CH3D, and 13CH3D during aerobic oxidation of methane by Methylococcus capsulatus (Bath)

    NASA Astrophysics Data System (ADS)

    Wang, David T.; Welander, Paula V.; Ono, Shuhei

    2016-11-01

    Aerobic oxidation of methane plays a major role in reducing the amount of methane emitted to the atmosphere from freshwater and marine settings. We cultured an aerobic methanotroph, Methylococcus capsulatus (Bath) at 30 and 37 °C, and determined the relative abundance of 12CH4, 13CH4, 12CH3D, and 13CH3D (a doubly-substituted, or ;clumped; isotopologue of methane) to characterize the clumped isotopologue effect associated with aerobic methane oxidation. In batch culture, the residual methane became enriched in 13C and D relative to starting methane, with D/H fractionation a factor of 9.14 (Dε/13ε) larger than that of 13C/12C. As oxidation progressed, the Δ13CH3D value (a measure of the excess in abundance of 13CH3D relative to a random distribution of isotopes among isotopologues) of residual methane decreased. The isotopologue fractionation factor for 13CH3D/12CH4 was found to closely approximate the product of the measured fractionation factors for 13CH4/12CH4 and 12CH3D/12CH4 (i.e., 13C/12C and D/H). The results give insight into enzymatic reversibility in the aerobic methane oxidation pathway. Based on the experimental data, a mathematical model was developed to predict isotopologue signatures expected for methane in the environment that has been partially-oxidized by aerobic methanotrophy. Measurement of methane clumped isotopologue abundances can be used to distinguish between aerobic methane oxidation and alternative methane-cycling processes.

  17. A Bioorthogonal Reaction of N-Oxide and Boron Reagents.

    PubMed

    Kim, Justin; Bertozzi, Carolyn R

    2015-12-21

    The development of bioorthogonal reactions has classically focused on bond-forming ligation reactions. In this report, we seek to expand the functional repertoire of such transformations by introducing a new bond-cleaving reaction between N-oxide and boron reagents. The reaction features a large dynamic range of reactivity, showcasing second-order rate constants as high as 2.3×10(3)  M(-1)  s(-1) using diboron reaction partners. Diboron reagents display minimal cell toxicity at millimolar concentrations, penetrate cell membranes, and effectively reduce N-oxides inside mammalian cells. This new bioorthogonal process based on miniscule components is thus well-suited for activating molecules within cells under chemical control. Furthermore, we demonstrate that the metabolic diversity of nature enables the use of naturally occurring functional groups that display inherent biocompatibility alongside abiotic components for organism-specific applications.

  18. Divergence between organometallic and single-electron-transfer mechanisms in copper(II)-mediated aerobic C-H oxidation.

    PubMed

    Suess, Alison M; Ertem, Mehmed Z; Cramer, Christopher J; Stahl, Shannon S

    2013-07-03

    Copper(II)-mediated C-H oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from Cu(II)-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Under basic conditions, the benzamide group undergoes directed C-H methoxylation or chlorination. Under acidic conditions, the quinoline group undergoes nondirected chlorination. Experimental and computational mechanistic studies implicate an organometallic C-H activation/functionalization mechanism under the former conditions and a single-electron-transfer mechanism under the latter conditions. This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding Cu(II)-mediated C-H oxidation reactions.

  19. Highly efficient direct aerobic oxidative esterification of cinnamyl alcohol with alkyl alcohols catalysed by gold nanoparticles incarcerated in a nanoporous polymer matrix: a tool for investigating the role of the polymer host.

    PubMed

    Buonerba, Antonio; Noschese, Annarita; Grassi, Alfonso

    2014-04-25

    The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi-block copolymer matrix, which consisted of syndiotactic polystyrene-co-cis-1,4-polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base-catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10-45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2-propanol, 1-butanol, 1-hexanol or 1-octanol. The rate constants of the latter reaction are pseudo-zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1-butanol (Ea = 57.8±11.5 and 62.7±16.7 kJ mol(-1) for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2-phenylethanol follows pseudo-first-order kinetics with respect to 2-phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction.

  20. Ozone oxidation and aerobic biodegradation with spent mushroom compost for detoxification and benzo(a)pyrene removal from contaminated soil.

    PubMed

    Russo, Lara; Rizzo, Luigi; Belgiorno, Vincenzo

    2012-05-01

    The combination of ozonation and spent mushroom compost (SMC)-mediated aerobic biological treatment was investigated in the removal of benzo(a)pyrene from contaminated soil. The performances of the process alone and combined were evaluated in terms of benzo(a)pyrene removal efficiency, mineralization efficiency (as total organic carbon removal), and soil residual toxicity (phytotoxicity to Lepidium Sativum and toxicity to Vibrio fischeri). In spite of the removal efficiency (35%) obtained by SMC-mediated biological process as a stand-alone treatment, the combined process showed a benzo(a)pyrene concentration reduction higher than 75%; the best removal (82%) was observed after 10 min pre-ozonation treatment. In particular, ozonation improved the biodegradability of the contaminant, as confirmed by the increase of CO(2) production (close to 70% compared to the control), mineralization (greater than 60%) and bacterial density (which increased by two orders of magnitude). Moreover, according to phytotoxicity tests on L. Sativum, the aerobic biological process of pre-ozonated soil decreased toxicity. According to the results achieved in the present study, ozonation pre-treatment showed an high potential to overcome the limitation of bioremediation of recalcitrant compound, but it should be carefully operated in order to maximize PAH removal efficiency as well as to minimize soil residual toxicity which can result from the formation of the oxidation intermediates.

  1. Organization of the Escherichia coli aerobic enzyme complexes of oxidative phosphorylation in dynamic domains within the cytoplasmic membrane

    PubMed Central

    Erhardt, Heiko; Dempwolff, Felix; Pfreundschuh, Moritz; Riehle, Marc; Schäfer, Caspar; Pohl, Thomas; Graumann, Peter; Friedrich, Thorsten

    2014-01-01

    The Escherichia coli cytoplasmic membrane contains the enzyme complexes of oxidative phosphorylation (OXPHOS). Not much is known about their supramolecular organization and their dynamics within the membrane in this model organism. In mitochondria and other bacteria, it was demonstrated by nondenaturing electrophoretic methods and electron microscopy that the OXPHOS complexes are organized in so-called supercomplexes, stable assemblies with a defined number of the individual enzyme complexes. To investigate the organization of the E. coli enzyme complexes of aerobic OXPHOS in vivo, we established fluorescent protein fusions of the NADH:ubiquinone oxidoreductase, the succinate:ubiquinone oxidoreductase, the cytochrome bd-I, and the cytochrome bo3 terminal oxidases, and the FoF1 ATP-synthase. The fusions were integrated in the chromosome to prevent artifacts caused by protein overproduction. Biochemical analysis revealed that all modified complexes were fully assembled, active, and stable. The distribution of the OXPHOS complexes in living cells was determined using total internal reflection fluorescence microscopy. The dynamics within the membrane were detected by fluorescence recovery after photobleaching. All aerobic OXPHOS complexes showed an uneven distribution in large mobile patches within the E. coli cytoplasmic membrane. It is discussed whether the individual OXPHOS complexes are organized as clustered individual complexes, here called “segrazones.” PMID:24729508

  2. Aerobic Oxidation of Cyclohexane on Catalysts Based on Twinned and Single-Crystal Au75Pd25 Bimetallic Nanocrystals.

    PubMed

    Wang, Liangbing; Zhao, Songtao; Liu, Chenxuan; Li, Chen; Li, Xu; Li, Hongliang; Wang, Youcheng; Ma, Chao; Li, Zhenyu; Zeng, Jie

    2015-05-13

    Bimetallic Au75Pd25 nanocrystals with shapes of icosahedron and octahedron were synthesized by adding different amounts of iodide ions, and were employed as catalysts for solvent-free aerobic oxidation of cyclohexane. Although both icosahedrons and octahedrons were bounded by {111} facets, the turnover frequency number of Au75Pd25 icosahedrons reached 15,106 h(-1), almost three times as high as that of Au75Pd25 octahedrons. The conversion of cyclohexane reached 28.1% after 48 h using Au75Pd25 icosahedrons, with the selectivity of 84.3% to cyclohexanone. Density functional theory calculations along with X-ray photoelectron spectroscopy examinations reveal that the excellent catalytic performance of AuPd icosahedrons could be ascribed to twin-induced strain and highly negative charge density of Au atoms on the surface.

  3. Kinetics of oxytetracycline reaction with a hydrous manganese oxide.

    PubMed

    Rubert, Kennedy F; Pedersen, Joel A

    2006-12-01

    Tetracycline antibiotics comprise a class of broad spectrum antimicrobial agents finding application in human therapy, animal husbandry, aquaculture, and fruit crop production. To better understand the processes affecting these antibiotics in soils and sediments, the kinetics of oxytetracycline transformation by a hydrous manganese oxide (MnO2) were investigated as a function of reactant concentration, pH, and temperature. Oxytetracycline was rapidly degraded by MnO2. Initial reaction rates exhibited pronounced pH-dependence, increasing as pH decreased. Reaction of oxytetracycline with MnO2 was accompanied by generation of Mn(II) ions, suggesting oxidative transformation of the antibiotic. At pH 5.6, apparent reaction orders for oxytetracycline and MnO2 were 0.7 and 0.8. Reaction order with respect to H+ was 0.6 between pH 4 and 9. Initial reaction rates increased by a factor of approximately 2.4 for 10 degrees C temperature increases; the apparent activation energy (60 kJ x mol(-1)) was consistent with a surface-controlled reaction. Reactivity of tetracycline antibiotics toward MnO2 increased in the following order: rolitetracyline oxytetracycline < or =tetracycline approximately meclocycline < chlortetracycline. The initial rate of chlortetracycline degradation by MnO2 was substantially larger than that of the other tetracycline antibiotics investigated. MnO2 reactivity toward oxytetracycline decreased with time; a retarded rate equation was used to describe oxytetracycline reaction with MnO2 under declining rate conditions. This study indicates that natural manganese oxides in soils and sediments are likely to promote appreciable degradation of tetracycline antibiotics, and that reaction rates are strongly dependent on reaction time scale and solution conditions.

  4. Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

    NASA Technical Reports Server (NTRS)

    Fox, D. S.

    1994-01-01

    Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

  5. L-Proline: an efficient N,O-bidentate ligand for copper-catalyzed aerobic oxidation of primary and secondary benzylic alcohols at room temperature.

    PubMed

    Zhang, Guofu; Han, Xingwang; Luan, Yuxin; Wang, Yong; Wen, Xin; Ding, Chengrong

    2013-09-18

    A novel and highly practical copper-catalyzed aerobic alcohol oxidation system with L-proline as the ligand at room temperature has been developed. A wide range of primary and secondary benzylic alcohols tested have been smoothly transformed into corresponding aldehydes and ketones with high yields and selectivities.

  6. New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

    PubMed

    Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

    2016-08-01

    Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation.

  7. The influence of pyrite grain size on the final oxygen isotope difference between sulphate and water in aerobic pyrite oxidation experiments.

    PubMed

    Heidel, Claudia; Tichomirowa, Marion; Junghans, Manuela

    2009-12-01

    Oxidation experiments with different pyrite grain sizes (63-100, 100-140, 140-180 microm) were carried out to investigate the oxygen and sulphur isotope composition of sulphate produced under aerobic acid conditions, which may help to understand oxidation mechanisms and to interpret data from natural sites. Long-term experiments with grain size 63-100 microm showed that constant delta (18)O(SO4) values were not achieved before 100 days. The final oxygen isotope difference between water and sulphate indicates that a small proportion of molecular oxygen is incorporated into sulphate even in the later course of the oxidation due to sulphite oxidation by molecular oxygen. However, most of the sulphate oxygen derives from water. Similar delta (18)O(SO4) values from experiments with grain sizes 63-100, 100-140, and 140-180 microm indicate similar oxidation mechanisms for all three grain sizes. These results differed from previous results of identical experiments with grain size<63 microm, where higher delta (18)O(SO4) values were obtained. We propose that the greater proportion of molecular oxygen in sulphate from oxidised fine-grained pyrite is caused by an intensified adsorption of molecular oxygen on sulphur sites of ultrafine pyrite particles. Hence, the formation of sulphate from the (initial) reaction on sulphur sites of pyrite and from sulphite oxidation should be more dominant if ultrafine material is present. The delta (34)S(SO4) values (2.0-2.7) obtained from experiments with the coarser grain sizes agreed with the delta (34)S value of pyrite (2.4), whereas sulphur isotopes of sulphate obtained from previous experiments with fine-grained pyrite showed an initial (32)S enrichment compared with pyrite. Due to the lack of delta (34)S(SO4) values from the beginning of the experiments with coarser grain sizes, it remains speculative that sulphur isotopes indicate at least initial differences in oxidation mechanisms between fine and coarser pyrite grain sizes.

  8. Investigation of oxidative phosphorylation in continuous cultures. A non-equilibrium thermodynamic approach to energy transduction for Escherichia coli in aerobic condition

    NASA Astrophysics Data System (ADS)

    Ghafuri, Mohazabeh; Nosrati, Mohsen; Hosseinkhani, Saman

    2015-03-01

    Adenosine triphosphate (ATP) production in living cells is very important. Different researches have shown that in terms of mathematical modeling, the domain of these investigations is essentially restricted. Recently the thermodynamic models have been suggested for calculation of the efficiency of oxidative phosphorylation process and rate of energy loss in animal cells using chemiosmotic theory and non-equilibrium thermodynamics equations. In our previous work, we developed a mathematical model for mitochondria of animal cells. In this research, according to similarities between oxidative phosphorylation process in microorganisms and animal cells, Golfar's model was developed to predict the non-equilibrium thermodynamic behavior of the oxidative phosphorylation process for bacteria in aerobic condition. With this model the rate of energy loss, P/O ratio, and efficiency of oxidative phosphorylation were calculated for Escherichia coli in aerobic condition. The results then were compared with experimental data given by other authors. The thermodynamic model had an acceptable agreement with the experimental data.

  9. Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO.

    PubMed

    Yuan, Gaoqing; Zheng, Junhua; Gao, Xiaofang; Li, Xianwei; Huang, Liangbin; Chen, Huoji; Jiang, Huanfeng

    2012-08-04

    With atmospheric oxygen as the oxidant, a novel copper(I)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation.

  10. Influence of composition of reaction mixture on selectivity in oxidation of aromatic compounds on oxide catalysts

    SciTech Connect

    Belokopytov, Yu.V.; Pyatnitskii, Yu.I.; Tatarinova, T.A.; Strashnenko, A.V.

    1985-07-01

    A general outline is given of a kinetic model of oxidation of a hydrocarbon under the conditions of coexistence on the catalyst surface of sections of different oxidation levels. An analytical dependence has been obtained of the selectivity of the process and conversion on the composition of the reaction mixture. A qualitative agreement has been established between the theoretical and experimental dependences of selectivity and conversion on the ratio of the benzene and oxygen concentrations in the reaction mixture.

  11. Biofilter for removal of nitrogen oxides from contaminated gases under aerobic conditions

    DOEpatents

    Apel, W.A.

    1998-08-18

    A biofilter is described for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method is described of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described. 6 figs.

  12. Biofilter for removal of nitrogen oxides from contaminated gases under aerobic conditions

    DOEpatents

    Apel, William A.

    1998-01-01

    A biofilter for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described.

  13. Method for facilitating catalyzed oxidation reactions, device for facilitating catalyzed oxidation reactions

    DOEpatents

    Beuhler, Robert J.; White, Michael G.; Hrbek, Jan

    2006-08-15

    A catalytic process for the oxidation of organic. Oxygen is loaded into a metal foil by heating the foil while in contact with an oxygen-containing fluid. After cooling the oxygen-activated foil to room temperature, oxygen diffuses through the foil and oxidizes reactants exposed to the other side of the foil.

  14. The history of aerobic ammonia oxidizers: from the first discoveries to today.

    PubMed

    Monteiro, Maria; Séneca, Joana; Magalhães, Catarina

    2014-07-01

    Nitrification, the oxidation of ammonia to nitrite and nitrate, has long been considered a central biological process in the global nitrogen cycle, with its first description dated 133 years ago. Until 2005, bacteria were considered the only organisms capable of nitrification. However, the recent discovery of a chemoautotrophic ammonia-oxidizing archaeon, Nitrosopumilus maritimus, changed our concept of the range of organisms involved in nitrification, highlighting the importance of ammonia-oxidizing archaea (AOA) as potential players in global biogeochemical nitrogen transformations. The uniqueness of these archaea justified the creation of a novel archaeal phylum, Thaumarchaeota. These recent discoveries increased the global scientific interest within the microbial ecology society and have triggered an analysis of the importance of bacterial vs archaeal ammonia oxidation in a wide range of natural ecosystems. In this mini review we provide a chronological perspective of the current knowledge on the ammonia oxidation pathway of nitrification, based on the main physiological, ecological and genomic discoveries.

  15. Archaea produce lower yields of N2 O than bacteria during aerobic ammonia oxidation in soil.

    PubMed

    Hink, Linda; Nicol, Graeme W; Prosser, James I

    2016-03-11

    Nitrogen fertilisation of agricultural soil contributes significantly to emissions of the potent greenhouse gas nitrous oxide (N2 O), which is generated during denitrification and, in oxic soils, mainly by ammonia oxidisers. Although laboratory cultures of ammonia oxidising bacteria (AOB) and archaea (AOA) produce N2 O, their relative activities in soil are unknown. This work tested the hypothesis that AOB dominate ammonia oxidation and N2 O production under conditions of high inorganic ammonia (NH3 ) input, but result mainly from the activity of AOA when NH3 is derived from mineralisation. 1-octyne, a recently discovered inhibitor of AOB, was used to distinguish N2 O production resulting from archaeal and bacterial ammonia oxidation in soil microcosms, and specifically inhibited AOB growth, activity and N2 O production. In unamended soils, ammonia oxidation and N2 O production were lower and resulted mainly from ammonia oxidation by AOA. The AOA N2 O yield relative to nitrite produced was half that of AOB, likely due to additional enzymatic mechanisms in the latter, but ammonia oxidation and N2 O production were directly linked in all treatments. Relative contributions of AOA and AOB to N2 O production, therefore, reflect their respective contributions to ammonia oxidation. These results suggest potential mitigation strategies for N2 O emissions from fertilised agricultural soils.

  16. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    DOEpatents

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  17. The effects of periodized concurrent and aerobic training on oxidative stress parameters, endothelial function and immune response in sedentary male individuals of middle age.

    PubMed

    Schaun, Maximiliano Isoppo; Dipp, Thiago; Rossato, Juliane da Silva; Wilhelm, Eurico Nestor; Pinto, Ronei; Rech, Anderson; Plentz, Rodrigo Della Méa; Homem de Bittencourt, Paulo I; Reischak-Oliveira, Alvaro

    2011-10-01

    The vascular endothelium plays a key role in arterial wall homeostasis by preventing atherosclerotic plaque formation. A primary causal factor of endothelial dysfunction is the reactive oxygen species. Aerobic exercise is ascribed as an important adjuvant therapy in endothelium-dependent cardiovascular disease. However, little is known about the effects of concurrent (aerobic + strength) training on that. For a comparison of the effects of aerobic and concurrent physical training on endothelial function, oxidative stress parameters and the immunoinflammatory activity of monocytes/macrophages, 20 adult male volunteers of middle age were divided into a concurrent training (CT) programme group and an aerobic training group. The glutathione disulphide to glutathione ratio (GSSG/GSH) and plasma lipoperoxide (LPO) levels, as well as flow-mediated dilation (FMD), monocyte/macrophage functional activity (zymosan phagocytosis), body lipid profiles, aerobic capacity (maximal oxygen uptake) and strength parameters (one-repetition maximum test), were measured before and after the exercise training programmes. The CT exhibited reduced acute effects of exercise on the GSSG/GSH ratio, plasma LPO levels and zymosan phagocytosis. The CT also displayed improved lipid profiles, glycaemic control, maximal oxygen uptake and one-repetition maximum test values. In both the aerobic training and the CT, training improved the acute responses to exercise, as inferred from a decrease in the GSSG/GSH ratios. The aerobic sessions did not alter basal levels of plasma LPO or macrophage phagocytic activity but improved FMD values as well as lipid profiles and glycaemic control. In summary, both training programmes improve systemic redox status and antioxidant defences. However, the aerobic training was more efficient in improving FMD in the individuals studied.

  18. A Gallium Oxide-Graphene Oxide Hybrid Composite for Enhanced Photocatalytic Reaction

    PubMed Central

    Kim, Seungdu; Han, Kook In; Lee, In Gyu; Park, Won Kyu; Yoon, Yeojoon; Yoo, Chan Sei; Yang, Woo Seok; Hwang, Wan Sik

    2016-01-01

    Hybrid composites (HCs) made up of gallium oxide (GaO) and graphene oxide (GO) were investigated with the intent of enhancing a photocatalytic reaction under ultraviolet (UV) radiation. The material properties of both GaO and GO were preserved, even after the formation of the HCs. The incorporation of the GO into the GaO significantly enhanced the photocatalytic reaction, as indicated by the amount of methylene blue (MB) degradation. The improvements in the reaction were discussed in terms of increased surface area and the retarded recombination of generated charged carriers. PMID:28335255

  19. Aerobic Lineage of the Oxidative Stress Response Protein Rubrerythrin Emerged in an Ancient Microaerobic, (Hyper)Thermophilic Environment.

    PubMed

    Cardenas, Juan P; Quatrini, Raquel; Holmes, David S

    2016-01-01

    Rubrerythrins (RBRs) are non-heme di-iron proteins belonging to the ferritin-like superfamily. They are involved in oxidative stress defense as peroxide scavengers in a wide range of organisms. The vast majority of RBRs, including classical forms of this protein, contain a C-terminal rubredoxin-like domain involved in electron transport that is used during catalysis in anaerobic conditions. Rubredoxin is an ancient and large protein family of short length (<100 residues) that contains a Fe-S center involved in electron transfer. However, functional forms of the enzyme lacking the rubredoxin-like domain have been reported (e.g., sulerythrin and ferriperoxin). In this study, phylogenomic evidence is presented that suggests that a complete lineage of rubrerythrins, lacking the rubredoxin-like domain, arose in an ancient microaerobic and (hyper)thermophilic environments in the ancestors of the Archaea Thermoproteales and Sulfolobales. This lineage (termed the "aerobic-type" lineage) subsequently evolved to become adapted to environments with progressively lower temperatures and higher oxygen concentrations via the acquisition of two co-localized genes, termed DUF3501 and RFO, encoding a conserved protein of unknown function and a predicted Fe-S oxidoreductase, respectively. Proposed Horizontal Gene Transfer events from these archaeal ancestors to Bacteria expanded the opportunities for further evolution of this RBR including adaption to lower temperatures. The second lineage (termed the cyanobacterial lineage) is proposed to have evolved in cyanobacterial ancestors, maybe in direct response to the production of oxygen via oxygenic photosynthesis during the Great Oxygen Event (GOE). It is hypothesized that both lineages of RBR emerged in a largely anaerobic world with "whiffs" of oxygen and that their subsequent independent evolutionary trajectories allowed microorganisms to transition from this anaerobic world to an aerobic one.

  20. Aerobic Lineage of the Oxidative Stress Response Protein Rubrerythrin Emerged in an Ancient Microaerobic, (Hyper)Thermophilic Environment

    PubMed Central

    Cardenas, Juan P.; Quatrini, Raquel; Holmes, David S.

    2016-01-01

    Rubrerythrins (RBRs) are non-heme di-iron proteins belonging to the ferritin-like superfamily. They are involved in oxidative stress defense as peroxide scavengers in a wide range of organisms. The vast majority of RBRs, including classical forms of this protein, contain a C-terminal rubredoxin-like domain involved in electron transport that is used during catalysis in anaerobic conditions. Rubredoxin is an ancient and large protein family of short length (<100 residues) that contains a Fe-S center involved in electron transfer. However, functional forms of the enzyme lacking the rubredoxin-like domain have been reported (e.g., sulerythrin and ferriperoxin). In this study, phylogenomic evidence is presented that suggests that a complete lineage of rubrerythrins, lacking the rubredoxin-like domain, arose in an ancient microaerobic and (hyper)thermophilic environments in the ancestors of the Archaea Thermoproteales and Sulfolobales. This lineage (termed the “aerobic-type” lineage) subsequently evolved to become adapted to environments with progressively lower temperatures and higher oxygen concentrations via the acquisition of two co-localized genes, termed DUF3501 and RFO, encoding a conserved protein of unknown function and a predicted Fe-S oxidoreductase, respectively. Proposed Horizontal Gene Transfer events from these archaeal ancestors to Bacteria expanded the opportunities for further evolution of this RBR including adaption to lower temperatures. The second lineage (termed the cyanobacterial lineage) is proposed to have evolved in cyanobacterial ancestors, maybe in direct response to the production of oxygen via oxygenic photosynthesis during the Great Oxygen Event (GOE). It is hypothesized that both lineages of RBR emerged in a largely anaerobic world with “whiffs” of oxygen and that their subsequent independent evolutionary trajectories allowed microorganisms to transition from this anaerobic world to an aerobic one. PMID:27917155

  1. The oxidative burst reaction in mammalian cells depends on gravity.

    PubMed

    Adrian, Astrid; Schoppmann, Kathrin; Sromicki, Juri; Brungs, Sonja; von der Wiesche, Melanie; Hock, Bertold; Kolanus, Waldemar; Hemmersbach, Ruth; Ullrich, Oliver

    2013-12-20

    Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in "functional weightlessness" were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and function

  2. The oxidative burst reaction in mammalian cells depends on gravity

    PubMed Central

    2013-01-01

    Gravity has been a constant force throughout the Earth’s evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in “functional weightlessness” were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and

  3. Reactions of metal ions at surfaces of hydrous iron oxide

    USGS Publications Warehouse

    Hem, J.D.

    1977-01-01

    Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

  4. Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants.

    PubMed

    Zhang, Yang; Shu, Jinian; Zhang, Yuanxun; Yang, Bo

    2013-09-01

    The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10-dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.

  5. New Insights of the Fenton Reaction Using Glycerol as the Experimental Model. Effect of O2, Inhibition by Mg(2+), and Oxidation State of Fe.

    PubMed

    Vitale, Arturo Alberto; Bernatene, Eduardo A; Vitale, Martín Gustavo; Pomilio, Alicia Beatriz

    2016-07-21

    The use of iron ions as catalyst of oxidation with hydrogen peroxide, known as the Fenton reaction, is important for industry and biological systems. It has been widely studied since its discovery in the 19th century, but important aspects of the reaction as which is the oxidant, the role of oxygen, and the oxidation state of Fe still remain unclear. In this work new mechanistic insights of the oxidation of carbohydrates by the Fenton reaction using glycerol as experimental model are described. The reaction was studied by means of oxidation reduction potential (ORP) measures. The stoichiometry was measured, showing the important role of oxygen for lowering H2O2 consumption under aerobic conditions. Evidence is provided to demonstrate that in this system Fe(2+) generates a catalyst by reacting with a substrate to produce a complex, which gives rise to singlet oxygen after reacting with H2O2. This is the first time that the inhibitor effect of Mg(2+) is reported in this reaction, and its participation in the mechanism is described. A rational mechanism for the oxidation of glycerol using the Fenton reaction under these specific conditions is proposed. The role of oxygen, the participation of Fe(2+), and the inhibition by Mg(2+) are fully demonstrated experimentally.

  6. Hydrogen production from methane through catalytic partial oxidation reactions

    NASA Astrophysics Data System (ADS)

    Freni, S.; Calogero, G.; Cavallaro, S.

    This paper reviews recent developments in syn-gas production processes used for partial methane oxidation with and/or without steam. In particular, we examined different process charts (fixed bed, fluidised bed, membrane, etc.), kinds of catalysts (powders, foams, monoliths, etc.) and catalytically active phases (Ni, Pt, Rh, etc.). The explanation of the various suggested technical solutions accounted for the reaction mechanism that may selectively lead to calibrated mixtures of CO and H 2 or to the unwanted formation of products of total oxidation (CO 2 and H 2O) and pyrolysis (coke). Moreover, the new classes of catalysts allow the use of small reactors to treat large amounts of methane (monoliths) or separate hydrogen in situ from the other reaction products (membrane). This leads to higher conversions and selectivity than could have been expected thermodynamically. Although catalysts based on Rh are extremely expensive, they can be used to minimise H 2O formation by maximising H 2 yield.

  7. Reaction Mechanism and Kinetics of Enargite Oxidation at Roasting Temperatures

    NASA Astrophysics Data System (ADS)

    Padilla, Rafael; Aracena, Alvaro; Ruiz, Maria C.

    2012-10-01

    Roasting of enargite (Cu3AsS4) in the temperature range of 648 K to 898 K (375 °C to 625 °C) in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric methods. From the experimental results of weight loss/gain data and X-ray diffraction (XRD) analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was determined, which occurred in three sequential stages:

  8. Copper-catalyzed aerobic oxidative synthesis of aryl nitriles from benzylic alcohols and aqueous ammonia.

    PubMed

    Tao, Chuanzhou; Liu, Feng; Zhu, Youmin; Liu, Weiwei; Cao, Zhiling

    2013-05-28

    Copper-catalyzed direct conversion of benzylic alcohols to aryl nitriles was realized using NH3(aq.) as the nitrogen source, O2 as the oxidant and TEMPO as the co-catalyst. Furthermore, copper-catalyzed one-pot synthesis of primary aryl amides from alcohols was also achieved.

  9. Combination Sorbent and Reactive Chemistries for Use in Highly Efficient Aerobic Oxidations (W911NF0510081)

    DTIC Science & Technology

    2009-07-14

    oxidation of alcohols to carbonyl compounds is a common and important transformation in organic synthesis . Although there are many different methods...Metals for Organic Synthesis , 2nd ed. (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim, 2004, pp. 437-478; d) B.-Z. Zhan, A. Thompson, Tetrahedron

  10. Nitrite-Driven Nitrous Oxide Production Under Aerobic Soil Conditions: Kinetics and Biochemical Controls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

  11. Physical Training Status Determines Oxidative Stress and Redox Changes in Response to an Acute Aerobic Exercise

    PubMed Central

    Damirchi, Arsalan; Farjaminezhad, Manoochehr

    2016-01-01

    Objective. To assess the influence of different physical training status on exercise-induced oxidative stress and changes in cellular redox state. Methods. Thirty male subjects participated in this study and were assigned as well-trained (WT), moderately trained (MT), and untrained (UT) groups. The levels of cortisol, creatine kinase, plasma reduced glutathione to oxidized glutathione (GSH/GSSG), cysteine/cystine (Cys/CySS), and GSH/GSSG ratio in red blood cells (RBCs) were measured immediately and 10 and 30 min after exercise. Results. Following the exercise, plasma GSH/GSSG (p = 0.001) and Cys/CySS (p = 0.005) were significantly reduced in all groups. Reduction in plasma GSH/GSSG ratio in all groups induced a transient shift in redox balance towards a more oxidizing environment without difference between groups (p = 0.860), while RBCs GSH/GSSG showed significant reduction (p = 0.003) and elevation (p = 0.007) in UT and MT groups, respectively. The highest level of RBCs GSH/GSSG ratio was recorded in MT group, and the lowest one was recorded in the WT group. Conclusion. Long term regular exercise training with moderate intensity shifts redox balance towards more reducing environment, versus intensive exercise training leads to more oxidizing environment and consequently development of related diseases. PMID:27064342

  12. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    NASA Technical Reports Server (NTRS)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  13. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    NASA Astrophysics Data System (ADS)

    Tsotsis, T. T.; Sane, R. C.

    1987-04-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  14. Kinetics of the reaction of nitric oxide with hydrogen

    NASA Technical Reports Server (NTRS)

    Flower, W. L.; Hanson, R. K.; Kruger, C. H.

    1974-01-01

    Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

  15. Reaction between nitric oxide and ozone in solid nitrogen

    NASA Technical Reports Server (NTRS)

    Lucas, D.; Pimentel, G. C.

    1979-01-01

    Nitrogen dioxide, NO2, is produced when nitric oxide, NO, and ozone, O3, are suspended in a nitrogen matrix at 11-20 K. The NO2 is formed with first-order kinetics, a 12 K rate constant of (1.4 + or - 0.2) x 0.00001/sec, and an apparent activation energy of 106 + or - 10 cal/mol. Isotopic labeling, variation of concentrations, and cold shield experiments show that the growth of NO2 is due to reaction between ozone molecules and NO monomers, and that the reaction is neither infrared-induced nor does it seem to be a heavy atom tunneling process. Reaction is attributed to nearest-neighbor NO.O3 pairs probably held in a specific orientational relationship that affects the kinetic behavior. When the temperature is raised, more such reactive pairs are generated, presumably by local diffusion. Possible mechanisms are discussed.

  16. Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment in an aerobic bioreactor packed with carbon fibers.

    PubMed

    Yamashita, Takahiro; Yamamoto-Ikemoto, Ryoko; Yokoyama, Hiroshi; Kawahara, Hirofumi; Ogino, Akifumi; Osada, Takashi

    2015-03-01

    Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment was demonstrated in an aerobic bioreactor packed with carbon fibers (CF reactor). The CF reactor had a demonstrated advantage in mitigating N2 O emission and avoiding NOx (NO3  + NO2 ) accumulation. The N2 O emission factor was 0.0003 g N2 O-N/gTN-load in the CF bioreactor compared to 0.03 gN2 O-N/gTN-load in an activated sludge reactor (AS reactor). N2 O and CH4 emissions from the CF reactor were 42 g-CO2 eq/m(3) /day, while those from the AS reactor were 725 g-CO2 eq/m(3) /day. The dissolved inorganic nitrogen (DIN) in the CF reactor removed an average of 156 mg/L of the NH4 -N, and accumulated an average of 14 mg/L of the NO3 -N. In contrast, the DIN in the AS reactor removed an average 144 mg/L of the NH4 -N and accumulated an average 183 mg/L of the NO3 -N. NO2 -N was almost undetectable in both reactors.

  17. Integrated thermophilic submerged aerobic membrane bioreactor and electrochemical oxidation for pulp and paper effluent treatment--towards system closure.

    PubMed

    Qu, X; Gao, W J; Han, M N; Chen, A; Liao, B Q

    2012-07-01

    A novel integrated thermophilic submerged aerobic membrane bioreactor (TSAMBR) and electrochemical oxidation (EO) technology was developed for thermomechanical pulping pressate treatment with the aim of system closure. The TSAMBR was able to achieve a chemical oxygen demand (COD) removal efficiency of 88.6 ± 1.9-92.3 ± 0.7% under the organic loading rate of 2.76 ± 0.13-3.98 ± 0.23 kg COD/(m(3) d). An optimal hydraulic retention time (HRT) of 1.1 ± 0.1d was identified for COD removal. Cake formation was identified as the dominant mechanism of membrane fouling. The EO of the TSAMBR permeate was performed using a Ti/SnO(2)-Sb(2)O(5)-IrO(2) electrode. After 6-h EO, a complete decolourization was achieved and the COD removal efficiency was increased to 96.2 ± 1.2-98.2 ± 0.3%. The high-quality effluent produced by the TSAMBR-EO system can be reused as process water for system closure in pulp and paper mill.

  18. Reaction and spectroscopic study of supported metal oxide catalysts

    NASA Astrophysics Data System (ADS)

    Ramani, Narayanan C.

    The role of surface structure, cation reducibility, surface acidity and the effect of the support was examined in the reaction of 1-butene over well characterized, supported metal oxide catalysts. Cr, Mo and W oxides supported on SiOsb2 were used to study the effect of structure, surface acidity and cation reducibility in the isomerization and selective oxidation of 1-butene. Supported oxides of Mo on TiOsb2,\\ Alsb2Osb3 and SiOsb2 were used to understand the role of the support in the selective oxidation of 1-butene. The surface acidity of SiOsb2 supported Cr, Mo, W and V oxide catalysts was examined by pyridine adsorption. Existing theoretical models of acidity were compared against experimental data. Over Mo(VI)/SiOsb2 and W(VI)/SiOsb2, isomerization through both a Bronsted catalyzed pathway and an allylic pathway were observed, while only the allylic pathway was observed over Cr(VI)/SiOsb2. The greater reducibility of the Cr cation compared to Mo and W cations was identified as the reason for the allylic pathway being dominant over Cr(VI)/SiOsb2. Cation reducibility was again seen to play an important role in the selective oxidation of 1-butene over SiOsb2 supported metal oxides. The turn over frequencies for 1,3-butadiene formation followed the trend in red-ox ability, with Cr > Mo > W. The activity to 1,3-butadiene formation did not change with increasing weight loading of Mo over TiOsb2 and Alsb2Osb3 supports. An analysis of the turn over frequencies of the supports and the supported cations revealed that a support effect, through the bridging oxygen ligand, dominated the intrinsic cation reducibility of Mo for these catalysts. The existence of Bronsted acidity over SiOsb2 supported Cr, Mo and V oxides was shown by an analysis of the OH region of the infrared spectrum, and by the adsorption of 1-butene and pyridine. Existing theoretical models for Bronsted acidity over supported metal oxides were shown to be inadequate to describe the observed results over

  19. Selective aerobic oxidation of 1,3-propanediol to 3-hydroxypropanoic acid using hydrotalcite supported bimetallic gold nanoparticle catalyst in water

    NASA Astrophysics Data System (ADS)

    Mohammad, Mujahid; Nishimura, Shun; Ebitani, Kohki

    2015-02-01

    Selective oxidation of 1,3-propanediol (1,3-PD) to 3-hydroxypropanoic acid (3-HPA), an important industrial building block, was successfully achieved using hydrotalcite-supported bimetallic Au nanoparticle catalysts in water at 343 K under aerobic and base-free conditions. The highest yield of 42% with 73% selectivity towards 3-HPA was afforded by 1wt% Au0.8Pd0.2-PVP/HT catalyst.

  20. Aerobic oxidative cyclization of benzamides via meta-selective C-H tert-alkylation: rapid entry to 7-alkylated isoquinolinediones.

    PubMed

    Tang, Shi; Deng, You-Lin; Li, Jie; Wang, Wen-Xin; Wang, Ying-Chun; Li, Zeng-Zeng; Yuan, Li; Chen, Shi-Lu; Sheng, Rui-Long

    2016-03-25

    A novel copper-catalyzed aerobic oxidative cyclization of benzamides via meta-selective C-H tert-alkylation using AIBN and analogues as radical precursors was described. This strategy provides an elusive and rapid means to 7-tert-alkylated isoquinolinediones, as well as the construction of tertiary alkyl-aryl C(sp(3))-C(sp(2)) bonds with positional selectivity.

  1. Photovoltaic-driven organic electrosynthesis and efforts toward more sustainable oxidation reactions

    PubMed Central

    Nguyen, Bichlien H; Perkins, Robert J; Smith, Jake A

    2015-01-01

    Summary The combination of visible light, photovoltaics, and electrochemistry provides a convenient, inexpensive platform for conducting a wide variety of sustainable oxidation reactions. The approach presented in this article is compatible with both direct and indirect oxidation reactions, avoids the need for a stoichiometric oxidant, and leads to hydrogen gas as the only byproduct from the corresponding reduction reaction. PMID:25815081

  2. 40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for...

  3. 40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for...

  4. Ionic Conductivity and its Role in Oxidation Reactions

    NASA Astrophysics Data System (ADS)

    Tamimi, Mazin Abdulla

    In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the

  5. Effect of process design and operating parameters on aerobic methane oxidation in municipal WWTPs.

    PubMed

    Daelman, Matthijs R J; Van Eynde, Tamara; van Loosdrecht, Mark C M; Volcke, Eveline I P

    2014-12-01

    Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere.

  6. Reaction of lincosamide antibiotics with manganese oxide in aqueous solution.

    PubMed

    Chen, Wan-Ru; Ding, Yunjie; Johnston, Cliff T; Teppen, Brian J; Boyd, Stephen A; Li, Hui

    2010-06-15

    Lincosamides are among the most frequently detected antibacterial agents in effluents from wastewater treatment plants and surface runoff at agricultural production systems. Little is known about their transformations in the environment. This study revealed that manganese oxide caused rapid and extensive decomposition of clindamycin and lincomycin in aqueous solution. The reactions occurred mainly at the pyranose ring of lincosamides, initially by formation of complexes with Mn and cleavage of the ether linkage, leading to the formation of a variety of degradation products via subsequent hydrolytic and oxidative reactions. The results of LC-MS/MS and FTIR analysis confirm cleavage of the C-O-C bond in the pyranose ring, formation of multiple carbonyl groups, and transformation of the methylthio moiety to sulfur oxide. The overall transformation was controlled by interactions of cationic species of lincosamides with MnO(2) surfaces. The presence of electrolytes (i.e., NaCl, CaCl(2), and MnCl(2)) and dissolved organic matter in aqueous solution, and increase of solution pH, diminished lincosamide binding to MnO(2) hence reducing the rate and magnitude of the transformations. Results from this study indicate that manganese dioxides in soils and sediments could contribute to the decomposition of lincosamide antibiotics released into the environment.

  7. Use of Advanced Oxidation and Aerobic Degradation for Remediation of Various Hydrocarbon Contaminates

    SciTech Connect

    Paul Fallgren

    2009-03-06

    Western Research Institute in conjunction with Sierra West Consultants, Inc., Tetra Tech, Inc., and the U.S. Department of Energy conducted laboratory and field studies to test different approaches to enhance degradation of hydrocarbons and associated contaminants. WRI in conjunction with Sierra West Consultants, Inc., conducted a laboratory and field study for using ozone to treat a site contaminated with MTBE and other hydrocarbons. Results from this study demonstrate that a TOD test can be used to resolve the O{sub 3} dosage problem by establishing a site-specific benchmark dosage for field ozone applications. The follow-up testing of the laboratory samples provided indications that intrinsic biodegradation could be stimulated by adding oxygen. Laboratory studies also suggests that O3 dosage in the full-scale field implementation could be dialed lower than stoichiometrically designed to eliminate the formation of Cr(VI). WRI conducted a study involving a series of different ISCO oxidant applications to diesel-contaminated soil and determined the effects on enhancing biodegradation to degrade the residual hydrocarbons. Soils treated with permanganate followed by nutrients and with persulfate followed by nutrients resulted in the largest decrease in TPH. The possible intermediates and conditions formed from NOM and TPH oxidation by permanganate and activated persulfate favors microbial TPH degrading activity. A 'passive-oxidation' method using microbial fuel cell (MFC) technology was conducted by WRI in conjunction with Tetra Tech, Inc., to degrade MTBE in groundwater. These experiments have demonstrated that a working MFC (i.e., one generating power) could be established in the laboratory using contaminated site water or buffered media inoculated with site water and spiked with MTBE, benzene, or toluene. Electrochemical methods were studied by WRI with goal of utilizing low voltage and amperage electrical sources for 'geo-oxidation' of organic contaminants. The

  8. Laccase-Functionalized Graphene Oxide Assemblies as Efficient Nanobiocatalysts for Oxidation Reactions

    PubMed Central

    Patila, Michaela; Kouloumpis, Antonios; Gournis, Dimitrios; Rudolf, Petra; Stamatis, Haralambos

    2016-01-01

    Multi-layer graphene oxide-enzyme nanoassemblies were prepared through the multi-point covalent immobilization of laccase from Trametes versicolor (TvL) on functionalized graphene oxide (fGO). The catalytic properties of the fGO-TvL nanoassemblies were found to depend on the number of the graphene oxide-enzyme layers present in the nanostructure. The fGO-TvL nanoassemblies exhibit an enhanced thermal stability at 60 °C, as demonstrated by a 4.7-fold higher activity as compared to the free enzyme. The multi-layer graphene oxide-enzyme nanoassemblies can efficiently catalyze the oxidation of anthracene, as well as the decolorization of an industrial dye, pinacyanol chloride. These materials retained almost completely their decolorization activity after five reaction cycles, proving their potential as efficient nano- biocatalysts for various applications. PMID:26927109

  9. Field and experimental evidence for low-O2 affinity of aerobic methane oxidizers in coastal waters

    NASA Astrophysics Data System (ADS)

    Steinle, Lea; Maltby, Johanna; Bange, Hermann; Kock, Annette; Lehmann, Moritz F.; Treude, Tina; Niemann, Helge

    2015-04-01

    The coastal ocean accounts for more than 75 % of the global oceanic methane emissions. An important process in mitigating methane emissions from the seawater to the atmosphere is aerobic methane oxidation (MOx). Coastal oceans are highly dynamic systems, in particular with regard to the variability of temperature, salinity, and oxygen concentrations, all of which are potential key environmental factors controlling MOx. We conducted a two-year time-series study of MOx measurements in the water column of a coastal inlet in the southwestern Baltic Sea (Eckernförde Bay, Boknis Eck Time Series Station, 54°31.823 N, 10°02.764 E, 28 m water depth; www.bokniseck.de). Physicochemical parameters at this station have been monitored since 1957. Seasonal stratification during summer/autumn leads to intermittent oxygen depletion (hypoxic to anoxic) in bottom waters in the later part of the stratification period. The duration of these low-oxygen events increased since the 1970s (Lennartz et al., 2014). Furthermore, the organic-rich seafloor continuously produces methane, which leads to gas ebullition followed by accumulation of dissolved methane in bottom waters (up to 470 nM) and supersaturation (with respect to the atmospheric equilibrium) in surface waters (up to 27 nM). MOx communities were most active in bottom waters (1-5 nM/day), which usually contain the lowest oxygen concentrations (sometimes below the in situ detection limit of ~1 µM). In order to better understand the effect of low oxygen concentrations, and thus of hypoxic and suboxic events, on MOx in coastal systems, we conducted lab-based experiments, during which we adjusted oxygen concentrations to values between 0.2 - 220 µM in methane-rich (~100 nM) Eckernförde Bay waters. These samples were then incubated with trace amounts of tritium-labeled methane to assess first order rate constants of methane oxidation. Highest MOx rates were detected at oxygen concentrations of ~0.5 µM (considerably higher than at

  10. Reactions of oxidatively activated arylamines with thiols: reaction mechanisms and biologic implications. An overview.

    PubMed Central

    Eyer, P

    1994-01-01

    Aromatic amines belong to a group of compounds that exert their toxic effects usually after oxidative biotransformation, primarily in the liver. In addition, aromatic amines also undergo extrahepatic activation to yield free arylaminyl radicals. The reactive intermediates are potential promutagens and procarcinogens, and responsible for target tissue toxicity. Since thiols react with these intermediates at high rates, it is of interest to know the underlying reaction mechanisms and the toxicologic implications. Phenoxyl radicals from aminophenols and aminyl radicals from phenylenediamines quickly disproportionate to quinone imines and quinone diimines. Depending on the structure, Michael addition or reduction reactions with thiols may prevail. Products of sequential oxidation/addition reactions (e.g., S-conjugates of aminophenols) are occasionally more toxic than the parent compounds because of their higher autoxidizability and their accumulation in the kidney. Even after covalent binding of quinone imines to protein SH groups, the resulting thioethers are able to autoxidize. The quinoid thioethers can then cross-link the protein by addition to neighboring nucleophiles. The reactions of nitrosoarenes with thiols yield a so-called "semimercaptal" from which various branching reactions detach, depending on substituents. Compounds with strong pi-donors, like 4-nitrosophenetol, give a resonance-stabilized N-(thiol-S-yl)-arylamine cation that may lead to bicyclic products, thioethers, and DNA adducts. Examples of toxicologic implications of the interactions of nitroso compounds with thiols are given for nitrosoimidazoles, heterocyclic nitroso compounds from protein pyrolysates, and nitrosoarenes. These data indicate that interactions of activated arylamines with thiols may not be regarded exclusively as detoxication reactions. PMID:7889834

  11. Fly Ash and Mercury Oxidation/Chlorination Reactions

    SciTech Connect

    Sukh Sidhu; Patanjali Varanasi

    2008-12-31

    Mercury is a known pollutant that has detrimental effect on human health and environment. The anthropogenic emissions of mercury account for 10 to 30% of worldwide mercury emissions. There is a need to control/reduce anthropogenic mercury emissions. Many mercury control technologies are available but their effectiveness is dependent on the chemical form of mercury, because different chemical forms of mercury have different physical and chemical properties. Mercury leaves the boiler in its elemental form but goes through various transformations in the post-combustion zone. There is a need to understand how fly ash and flue gas composition affect speciation, partitioning, and reactions of mercury under the full range of post-combustion zone conditions. This knowledge can then be used to predict the chemical transformation of mercury (elemental, oxidized or particulate) in the post combustion zone and thus help with the control of mercury emissions from coal-burning power plants. To accomplish this goal present study was conducted using five coal fly ashes. These ashes were characterized and their catalytic activity was compared under selected reaction conditions in a fixed bed reactor. Based on the results from these fly ash experiments, three key components (carbon, iron oxide and calcium oxide) were chosen. These three components were then used to prepare model fly ashes. Silica/alumina was used as a base for these model fly ashes. One, two or three component model fly ashes were then prepared to investigate mercury transformation reactions. The third set of experiments was performed with CuO and CuCl2 catalysts to further understand the mercury oxidation process. Based on the results of these three studies the key components were predicted for different fly ash compositions under variety of flue gas conditions. A fixed bed reactor system was used to conduct this study. In all the experiments, the inlet concentration of Hg0(g) was maintained at 35 {micro}g/m3 using

  12. Aerobic exercise reduces oxidative stress and improves vascular changes of small mesenteric and coronary arteries in hypertension

    PubMed Central

    Roque, Fernanda R; Briones, Ana M; García-Redondo, Ana B; Galán, María; Martínez-Revelles, Sonia; Avendaño, Maria S; Cachofeiro, Victoria; Fernandes, Tiago; Vassallo, Dalton V; Oliveira, Edilamar M; Salaices, Mercedes

    2013-01-01

    Background and Purpose Regular physical activity is an effective non-pharmacological therapy for prevention and control of hypertension. We investigated the effects of aerobic exercise training in vascular remodelling and in the mechanical and functional alterations of coronary and small mesenteric arteries from spontaneously hypertensive rats (SHR). Experimental Approach Normotensive Wistar Kyoto (WKY), SHR and SHR trained on a treadmill for 12 weeks were used to evaluate vascular structural, mechanical and functional properties. Key Results Exercise did not affect lumen diameter, wall thickness and wall/lumen ratio but reduced vascular stiffness of coronary and mesenteric arteries from SHR. Exercise also reduced collagen deposition and normalized altered internal elastic lamina organization and expression of MMP-9 in mesenteric arteries from SHR. Exercise did not affect contractile responses of coronary arteries but improved the endothelium-dependent relaxation in SHR. In mesenteric arteries, training normalized the increased contractile responses induced by U46619 and by high concentrations of acetylcholine. In vessels from SHR, exercise normalized the effects of the NADPH oxidase inhibitor apocynin and the NOS inhibitor l-NAME in vasodilator or vasoconstrictor responses, normalized the increased O2− production and the reduced Cu/Zn superoxide dismutase expression and increased NO production. Conclusions and Implications Exercise training of SHR improves endothelial function and vascular stiffness in coronary and small mesenteric arteries. This might be related to the concomitant decrease of oxidative stress and increase of NO bioavailability. Such effects demonstrate the beneficial effects of exercise on the vascular system and could contribute to a reduction in blood pressure. PMID:22994554

  13. Mechanism of heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong; Xu, Wenqing; Yu, Yunbo

    2007-05-24

    Heterogeneous reaction of carbonyl sulfide (OCS) on magnesium oxide (MgO) under ambient conditions was investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), quadrupole mass spectrometer (QMS), and density functional theory (DFT) calculations. It reveals that OCS can be catalytically hydrolyzed by surface hydroxyl on MgO to produce carbon dioxide (CO2) and hydrogen sulfide (H2S), and then H2S can be further catalytically oxidized by surface oxygen or gaseous oxygen on MgO to form sulfite (SO3(2-)) and sulfate (SO4(2-)). Hydrogen thiocarbonate (HSCO2-) was found to be the crucial intermediate. Surface hydrogen sulfide (HS), sulfur dioxide (SO2), and surface sulfite (SO3(2-)) were also found to be intermediates for the formation of sulfate. Furthermore, the surface hydroxyl contributes not only to the formation of HSCO2- but also to HSCO2- decomposition. On the basis of experimental results, the heterogeneous reaction mechanism of OCS on MgO was discussed.

  14. Continuous Aerobic Training in Individualized Intensity Avoids Spontaneous Physical Activity Decline and Improves MCT1 Expression in Oxidative Muscle of Swimming Rats

    PubMed Central

    Scariot, Pedro P. M.; Manchado-Gobatto, Fúlvia de Barros; Torsoni, Adriana S.; dos Reis, Ivan G. M.; Beck, Wladimir R.; Gobatto, Claudio A.

    2016-01-01

    Although aerobic training has been shown to affect the lactate transport of skeletal muscle, there is no information concerning the effect of continuous aerobic training on spontaneous physical activity (SPA). Because every movement in daily life (i.e., SPA) is generated by skeletal muscle, we think that it is possible that an improvement of SPA could affect the physiological properties of muscle with regard to lactate transport. The aim of this study was to evaluate the effect of 12 weeks of continuous aerobic training in individualized intensity on SPA of rats and their gene expressions of monocarboxylate transporters (MCT) 1 and 4 in soleus (oxidative) and white gastrocnemius (glycolytic) muscles. We also analyzed the effect of continuous aerobic training on aerobic and anaerobic parameters using the lactate minimum test (LMT). Sixty-day-old rats were randomly divided into three groups: a baseline group in which rats were evaluated prior to initiation of the study; a control group (Co) in which rats were kept without any treatment during 12 weeks; and a chronic exercise group (Tr) in which rats swam for 40 min/day, 5 days/week at 80% of anaerobic threshold during 12 weeks. After the experimental period, SPA of rats was measured using a gravimetric method. Rats had their expression of MCTs determined by RT-PCR analysis. In essence, aerobic training is effective in maintaining SPA, but did not prevent the decline of aerobic capacity and anaerobic performance, leading us to propose that the decline of SPA is not fully attributed to a deterioration of physical properties. Changes in SPA were concomitant with changes in MCT1 expression in the soleus muscle of trained rats, suggestive of an additional adaptive response toward increased lactate clearance. This result is in line with our observation showing a better equilibrium on lactate production-remotion during the continuous exercise (LMT). We propose an approach to combat the decline of SPA of rats in their home

  15. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    SciTech Connect

    Zhuang Lina; Wang Wenjin; Hong Feng; Yang Shengchun; You Hongjun; Fang Jixiang; Ding Bingjun

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  16. The effect of low-level laser therapy on oxidative stress and functional fitness in aged rats subjected to swimming: an aerobic exercise.

    PubMed

    Guaraldo, Simone A; Serra, Andrey Jorge; Amadio, Eliane Martins; Antônio, Ednei Luis; Silva, Flávio; Portes, Leslie Andrews; Tucci, Paulo José Ferreira; Leal-Junior, Ernesto Cesar Pinto; de Carvalho, Paulo de Tarso Camillo

    2016-07-01

    The aim of the present study was to determine whether low-level laser therapy (LLLT) in conjunction with aerobic training interferes with oxidative stress, thereby influencing the performance of old rats participating in swimming. Thirty Wistar rats (Norvegicus albinus) (24 aged and six young) were tested. The older animals were randomly divided into aged-control, aged-exercise, aged-LLLT, aged-LLLT/exercise, and young-control. Aerobic capacity (VO2max(0.75)) was analyzed before and after the training period. The exercise groups were trained for 6 weeks, and the LLLT was applied at 808 nm and 4 J energy. The rats were euthanized, and muscle tissue was collected to analyze the index of lipid peroxidation thiobarbituric acid reactive substances (TBARS), glutathione (GSH), superoxide dismutase (SOD), and catalase (CAT) activities. VO2 (0.75)max values in the aged-LLLT/exercise group were significantly higher from those in the baseline older group (p <0.01) and the LLLT and exercise group (p <0.05). The results indicate that the activities of CAT, SOD, and GPx were higher and statistically significant (p <0.05) in the LLLT/exercise group than those in the LLLT and exercise groups. Young animals presented lesser and statistically significant activities of antioxidant enzymes compared to the aged group. The LLLT/exercise group and the LLLT and exercise group could also mitigate the concentration of TBARS (p > 0.05). Laser therapy in conjunction with aerobic training may reduce oxidative stress, as well as increase VO2 (0.75)max, indicating that an aerobic exercise such as swimming increases speed and improves performance in aged animals treated with LLLT.

  17. Effects of Sesame (Sesamum indicum L.) Supplementation on Creatine Kinase, Lactate Dehydrogenase, Oxidative Stress Markers, and Aerobic Capacity in Semi-Professional Soccer Players

    PubMed Central

    Barbosa, Carlos V. da Silva; Silva, Alexandre S.; de Oliveira, Caio V. C.; Massa, Nayara M. L.; de Sousa, Yasmim R. F.; da Costa, Whyara K. A.; Silva, Ayice C.; Delatorre, Plínio; Carvalho, Rhayane; Braga, Valdir de Andrade; Magnani, Marciane

    2017-01-01

    Nutritional intervention with antioxidants rich foods has been considered a strategy to minimize the effects of overtraining in athletes. This experimental, randomized, and placebo-controlled study evaluated the effects of consumption of sesame (Sesamum indicum L.) on muscle damage markers, oxidative stress, systemic inflammation, and aerobic performance in male semi-professional soccer players. Twenty athletes were randomly assigned to groups that received 40 g (two tablespoons) per day of sesame or a placebo during 28 days of regular training (exposed to routine training that includes loads of heavy training in the final half of the season). Before and after intervention, creatine kinase (CK), lactate dehydrogenase (LDH), malondialdehyde (MDA), superoxide dismutase (SOD), C-reactive protein (hs-CRP), and aerobic capacity were evaluated. Before intervention, a physiologic imbalance was noted in both groups related to CK and LDH levels. Sesame intake caused a reduction of CK (19%, p < 0.05), LDH (37%, p < 0.05), MDA (55%, p < 0.05) and hs-CRP (53%, p < 0.05) and increased SOD (14%, p < 0.05), vitamin A (25%, p < 0.05), and vitamin E (65%, p < 0.05) in the experimental group. These phenomena were accompanied by increased aerobic capacity (17%, p < 0.05). The placebo group showed an increase in CK (5%, p < 0.05) and no significant change in LDH, SOD or vitamin A. MDA levels decreased (21%, p < 0.05) and vitamin E increased (14%, p < 0.05) in the placebo group, but to a much lesser extent than in the experimental group. These results show that sesame consumption may reduce muscle damage and oxidative stress while improving the aerobic capacity in soccer players.

  18. Mass transfer model for two-layer TBP oxidation reactions

    SciTech Connect

    Laurinat, J.E.

    1994-09-28

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development.

  19. Oxidative-coupling reaction of TNT reduction products by manganese oxide.

    PubMed

    Kang, Ki-Hoon; Lim, Dong-Min; Shin, Hyunsang

    2006-03-01

    Abiotic transformation of TNT reduction products via oxidative-coupling reaction was investigated using Mn oxide. In batch experiments, all the reduction products tested were completely transformed by birnessite, one of natural Mn oxides present in soil. Oxidative-coupling was the major transformation pathway, as confirmed by mass spectrometric analysis. Using observed pseudo-first-order rate constants with respect to birnessite loadings, surface area-normalized specific rate constants, ksurf, were determined. As expected, ksurf of diaminonitrotoluenes (DATs) (1.49-1.91L/m2 d) are greater about 2 orders than that of dinitroaminotoluenes (DNTs) (1.15 x 10(-2)-2.09 x 10(-2)L/m2d) due to the increased number of amine group. In addition, by comparing the value of ksurf between DNTs or DATs, amine group on ortho position is likely to be more preferred for the oxidation by birnessite. Although cross-coupling of TNT in the presence of various mediator compounds was found not to be feasible, transformation of TNT by reduction using Fe0 followed by oxidative-coupling using Mn oxide was efficient, as evaluated by UV-visible spectrometry.

  20. A factorial randomized controlled trial to evaluate the effect of micronutrients supplementation and regular aerobic exercise on maternal endothelium-dependent vasodilatation and oxidative stress of the newborn

    PubMed Central

    2011-01-01

    Background Many studies have suggested a relationship between metabolic abnormalities and impaired fetal growth with the development of non-transmissible chronic diseases in the adulthood. Moreover, it has been proposed that maternal factors such as endothelial function and oxidative stress are key mechanisms of both fetal metabolic alterations and subsequent development of non-transmissible chronic diseases. The objective of this project is to evaluate the effect of micronutrient supplementation and regular aerobic exercise on endothelium-dependent vasodilation maternal and stress oxidative of the newborn. Methods and design 320 pregnant women attending to usual prenatal care in Cali, Colombia will be included in a factorial randomized controlled trial. Women will be assigned to the following intervention groups: 1. Control group: usual prenatal care (PC) and placebo (maltodextrine). 2. Exercise group: PC, placebo and aerobic physical exercise. 3. Micronutrients group: PC and a micronutrients capsule consisting of zinc (30 mg), selenium (70 μg), vitamin A (400 μg), alphatocopherol (30 mg), vitamin C (200 mg), and niacin (100 mg). 4. Combined interventions Group: PC, supplementation of micronutrients, and aerobic physical exercise. Anthropometric measures will be taken at the start and at the end of the interventions. Discussion Since in previous studies has been showed that the maternal endothelial function and oxidative stress are related to oxidative stress of the newborn, this study proposes that complementation with micronutrients during pregnancy and/or regular physical exercise can be an early and innovative alternative to strengthen the prevention of chronic diseases in the population. Trial registration NCT00872365. PMID:21356082

  1. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Li, Wenyuan

    Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching

  2. Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

    ERIC Educational Resources Information Center

    Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

    2011-01-01

    Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

  3. Oxidative stress and inflammatory reaction modulation by white wine.

    PubMed

    Bertelli, Alberto A E; Migliori, Massamiliano; Panichi, Vincenzo; Longoni, Bianamaria; Origlia, Nicola; Ferretti, Agnese; Cuttano, Maria Giuseppa; Giovannini, Luca

    2002-05-01

    Wine and olive oil, essential components of the Mediterranean diet, are considered important factors for a healthy life style. Tyrosol (T) and caffeic acid (CA) are found in both extra virgin olive oil and in white wine. Three white wines from the northeast Italy and four white wines from Germany were analyzed for their content of T and CA. These compounds were tested for their antioxidant activity and their capacity to modulate three different cytokines: IL-1 beta, IL-6, and TNF-alpha, which are currently considered to be the major cytokines influencing the acute phase of the inflammatory response. Furthermore, the antioxidant activity of T and CA was analyzed by monitoring the oxidation of a redox-sensitive probe by using laser scanning confocal microscopy. T and CA, applied at nanomolar range, were found to significantly reduce the generation of oxidants induced by azobis-amidinopropanedihydrochloride. Peripheral blood mononuclear cells (PBMC) from healthy volunteers were incubated at 37 degrees C for 12 hours with 100 ng LPS (E. coli and P. maltofilia). Increasing doses of T and CA (150 nM to 300 microM) were added and cell-associated IL-1 beta and TNF-alpha were determined by immunoreactive tests after three freeze-thaw cycles. IL-6 release was also determined in cell surnatants. LPS-stimulated PBMC showed a significant increase in cytokine release, while T and CA, used at nanomolar concentrations, were able to modulate their expression. Taken together, these results suggest a remarkable effect of white wine non-alcoholic compounds on oxidative stress and inflammatory reaction.

  4. Theoretical study on the catalytic reactivity of N-hydroxyphthalimide tuned by different heterocyclic substitutions on its phenyl ring for aerobic oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Kexian; Xie, Haiying; Jiang, Kezhi; Mao, Jianyong

    2016-07-01

    The structure-reactivity relationship of new hydroxyimide organocatalysts based on the heterocyclic replacements of the phenyl ring of N-hydroxyphthalimide (NHPI) has been theoretically investigated to gain a mature understanding of this particular catalysis for aerobic oxidation. We find that the reactivity of catalysts with the common five-member aromatic rings is lower than that of NHPI. The catalyst with the recyclable structure of imidazolium ionic liquid may serve as a novel model catalyst for further improvements due to its reactivity comparable to that of NHPI. The catalytic reactivity of multi-nitroxyl catalysts is theoretically more fascinating than that of the highly efficient N,N-dihydroxypyromellitimide.

  5. CFD Study of Full-Scale Aerobic Bioreactors: Evaluation of Dynamic O2 Distribution, Gas-Liquid Mass Transfer and Reaction

    SciTech Connect

    Humbird, David; Sitaraman, Hariswaran; Stickel, Jonathan; Sprague, Michael A.; McMillan, Jim

    2016-11-18

    If advanced biofuels are to measurably displace fossil fuels in the near term, they will have to operate at levels of scale, efficiency, and margin unprecedented in the current biotech industry. For aerobically-grown products in particular, scale-up is complex and the practical size, cost, and operability of extremely large reactors is not well understood. Put simply, the problem of how to attain fuel-class production scales comes down to cost-effective delivery of oxygen at high mass transfer rates and low capital and operating costs. To that end, very large reactor vessels (>500 m3) are proposed in order to achieve favorable economies of scale. Additionally, techno-economic evaluation indicates that bubble-column reactors are more cost-effective than stirred-tank reactors in many low-viscosity cultures. In order to advance the design of extremely large aerobic bioreactors, we have performed computational fluid dynamics (CFD) simulations of bubble-column reactors. A multiphase Euler-Euler model is used to explicitly account for the spatial distribution of air (i.e., gas bubbles) in the reactor. Expanding on the existing bioreactor CFD literature (typically focused on the hydrodynamics of bubbly flows), our simulations include interphase mass transfer of oxygen and a simple phenomenological reaction representing the uptake and consumption of dissolved oxygen by submerged cells. The simulations reproduce the expected flow profiles, with net upward flow in the center of column and downward flow near the wall. At high simulated oxygen uptake rates (OUR), oxygen-depleted regions can be observed in the reactor. By increasing the gas flow to enhance mixing and eliminate depleted areas, a maximum oxygen transfer (OTR) rate is obtained as a function of superficial velocity. These insights regarding minimum superficial velocity and maximum reactor size are incorporated into NREL's larger techno-economic models to supplement standard reactor design equations.

  6. Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

    ERIC Educational Resources Information Center

    Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

    2008-01-01

    A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

  7. Short-term Regular Aerobic Exercise Reduces Oxidative Stress Produced by Acute High Intraluminal Pressure in the Adipose Microvasculature.

    PubMed

    Robinson, Austin T; Fancher, Ibra S; Sudhahar, Varadarajan; Bian, Jing Tan; Cook, Marc; Mahmoud, Abeer M; Ali, Mohamed; Ushio-Fukai, Masuko; Brown, Michael D; Fukai, Tohru; Phillips, Shane A

    2017-02-24

    High blood pressure has been shown to elicit impaired dilation in the vasculature. The purpose of this investigation was to elucidate the mechanisms through which high pressure may elicit vascular dysfunction, and determine the mechanisms through which regular aerobic exercise protects arteries against high pressure.

  8. The reaction of hydrogen peroxide with nitrogen dioxide and nitric oxide.

    NASA Technical Reports Server (NTRS)

    Gray, D.; Lissi, E.; Heicklen, J.

    1972-01-01

    The reactions were studied with the aid of a mass spectrometer. A pinhole bleed system provided continuous sampling of the gas mixture in the cell during the reaction. It was found that the homogeneous reactions of nitric oxide and nitrogen dioxide with hydrogen peroxide are too slow to be of any significance in the upper atmosphere. However, the heterogeneous reactions may be important in the conversion of nitric oxide to nitrogen dioxide in the case of polluted urban atmospheres.

  9. Uraninite oxidation and dissolution induced by manganese oxide: A redox reaction between two insoluble minerals

    NASA Astrophysics Data System (ADS)

    Wang, Zimeng; Lee, Sung-Woo; Kapoor, Pratyul; Tebo, Bradley M.; Giammar, Daniel E.

    2013-01-01

    The longevity of subsurface U(IV) produced by reduction of U(VI) during in situ bioremediation can be limited by reoxidation to more mobile U(VI) species. Coupling of the biogeochemical cycles of U and Mn may affect the fate and transport of uranium. Manganese oxides can act as a powerful oxidant that accelerates the oxidative dissolution of UO2. This study investigated the physical and chemical factors controlling the interaction between UO2 and MnO2, which are both poorly soluble minerals. A multi-chamber reactor with a permeable membrane was used to eliminate direct contact of the two minerals while still allowing transport of aqueous species. The oxidation of UO2 was not significantly enhanced by MnO2 if the two solids were physically separated. Complete mixing of MnO2 with UO2 led to a much greater extent and rate of U oxidation. When direct contact is not possible, the reaction slowly progresses through release of soluble U(IV) with its adsorption and oxidation on MnO2. Continuously-stirred tank reactors (CSTRs) were used to quantify the steady-state rates of UO2 dissolution induced by MnO2. MnO2 dramatically promoted UO2 dissolution, but the degree of promotion leveled off once the MnO2:UO2 ratio exceeded a critical value. Substantial amounts of U(VI) and Mn(II) were retained on MnO2 surfaces. The total production of Mn(II) was less than that of U(VI), indicating that the fate of Mn products and their impact on UO2-MnO2 reaction kinetics were complicated and may involve formation of Mn(III) phases. At higher dissolved inorganic carbon concentrations, UO2 oxidation by MnO2 was faster and less U(VI) was adsorbed to MnO2. Such an inverse relationship suggested that U(VI) may passivate MnO2 surfaces. A conceptual model was developed to describe the oxidation rate of UO2 by MnO2. This model is potentially applicable to a broad range of water chemistry conditions and is relevant to other environmental redox processes involving two poorly soluble minerals.

  10. Thermochemistry and reaction paths in the oxidation reaction of benzoyl radical: C6H5C•(═O).

    PubMed

    Sebbar, Nadia; Bozzelli, Joseph W; Bockhorn, Henning

    2011-10-27

    Alkyl substituted aromatics are present in fuels and in the environment because they are major intermediates in the oxidation or combustion of gasoline, jet, and other engine fuels. The major reaction pathways for oxidation of this class of molecules is through loss of a benzyl hydrogen atom on the alkyl group via abstraction reactions. One of the major intermediates in the combustion and atmospheric oxidation of the benzyl radicals is benzaldehyde, which rapidly loses the weakly bound aldehydic hydrogen to form a resonance stabilized benzoyl radical (C6H5C(•)═O). A detailed study of the thermochemistry of intermediates and the oxidation reaction paths of the benzoyl radical with dioxygen is presented in this study. Structures and enthalpies of formation for important stable species, intermediate radicals, and transition state structures resulting from the benzoyl radical +O2 association reaction are reported along with reaction paths and barriers. Enthalpies, ΔfH298(0), are calculated using ab initio (G3MP2B3) and density functional (DFT at B3LYP/6-311G(d,p)) calculations, group additivity (GA), and literature data. Bond energies on the benzoyl and benzoyl-peroxy systems are also reported and compared to hydrocarbon systems. The reaction of benzoyl with O2 has a number of low energy reaction channels that are not currently considered in either atmospheric chemistry or combustion models. The reaction paths include exothermic, chain branching reactions to a number of unsaturated oxygenated hydrocarbon intermediates along with formation of CO2. The initial reaction of the C6H5C(•)═O radical with O2 forms a chemically activated benzoyl peroxy radical with 37 kcal mol(-1) internal energy; this is significantly more energy than the 21 kcal mol(-1) involved in the benzyl or allyl + O2 systems. This deeper well results in a number of chemical activation reaction paths, leading to highly exothermic reactions to phenoxy radical + CO2 products.

  11. Anti-Campylobacter, anti-aerobic, and anti-oxidative effects of roselle calyx extract and protocatechuic acid in ground beef.

    PubMed

    Yin, Mei-chin; Chao, Che-yi

    2008-09-30

    The inhibitory effect of roselle calyx extract and protocatechuic acid against susceptible and antibiotic-resistant Campylobacter jejuni, C. coli and C. fetus in agar plate and ground beef was examined. The minimal inhibitory concentrations of roselle calyx extract and protocatechuic acid against susceptible and antibiotic-resistant Campylobacter species were in the range of 96-152 and 20-44 microg/ml, respectively. Temperature treatments from 25 to 100 degrees C did not affect the anti-Campylobacter activity of protocatechuic acid. In ground beef stored at 15 degrees C for 6 days, roselle calyx extract and protocatechuic acid inhibited the survival and growth of aerobes, and susceptible and antibiotic-resistant Campylobacter species, in which protocatechuic acid exhibited dose-dependent effect. Both roselle calyx extract and protocatechuic acid decreased lipid oxidation levels in ground beef, in which protocatechuic acid also exhibited dose-dependent effect. The addition of roselle calyx extract or protocatechuic acid did not affect cooking loss, pH value, sensory attributes and content of fat, protein and moisture of beef samples during storage at 4 degrees C for 15 days. These data support that roselle calyx extract and protocatechuic acid may be used for muscle foods to prevent contamination from Campylobacter and aerobes, as well as delay lipid oxidation.

  12. Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation

    NASA Astrophysics Data System (ADS)

    Verginelli, Iason; Baciocchi, Renato

    2011-11-01

    A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.

  13. Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation.

    PubMed

    Verginelli, Iason; Baciocchi, Renato

    2011-11-01

    A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.

  14. Activation energy of tantalum-tungsten oxide thermite reactions

    SciTech Connect

    Cervantes, Octavio G.; Munir, Zuhair A.; Kuntz, Joshua D.; Gash, Alexander E.

    2011-01-15

    The activation energy of a sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the high-pressure spark plasma sintering (HPSPS) technique at 300 and 400 C. The ignition temperatures were investigated under high heating rates (500-2000 C min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Samples consolidated at 300 C exhibit an abrupt change in temperature response prior to the main ignition temperature. This change in temperature response is attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465 to 670 C. The activation energies of the SG derived Ta-WO{sub 3} thermite composite consolidated at 300 and 400 C were determined to be 38{+-} 2 kJ mol{sup -1} and 57 {+-} 2 kJ mol{sup -1}, respectively. (author)

  15. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

    SciTech Connect

    Cervantes, O; Kuntz, J; Gash, A; Munir, Z

    2010-02-25

    The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300 C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.

  16. Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

    PubMed

    Xiong, Shangchao; Xiao, Xin; Huang, Nan; Dang, Hao; Liao, Yong; Zou, Sijie; Yang, Shijian

    2017-01-03

    The design of a high-performance catalyst for Hg(0) oxidation and predicting the extent of Hg(0) oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg(0) oxidation, and the reaction mechanism and the reaction kinetics of Hg(0) oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg(0) oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg(0) concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg(0) oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg(0) with adsorbed HCl), and the rate of Hg(0) oxidation mainly depended on Cl(•) concentration on the surface. As H2O, SO2, and NO not only inhibited Cl(•) formation on the surface but also interfered with the interface reaction between gaseous Hg(0) and Cl(•) on the surface, Hg(0) oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H2O, SO2, and NO. Furthermore, the extent of Hg(0) oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter kE-R, and the predicted result was consistent with the experimental result.

  17. The genes required for heme synthesis in Salmonella typhimurium include those encoding alternative functions for aerobic and anaerobic coproporphyrinogen oxidation.

    PubMed Central

    Xu, K; Delling, J; Elliott, T

    1992-01-01

    Insertion mutagenesis has been used to isolate Salmonella typhimurium strains that are blocked in the conversion of 5-aminolevulinic acid (ALA) to heme. These mutants define the steps of the heme biosynthetic pathway after ALA. Insertions were recovered at five unlinked loci: hemB, hemCD, and hemE, which have been mapped previously in S. typhimurium, and hemG and hemH, which have been described only for Escherichia coli. No other simple hem mutants were found. However, double mutants are described that are auxotrophic for heme during aerobic growth and fail to convert coproporphyrinogen III to protoporphyrinogen IX. These mutant strains are defective in two genes, hemN and hemF. Single mutants defective only in hemN require heme for anaerobic growth on glycerol plus nitrate but not for aerobic growth on glycerol. Mutants defective only in hemF have no apparent growth defect. We suggest that these two genes encode alternative forms of coproporphyrinogen oxidase. Anaerobic heme synthesis requires hemN function, while either hemN or hemF is sufficient for aerobic heme synthesis. These phenotypes are consistent with the requirement of a well-characterized class of coproporphyrinogen oxidase for molecular oxygen. PMID:1317844

  18. Aerobic Tennis.

    ERIC Educational Resources Information Center

    Stewart, Michael J.; Ahlschwede, Robert

    1989-01-01

    Increasing the aerobic nature of tennis drills in the physical education class may be necessary if tennis is to remain a part of the public school curriculum. This article gives two examples of drills that can be modified by teachers to increase activity level. (IAH)

  19. Reactions of. cap alpha. -oxides in the presence of hexamethylenetetramine and glycerine diphenyl ether

    SciTech Connect

    Nikolaev, P.V.; Sveshnikova, N.F.; Ignatov, V.A.

    1987-11-20

    Hexamethylenetetramine (HMTA) is widely used as a catalyst for the condensation and hardening of compositions based on epoxide oligomer. To provide objective information about the reaction scheme and the kinetics of reactions in which epoxide oligomers participate we studied a model reaction system. The model epoxide oligomer selected was phenyl glycidyl ether (PGE) and the ..cap alpha..,..gamma..-diphenyl ether of glycerine (GDPE). The reference substances in the differential thermal analysis were magnesium oxide, aluminum oxide, and GDPE. Monitoring of the progress of the isothermal reaction was effected by determining the ..cap alpha..-oxide group mercurimetrically. The concentration of HMTA was determined iodometrically.

  20. Surface Reactions of Uranium Oxide Powder, Thin Films and Single Crystals

    SciTech Connect

    Idriss, H.

    2010-01-01

    The review deals with surface reactions of the complex uranium oxide systems with relevance to catalysis and the environment. After a brief introduction on the properties of uranium oxides, the focus of the review is on surface science studies of defined structures of uranium oxides which are entirely on UO{sub 2} because of the lack of available model on other uranium oxide systems. Powder work is also included as it has given considerable information related to the dynamics between the many phases of uranium oxides. Many chemical reactions are mapped and these include water dissociative adsorption and reaction, CO oxidation and reductive coupling, as well as the reaction of oxygen containing organic compounds such as alcohols, aldehydes, ketones and carboxylic acids in addition to a few examples of sulfur and nitrogen containing compounds.

  1. Stochastic-convective transport with nonlinear reaction and mixing: application to intermediate-scale experiments in aerobic biodegradation in saturated porous media.

    PubMed

    Ginn, T R; Murphy, E M; Chilakapati, A; Seeboonruang, U

    2001-03-01

    Aerobic biodegradation of benzoate by Pseudomonas cepacia sp. in a saturated heterogeneous porous medium was simulated using the stochastic-convective reaction (SCR) approach. A laboratory flow cell was randomly packed with low permeability silt-size inclusions in a high permeability sand matrix. In the SCR upscaling approach, the characteristics of the flow field are determined by the breakthrough of a conservative tracer. Spatial information on the actual location of the heterogeneities is not used. The mass balance equations governing the nonlinear and multicomponent reactive transport are recast in terms of reactive transports in each of a finite number of discrete streamtubes. The streamtube ensemble members represent transport via a steady constant average velocity per streamtube and a conventional Fickian dispersion term, and their contributions to the observed breakthroughs are determined by flux-averaging the streamtube solute concentrations. The resulting simulations were compared to those from a high-resolution deterministic simulation of the reactive transport, and to alternative ensemble representations involving (i) effective Fickian travel time distribution function, (ii) purely convective streamtube transport, and (iii) streamtube ensemble subset simulations. The results of the SCR simulation compare favorably to that of a sophisticated high-resolution deterministic approach.

  2. Stochastic-convective transport with nonlinear reaction and mixing: application to intermediate-scale experiments in aerobic biodegradation in saturated porous media

    NASA Astrophysics Data System (ADS)

    Ginn, T. R.; Murphy, E. M.; Chilakapati, A.; Seeboonruang, U.

    2001-03-01

    Aerobic biodegradation of benzoate by Pseudomonas cepacia sp. in a saturated heterogeneous porous medium was simulated using the stochastic-convective reaction (SCR) approach. A laboratory flow cell was randomly packed with low permeability silt-size inclusions in a high permeability sand matrix. In the SCR upscaling approach, the characteristics of the flow field are determined by the breakthrough of a conservative tracer. Spatial information on the actual location of the heterogeneities is not used. The mass balance equations governing the nonlinear and multicomponent reactive transport are recast in terms of reactive transports in each of a finite number of discrete streamtubes. The streamtube ensemble members represent transport via a steady constant average velocity per streamtube and a conventional Fickian dispersion term, and their contributions to the observed breakthroughs are determined by flux-averaging the streamtube solute concentrations. The resulting simulations were compared to those from a high-resolution deterministic simulation of the reactive transport, and to alternative ensemble representations involving (i) effective Fickian travel time distribution function, (ii) purely convective streamtube transport, and (iii) streamtube ensemble subset simulations. The results of the SCR simulation compare favorably to that of a sophisticated high-resolution deterministic approach.

  3. Development of Nitric Oxide Oxidation Catalysts for the Fast SCR Reaction

    SciTech Connect

    Mark Crocker

    2005-09-30

    This study was undertaken in order to assess the potential for oxidizing NO to NO{sub 2} in flue gas environments, with the aim of promoting the so-called fast SCR reaction. In principle this can result in improved SCR kinetics and reduced SCR catalyst volumes. Prior to commencing experimental work, a literature study was undertaken to identify candidate catalysts for screening. Selection criteria comprised (1) proven (or likely) activity for NO oxidation, (2) low activity for SO2 oxidation (where data were available), and (3) inexpensive component materials. Catalysts identified included supported base metal oxides, supported and unsupported mixed metal oxides, and metal ion exchanged ZSM-5 (Fe, Co, Cu). For comparison purposes, several low loaded Pt catalysts (0.5 wt% Pt) were also included in the study. Screening experiments were conducted using a synthetic feed gas representative of flue gas from coal-fired utility boilers: [NO] = 250 ppm, [SO{sub 2}] = 0 or 2800 ppm, [H{sub 2}O] = 7%, [CO{sub 2}] = 12%, [O{sub 2}] = 3.5%, balance = N{sub 2}; T = 275-375 C. Studies conducted in the absence of SO{sub 2} revealed a number of supported and unsupported metal oxides to be extremely active for NO oxidation to NO{sub 2}. These included known catalysts (Co{sub 3}O{sub 4}/SiO{sub 2}, FeMnO{sub 3}, Cr{sub 2}O{sub 3}/TiO{sub 2}), as well as a new one identified in this work, CrFeO{sub x}/SiO{sub 2}. However, in the presence of SO{sub 2}, all the catalysts tested were found to be severely deactivated with respect to NO oxidation. Of these, Co{sub 3}O{sub 4}/SiO{sub 2}, Pt/ZSM-5 and Pt/CeO{sub 2} showed the highest activity for NO oxidation in the presence of SO{sub 2} (based on peak NO conversions to NO{sub 2}), although in no cases did the NO conversion exceed 7%. Reactor studies indicate there are two components to SO{sub 2}-induced deactivation of Co{sub 3}O{sub 4}/SiO{sub 2}, corresponding to an irreversible deactivation due to sulfation of the surface of the Co{sub 3

  4. Exothermic Surface Reactions in Alumina-Aluminum Shell-Core Nanoparticles with Iodine Oxide Decomposition Fragments

    DTIC Science & Technology

    2014-02-22

    AND SUBTITLE Sa. CONTRACT NUMBER Exothennic smface reactions in alumina-aluminum shell-core W911NF-11-1-0439 nanoprui icles with iodine oxide...is observed for aluminum and an iodine -containing oxidizer. This PIR is exothermic and precedes the main exothennic reaction conesponding to aluminum...combustion. For the aluminum and iodine oxide system, exothennic smface chemistiy was recently predicted for I-0 fragments fonning bridge bonds with

  5. Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater.

    PubMed

    Suarez-Ojeda, María Eugenia; Guisasola, Albert; Baeza, Juan A; Fabregat, Azael; Stüber, Frank; Fortuny, Agustí; Font, Josep; Carrera, Julián

    2007-02-01

    This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.

  6. Reactions Leading to Ignition in Nanocomposite Al-oxide Systems

    DTIC Science & Technology

    2010-03-01

    processing at room temperature, and the nature of the interface present between aluminum and the oxidizer (metal oxide, e.g., CuO, MoO3, Bi2O3 , etc...at room temperature, and the nature of the interface present between aluminum and the oxidizer (metal oxide, e.g., CuO, MoO3, Bi2O3 , etc.) is

  7. Computational studies of the isomerization and hydration reactions of acetaldehyde oxide and methyl vinyl carbonyl oxide.

    PubMed

    Kuwata, Keith T; Hermes, Matthew R; Carlson, Matthew J; Zogg, Cheryl K

    2010-09-02

    Alkene ozonolysis is a major source of hydroxyl radical (*OH), the most important oxidant in the troposphere. Previous experimental and computational work suggests that for many alkenes the measured *OH yields should be attributed to the combined impact of both chemically activated and thermalized syn-alkyl Criegee intermediates (CIs), even though the thermalized CI should be susceptible to trapping by molecules such as water. We have used RRKM/master equation and variational transition state theory calculations to quantify the competition between unimolecular isomerization and bimolecular hydration reactions for the syn and anti acetaldehyde oxide formed in trans-2-butene ozonolysis and for the CIs formed in isoprene ozonolysis possessing syn-methyl groups. Statistical rate theory calculations were based on quantum chemical data provided by the B3LYP, QCISD, and multicoefficient G3 methods, and thermal rate constants were corrected for tunneling effects using the Eckart method. At tropospheric temperatures and pressures, all thermalized CIs with syn-methyl groups are predicted to undergo 1,4-hydrogen shifts from 2 to 8 orders of magnitude faster than they react with water monomer at its saturation number density. For thermalized anti acetaldehyde oxide, the rates of dioxirane formation and hydration should be comparable.

  8. Nitrososphaera viennensis gen. nov., sp. nov., an aerobic and mesophilic, ammonia-oxidizing archaeon from soil and a member of the archaeal phylum Thaumarchaeota

    PubMed Central

    Stieglmeier, Michaela; Klingl, Andreas; Alves, Ricardo J. E.; Rittmann, Simon K.-M. R.; Melcher, Michael; Leisch, Nikolaus

    2014-01-01

    A mesophilic, neutrophilic and aerobic, ammonia-oxidizing archaeon, strain EN76T, was isolated from garden soil in Vienna (Austria). Cells were irregular cocci with a diameter of 0.6–0.9 µm and possessed archaella and archaeal pili as cell appendages. Electron microscopy also indicated clearly discernible areas of high and low electron density, as well as tubule-like structures. Strain EN76T had an S-layer with p3 symmetry, so far only reported for members of the Sulfolobales. Crenarchaeol was the major core lipid. The organism gained energy by oxidizing ammonia to nitrite aerobically, thereby fixing CO2, but growth depended on the addition of small amounts of organic acids. The optimal growth temperature was 42 °C and the optimal pH was 7.5, with ammonium and pyruvate concentrations of 2.6 and 1 mM, respectively. The genome of strain EN76T had a DNA G+C content of 52.7 mol%. Phylogenetic analyses of 16S rRNA genes showed that strain EN76T is affiliated with the recently proposed phylum Thaumarchaeota, sharing 85 % 16S rRNA gene sequence identity with the closest cultivated relative ‘Candidatus Nitrosopumilus maritimus’ SCM1, a marine ammonia-oxidizing archaeon, and a maximum of 81 % 16S rRNA gene sequence identity with members of the phyla Crenarchaeota and Euryarchaeota and any of the other recently proposed phyla (e.g. ‘Korarchaeota’ and ‘Aigarchaeota’). We propose the name Nitrososphaera viennensis gen. nov., sp. nov. to accommodate strain EN76T. The type strain of Nitrososphaera viennensis is strain EN76T ( = DSM 26422T = JMC 19564T). Additionally, we propose the family Nitrososphaeraceae fam. nov., the order Nitrososphaerales ord. nov. and the class Nitrososphaeria classis nov. PMID:24907263

  9. Nitrososphaera viennensis gen. nov., sp. nov., an aerobic and mesophilic, ammonia-oxidizing archaeon from soil and a member of the archaeal phylum Thaumarchaeota.

    PubMed

    Stieglmeier, Michaela; Klingl, Andreas; Alves, Ricardo J E; Rittmann, Simon K-M R; Melcher, Michael; Leisch, Nikolaus; Schleper, Christa

    2014-08-01

    A mesophilic, neutrophilic and aerobic, ammonia-oxidizing archaeon, strain EN76(T), was isolated from garden soil in Vienna (Austria). Cells were irregular cocci with a diameter of 0.6-0.9 µm and possessed archaella and archaeal pili as cell appendages. Electron microscopy also indicated clearly discernible areas of high and low electron density, as well as tubule-like structures. Strain EN76(T) had an S-layer with p3 symmetry, so far only reported for members of the Sulfolobales. Crenarchaeol was the major core lipid. The organism gained energy by oxidizing ammonia to nitrite aerobically, thereby fixing CO2, but growth depended on the addition of small amounts of organic acids. The optimal growth temperature was 42 °C and the optimal pH was 7.5, with ammonium and pyruvate concentrations of 2.6 and 1 mM, respectively. The genome of strain EN76(T) had a DNA G+C content of 52.7 mol%. Phylogenetic analyses of 16S rRNA genes showed that strain EN76(T) is affiliated with the recently proposed phylum Thaumarchaeota, sharing 85% 16S rRNA gene sequence identity with the closest cultivated relative 'Candidatus Nitrosopumilus maritimus' SCM1, a marine ammonia-oxidizing archaeon, and a maximum of 81% 16S rRNA gene sequence identity with members of the phyla Crenarchaeota and Euryarchaeota and any of the other recently proposed phyla (e.g. 'Korarchaeota' and 'Aigarchaeota'). We propose the name Nitrososphaera viennensis gen. nov., sp. nov. to accommodate strain EN76(T). The type strain of Nitrososphaera viennensis is strain EN76(T) ( = DSM 26422(T) = JMC 19564(T)). Additionally, we propose the family Nitrososphaeraceae fam. nov., the order Nitrososphaerales ord. nov. and the class Nitrososphaeria classis nov.

  10. Aerobic Anoxygenic Phototrophic Bacteria

    PubMed Central

    Yurkov, Vladimir V.; Beatty, J. Thomas

    1998-01-01

    The aerobic anoxygenic phototrophic bacteria are a relatively recently discovered bacterial group. Although taxonomically and phylogenetically heterogeneous, these bacteria share the following distinguishing features: the presence of bacteriochlorophyll a incorporated into reaction center and light-harvesting complexes, low levels of the photosynthetic unit in cells, an abundance of carotenoids, a strong inhibition by light of bacteriochlorophyll synthesis, and the inability to grow photosynthetically under anaerobic conditions. Aerobic anoxygenic phototrophic bacteria are classified in two marine (Erythrobacter and Roseobacter) and six freshwater (Acidiphilium, Erythromicrobium, Erythromonas, Porphyrobacter, Roseococcus, and Sandaracinobacter) genera, which phylogenetically belong to the α-1, α-3, and α-4 subclasses of the class Proteobacteria. Despite this phylogenetic information, the evolution and ancestry of their photosynthetic properties are unclear. We discuss several current proposals for the evolutionary origin of aerobic phototrophic bacteria. The closest phylogenetic relatives of aerobic phototrophic bacteria include facultatively anaerobic purple nonsulfur phototrophic bacteria. Since these two bacterial groups share many properties, yet have significant differences, we compare and contrast their physiology, with an emphasis on morphology and photosynthetic and other metabolic processes. PMID:9729607

  11. 5-Carboxamido-5-formamido-2-iminohydantoin, in Addition to 8-oxo-7,8-Dihydroguanine, Is the Major Product of the Iron-Fenton or X-ray Radiation-Induced Oxidation of Guanine under Aerobic Reducing Conditions in Nucleoside and DNA Contexts

    PubMed Central

    2016-01-01

    Exogenously and endogenously produced reactive oxygen species attack the base and sugar moieties of DNA showing a preference for reaction at 2′-deoxyguanosine (dG) sites. In the present work, dG was oxidized by HO• via the Fe(II)-Fenton reaction or by X-ray radiolysis of water. The oxidized lesions observed include the 2′-deoxynucleosides of 8-oxo-7,8-dihydroguanine (dOG), spiroiminodihydantoin (dSp), 5-guanidinohydantoin (dGh), oxazolone (dZ), 5-carboxamido-5-formamido-2-iminohydantoin (d2Ih), 5′,8-cyclo-2′-deoxyguanosine (cyclo-dG), and the free base guanine (Gua). Reactions conducted with ascorbate or N-acetylcysteine as a reductant under aerobic conditions identified d2Ih as the major lesion formed. Studies were conducted to identify the role of O2 and the reductant in product formation. From these studies, mechanisms are proposed to support d2Ih as a major oxidation product detected under aerobic conditions in the presence of the reductant. These nucleoside observations were then validated in oxidations of oligodeoxynucleotide and λ-DNA contexts that demonstrated high yields of d2Ih in tandem with dOG, dSp, and dGh. These results identify dG oxidation to d2Ih to occur in high yields leading to a hypothesis that d2Ih could be found from in cells stressed with HO•. Further, the distorted ring structure of d2Ih likely causes this lesion to be highly mutagenic. PMID:26092110

  12. Palladium and gold nanotubes as oxygen reduction reaction and alcohol oxidation reaction catalysts in base.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2014-06-01

    Palladium (PdNTs) and gold nanotubes (AuNTs) were synthesized by the galvanic displacement of silver nanowires. PdNTs and AuNTs have wall thicknesses of 6 nm, outer diameters of 60 nm, and lengths of 5-10 and 5-20 μm, respectively. Rotating disk electrode experiments showed that the PdNTs and AuNTs have higher area normalized activities for the oxygen reduction reaction (ORR) than conventional nanoparticle catalysts. The PdNTs produced an ORR area activity that was 3.4, 2.2, and 3.7 times greater than that on carbon-supported palladium nanoparticles (Pd/C), bulk polycrystalline palladium, and carbon-supported platinum nanoparticles (Pt/C), respectively. The AuNTs produced an ORR area activity that was 2.3, 9.0, and 2.0 times greater than that on carbon-supported gold nanoparticles (Au/C), bulk polycrystalline gold, and Pt/C, respectively. The PdNTs also had lower onset potentials than Pd/C and Pt/C for the oxidation of methanol (0.236 V), ethanol (0.215 V), and ethylene glycol (0.251 V). In comparison to Pt/C, the PdNTs and AuNTs further demonstrated improved alcohol tolerance during the ORR.

  13. Thiomicrospira hydrogeniphila sp. nov., an aerobic, hydrogen- and sulfur-oxidizing chemolithoautotroph isolated from a seawater tank containing a block of beef tallow.

    PubMed

    Watsuji, Tomo-O; Hada, Emi; Miyazaki, Masayuki; Ichimura, Masako; Takai, Ken

    2016-09-01

    A moderately psychrophilic, aerobic, hydrogen- and sulfur-oxidizing bacterium, designated strain MAS2T, was isolated from a tank containing coastal seawater from Tokyo Bay and a block of beef tallow added as organic material. Growth occurred under aerobic chemolithoautotrophic conditions in the presence of molecular hydrogen, thiosulfate, tetrathionate, elemental sulfur or sulfide as the sole energy source and bicarbonate as a carbon source. The isolate represented a Gram-staining-negative rod with a single polar flagellum and grew in artificial seawater medium with thiosulfate at 2-40 °C (optimum 30 °C). The isolate grew in media with thiosulfate at Na+ concentrations between 30 and 1380 mM (optimum 270 mM). MAS2T possessed C16 : 0, C16 : 1 and C18 : 1 as the major fatty acids. The G+C content of the genomic DNA was 39.6 mol%. The 16S rRNA gene sequence similarity analysis showed that the isolate represented a member of the genus Thiomicrospira within the class Gammaproteobacteria and was most closely related to Thiomicrospira frisia JB-A2T. On the basis of phenotypic and molecular properties, the isolate represents a novel species of the genus Thiomicrospira, for which the name Thiomicrospira hydrogeniphila sp. nov. is proposed (type strain, MAS2T=JCM 30760T=DSM 100274T).

  14. Aerobic Production and Utilization of Lactate Satisfy Increased Energy Demands Upon Neuronal Activation in Hippocampal Slices and Provide Neuroprotection Against Oxidative Stress

    PubMed Central

    Schurr, Avital; Gozal, Evelyne

    2012-01-01

    Ever since it was shown for the first time that lactate can support neuronal function in vitro as a sole oxidative energy substrate, investigators in the field of neuroenergetics have been debating the role, if any, of this glycolytic product in cerebral energy metabolism. Our experiments employed the rat hippocampal slice preparation with electrophysiological and biochemical methodologies. The data generated by these experiments (a) support the hypothesis that lactate, not pyruvate, is the end-product of cerebral aerobic glycolysis; (b) indicate that lactate plays a major and crucial role in affording neural tissue to respond adequately to glutamate excitation and to recover unscathed post-excitation; (c) suggest that neural tissue activation is accompanied by aerobic lactate and NADH production, the latter being produced when the former is converted to pyruvate by mitochondrial lactate dehydrogenase (mLDH); (d) imply that NADH can be utilized as an endogenous scavenger of reactive oxygen species (ROS) to provide neuroprotection against ROS-induced neuronal damage. PMID:22275901

  15. Method and reaction pathway for selectively oxidizing organic compounds

    DOEpatents

    Camaioni, Donald M.; Lilga, Michael A.

    1998-01-01

    A method of selectively oxidizing an organic compound in a single vessel comprises: a) combining an organic compound, an acid solution in which the organic compound is soluble, a compound containing two oxygen atoms bonded to one another, and a metal ion reducing agent capable of reducing one of such oxygen atoms, and thereby forming a mixture; b) reducing the compound containing the two oxygen atoms by reducing one of such oxygen atoms with the metal ion reducing agent to, 1) oxidize the metal ion reducing agent to a higher valence state, and 2) produce an oxygen containing intermediate capable of oxidizing the organic compound; c) reacting the oxygen containing intermediate with the organic compound to oxidize the organic compound into an oxidized organic intermediate, the oxidized organic intermediate having an oxidized carbon atom; d) reacting the oxidized organic intermediate with the acid counter ion and higher valence state metal ion to bond the acid counter ion to the oxidized carbon atom and thereby produce a quantity of an ester incorporating the organic intermediate and acid counter ion; and e) reacting the oxidized organic intermediate with the higher valence state metal ion and water to produce a quantity of alcohol which is less than the quantity of ester, the acid counter ion incorporated in the ester rendering the carbon atom bonded to the counter ion less reactive with the oxygen containing intermediate in the mixture than is the alcohol with the oxygen containing intermediate.

  16. High-temperature oxidation behavior of reaction-formed silicon carbide ceramics

    NASA Technical Reports Server (NTRS)

    Ogbuji, Linus U. J. T.; Singh, M.

    1995-01-01

    The oxidation behavior of reaction-formed silicon carbide (RFSC) ceramics was investigated in the temperature range of 1100 to 1400 C. The oxidation weight change was recorded by TGA; the oxidized materials were examined by light and electron microscopy, and the oxidation product by x-ray diffraction analysis (XRD). The materials exhibited initial weight loss, followed by passive weight gain (with enhanced parabolic rates, k(sub p)), and ending with a negative (logarithmic) deviation from the parabolic law. The weight loss arose from the oxidation of residual carbon, and the enhanced k(sub p) values from internal oxidation and the oxidation of residual silicon, while the logarithmic kinetics is thought to have resulted from crystallization of the oxide. The presence of a small amount of MoSi, in the RFSC material caused a further increase in the oxidation rate. The only solid oxidation product for all temperatures studied was silica.

  17. Photo- and thermal-oxidation studies on methyl and phenyl linoleate: anti-oxidant behaviour and rates of reaction.

    PubMed

    Chacón, J N; Gaggini, P; Sinclair, R S; Smith, F J

    2000-09-01

    Photo-peroxidation of methyl and phenyl linoleate in methanol solutions at 25 degrees C, in the presence of methylene blue or 5,10,15,20-tetra(4-pyridyl)-porphyrin (TPP) as sensitisers of singlet oxygen, was found to proceed at more than 30 times the rate of the same polyunsaturated fatty acid (PUFA) ester species undergoing thermal-peroxidation in the bulk phase at 50 degrees C. The addition of anti-oxidants such as butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) quench the thermal-oxidation effectively but appear to only partially inhibit the photosensitized peroxidation reactions. The kinetics of the overall peroxidation reactions were followed by ultraviolet spectroscopy, measurements of hydroperoxide concentration and by high performance liquid chromatography (HPLC). The photo-peroxidation reaction proceeds more rapidly in chloroform solution as the lifetime of singlet oxygen is shown to be over ten times longer in chloroform than methanol. The initial fast reaction kinetics of the photo-peroxidation reactions were evaluated using a pulsed laser technique to show that singlet oxygen reacts competitively with both the anti-oxidants and the polyunsaturated fatty acid ester. Second order kinetic rate constants (in the range 10(5)-10(7) dm(3) mol(-1) s(-1)) were evaluated for the reactivity of singlet oxygen with a range of anti-oxidants and a singlet oxygen quencher, and the results used to explain the effect of anti-oxidants at different concentrations on the rate of the linoleate photo-peroxidation reaction.

  18. Microelectrode arrays: a general strategy for using oxidation reactions to site selectively modify electrode surfaces.

    PubMed

    Nguyen, Bichlien H; Kesselring, David; Tesfu, Eden; Moeller, Kevin D

    2014-03-04

    Oxidation reactions are powerful tools for synthesis because they allow for the functionalization of molecules. Here, we present a general method for conducting these reactions on a microelectrode array in a site-selective fashion. The reactions are run as a competition between generation of a chemical oxidant at the electrodes in the array and reduction of the oxidant by a "confining agent" in the solution above the array. The "confining agent" does not need to be more reactive than the substrate fixed to the surface of the array. In many cases, the same substrate placed on the surface of the array can also be used in solution as the confining agent.

  19. Enantioselective Pd(II)-catalyzed aerobic oxidative amidation of alkenes and insights into the role of electronic asymmetry in pyridine-oxazoline ligands.

    PubMed

    McDonald, Richard I; White, Paul B; Weinstein, Adam B; Tam, Chun Pong; Stahl, Shannon S

    2011-06-03

    Enantioselective intramolecular oxidative amidation of alkenes has been achieved using a (pyrox)Pd(II)(TFA)(2) catalyst (pyrox = pyridine-oxazoline, TFA = trifluoroacetate) and O(2) as the sole stoichiometric oxidant. The reactions proceed at room temperature in good-to-excellent yields (58-98%) and with high enantioselectivity (ee = 92-98%). Catalyst-controlled stereoselective cyclization reactions are demonstrated for a number of chiral substrates. DFT calculations suggest that the electronic asymmetry of the pyrox ligand synergizes with steric asymmetry to control the stereochemical outcome of the key amidopalladation step.

  20. Influence of Alumina Reaction Tube Impurities on the Oxidation of Chemically-Vapor-Deposited Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth

    1995-01-01

    Pure coupons of chemically vapor deposited (CVD) SiC were oxidized for 100 h in dry flowing oxygen at 1300 C. The oxidation kinetics were monitored using thermogravimetry (TGA). The experiments were first performed using high-purity alumina reaction tubes. The experiments were then repeated using fused quartz reaction tubes. Differences in oxidation kinetics, scale composition, and scale morphology were observed. These differences were attributed to impurities in the alumina tubes. Investigators interested in high-temperature oxidation of silica formers should be aware that high-purity alumina can have significant effects on experiment results.

  1. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    NASA Technical Reports Server (NTRS)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  2. Thermal oxidative degradation reactions of linear perfluoroalky lethers

    NASA Technical Reports Server (NTRS)

    Jones, W. R., Jr.; Paciorek, K. J. L.; Ito, T. I.; Kratzer, R. H.

    1982-01-01

    Thermal and thermal oxidative stability studies were performed on linear perfluoro alkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors are reported. The liner perfluoro alkylethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoro alkylether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating.

  3. Thermal oxidative degradation reactions of linear perfluoroalkyl ethers

    NASA Technical Reports Server (NTRS)

    Jones, W. R., Jr.; Paclorek, K. J. L.; Ito, T. I.; Kratzer, R. H.

    1983-01-01

    Thermal and thermal oxidative stability studies were performed on linear perfluoroalkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors is reported. The linear perfluoroalkyl ethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoroalkyl ether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating. Previously announced in STAR as N82-26468

  4. Influence of a reaction medium on the oxidation of aromatic nitrogen-containing compounds by peroxyacids

    NASA Astrophysics Data System (ADS)

    Dutka, V. S.; Matsyuk, N. V.; Dutka, Yu. V.

    2011-01-01

    The influence of different solvents on the oxidation reaction rate of pyridine (Py), quinoline (QN), acridine (AN), α-oxyquinoline (OQN) and α-picolinic acid (APA) by peroxydecanoic acid (PDA) was studied. It was found that the oxidation rate grows in the series Py < QN < AN, and the rate of the oxidation reaction of compounds containing a substituent in the α position from a reactive center is significantly lower than for unsubstituted analogues. The effective energies of activation of the oxidation reaction were found. It was shown that in the first stage, the reaction mechanism includes the rapid formation of an intermediate complex nitrogen-containing compound, peroxyacid, which forms products upon decomposing in the second stage. A kinetic equation that describes the studied process is offered. The constants of equilibrium of the intermediate complex formation ( K eq) and its decomposition constant ( k 2) in acetone and benzene were calculated. It was shown that the nature of the solvent influences the numerical values of both K p and k 2. It was established that introduction of acetic acid (which is able to form compounds with Py) into the reaction medium slows the rate of the oxidation process drastically. Correlation equations linking the polarity, polarizability, electrophilicity, and basicity of solvents with the constant of the PDA oxidation reaction rate for Py were found. It was concluded that the basicity and polarity of the solvent have a decisive influence on the oxidation reaction rate, while the polarizability and electrophilicity of the reaction medium do not influence the oxidation reaction rate.

  5. Phytosphingosine degradation pathway includes fatty acid α-oxidation reactions in the endoplasmic reticulum.

    PubMed

    Kitamura, Takuya; Seki, Naoya; Kihara, Akio

    2017-03-28

    Although normal fatty acids (FAs) are degraded via β-oxidation, unusual FAs such as 2-hydroxy (2-OH) FAs and 3-methyl-branched FAs are degraded via α-oxidation. Phytosphingosine (PHS) is one of the long-chain bases (the sphingolipid components) and exists in specific tissues, including the epidermis and small intestine in mammals. In the degradation pathway, PHS is converted to 2-OH palmitic acid and then to pentadecanoic acid (C15:0-COOH) via FA α-oxidation. However, the detailed reactions and genes involved in the α-oxidation reactions of the PHS degradation pathway have yet to be determined. In the present study, we reveal the entire PHS degradation pathway: PHS is converted to C15:0-COOH via six reactions [phosphorylation, cleavage, oxidation, CoA addition, cleavage (C1 removal), and oxidation], in which the last three reactions correspond to the α-oxidation. The aldehyde dehydrogenase ALDH3A2 catalyzes both the first and second oxidation reactions (fatty aldehydes to FAs). In Aldh3a2-deficient cells, the unmetabolized fatty aldehydes are reduced to fatty alcohols and are incorporated into ether-linked glycerolipids. We also identify HACL2 (2-hydroxyacyl-CoA lyase 2) [previous name, ILVBL; ilvB (bacterial acetolactate synthase)-like] as the major 2-OH acyl-CoA lyase involved in the cleavage (C1 removal) reaction in the FA α-oxidation of the PHS degradation pathway. HACL2 is localized in the endoplasmic reticulum. Thus, in addition to the already-known FA α-oxidation in the peroxisomes, we have revealed the existence of FA α-oxidation in the endoplasmic reticulum in mammals.

  6. Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

    2015-06-15

    We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.

  7. Process of forming catalytic surfaces for wet oxidation reactions

    NASA Technical Reports Server (NTRS)

    Jagow, R. B. (Inventor)

    1977-01-01

    A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

  8. PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)

    EPA Science Inventory

    The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...

  9. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

    EPA Science Inventory

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

  10. Bulk Gold-Catalyzed Reactions of Isocyanides, Amines, and Amine N-Oxides

    SciTech Connect

    Klobukowski, Erik; Angelici, Robert; Woo, Keith L.

    2012-01-26

    Bulk gold powder (5–50 μm particles) catalyzes the reactions of isocyanides with amines and amine N-oxides to produce ureas. The reaction of n-butyl isocyanide (nBu–N≡C) with di-n-propylamine and N-methylmorpholine N-oxide in acetonitrile, which was studied in the greatest detail, produced 3-butyl-1,1-dipropylurea (O═C(NHnBu)(NnPr2)) in 99% yield at 60 °C within 2 h. Sterically and electronically different isocyanides, amines, and amine N-oxides react successfully under these conditions. Detailed studies support a two-step mechanism that involves a gold-catalyzed reaction of adsorbed isocyanide with the amine N-oxide to form an isocyanate (RN═C═O), which rapidly reacts with the amine to give the urea product. These investigations show that bulk gold, despite its reputation for poor catalytic activity, is capable of catalyzing these reactions.

  11. New Insights into the Diels-Alder Reaction of Graphene Oxide.

    PubMed

    Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed

    2016-04-18

    Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies.

  12. Heterogeneous photochemical reactions of a propylene-nitrogen dioxide-metal oxide-dry air system

    NASA Astrophysics Data System (ADS)

    Takeuchi, Koji; Ibusuki, Takashi

    Photochemical reactions of a C 3H 6-NO 2-air system in the presence of metal oxide were investigated. The metal oxides showing strong photooxidation activity were found to be n-type semiconductor oxides with the energy band gap around 3 eV. Formation of cyano-compounds (HCN and CH 3CN) was also observed and the activity can be explained in terms of the adsorptivity of NO onto metal oxides. Coalfired fly ash as a model of mixed metal oxides was also examined and their photocatalytic action was discussed.

  13. Conversion Reaction-Based Oxide Nanomaterials for Lithium Ion Battery Anodes.

    PubMed

    Yu, Seung-Ho; Lee, Soo Hong; Lee, Dong Jun; Sung, Yung-Eun; Hyeon, Taeghwan

    2016-04-27

    Developing high-energy-density electrodes for lithium ion batteries (LIBs) is of primary importance to meet the challenges in electronics and automobile industries in the near future. Conversion reaction-based transition metal oxides are attractive candidates for LIB anodes because of their high theoretical capacities. This review summarizes recent advances on the development of nanostructured transition metal oxides for use in lithium ion battery anodes based on conversion reactions. The oxide materials covered in this review include oxides of iron, manganese, cobalt, copper, nickel, molybdenum, zinc, ruthenium, chromium, and tungsten, and mixed metal oxides. Various kinds of nanostructured materials including nanowires, nanosheets, hollow structures, porous structures, and oxide/carbon nanocomposites are discussed in terms of their LIB anode applications.

  14. Rapid and effective oxidative pretreatment of woody biomass at mild reaction conditions and low oxidant loadings

    PubMed Central

    2013-01-01

    Background One route for producing cellulosic biofuels is by the fermentation of lignocellulose-derived sugars generated from a pretreatment that can be effectively coupled with an enzymatic hydrolysis of the plant cell wall. While woody biomass exhibits a number of positive agronomic and logistical attributes, these feedstocks are significantly more recalcitrant to chemical pretreatments than herbaceous feedstocks, requiring higher chemical and energy inputs to achieve high sugar yields from enzymatic hydrolysis. We previously discovered that alkaline hydrogen peroxide (AHP) pretreatment catalyzed by copper(II) 2,2΄-bipyridine complexes significantly improves subsequent enzymatic glucose and xylose release from hybrid poplar heartwood and sapwood relative to uncatalyzed AHP pretreatment at modest reaction conditions (room temperature and atmospheric pressure). In the present work, the reaction conditions for this catalyzed AHP pretreatment were investigated in more detail with the aim of better characterizing the relationship between pretreatment conditions and subsequent enzymatic sugar release. Results We found that for a wide range of pretreatment conditions, the catalyzed pretreatment resulted in significantly higher glucose and xylose enzymatic hydrolysis yields (as high as 80% for both glucose and xylose) relative to uncatalyzed pretreatment (up to 40% for glucose and 50% for xylose). We identified that the extent of improvement in glucan and xylan yield using this catalyzed pretreatment approach was a function of pretreatment conditions that included H2O2 loading on biomass, catalyst concentration, solids concentration, and pretreatment duration. Based on these results, several important improvements in pretreatment and hydrolysis conditions were identified that may have a positive economic impact for a process employing a catalyzed oxidative pretreatment. These improvements include identifying that: (1) substantially lower H2O2 loadings can be used that

  15. Ceramic oxide reactions with V2O5 and SO3

    NASA Technical Reports Server (NTRS)

    Jones, R. L.; Williams, C. E.

    1985-01-01

    Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

  16. Reaction pathways during oxidation of cereal β-glucans.

    PubMed

    Mäkelä, Noora; Sontag-Strohm, Tuula; Schiehser, Sonja; Potthast, Antje; Maaheimo, Hannu; Maina, Ndegwa H

    2017-02-10

    Oxidation of cereal β-glucans may affect their stability in food products. Generally, polysaccharides oxidise via different pathways leading to chain cleavage or formation of oxidised groups within the polymer chain. In this study, oxidation pathways of oat and barley β-glucans were assessed with different concentrations of hydrogen peroxide (H2O2) or ascorbic acid (Asc) with ferrous iron (Fe(2+)) as a catalyst. Degradation of β-glucans was evaluated using high performance size exclusion chromatography and formation of carbonyl groups using carbazole-9-carbonyloxyamine labelling. Furthermore, oxidative degradation of glucosyl residues was studied. Based on the results, the oxidation with Asc mainly resulted in glycosidic bond cleavage. With H2O2, both glycosidic bond cleavage and formation of carbonyl groups within the β-glucan chain was found. Moreover, H2O2 oxidation led to production of formic acid, which was proposed to result from Ruff degradation where oxidised glucose (gluconic acid) is decarboxylated to form arabinose.

  17. Immobilization of cobalt(II) Schiff base complexes on polystyrene resin and a study of their catalytic activity for the aerobic oxidation of alcohols.

    PubMed

    Jain, Suman; Reiser, Oliver

    2008-01-01

    The copper-catalyzed [3+2] azide-alkyne cycloaddition and the Staudinger ligation are readily applicable and highly efficient for the immobilization of cobalt Schiff base complexes onto polystyrene resins. Stepwise synthesis of polymer-bound Schiff bases followed by their subsequent complexation with metal ions were successfully carried out. Direct covalent attachment of preformed homogeneous cobalt Schiff base complexes to the resins was also possible. The catalytic efficiency of the so-prepared polystyrene-bound cobalt Schiff bases was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were highly efficient and even more reactive than the corresponding homogenous analogues, thus affording better yields of oxidized products within shorter reaction times. The supported catalysts could easily be recovered from the reaction mixture by simple filtration and reused for subsequent experiments with consistent catalytic activity.

  18. [Formation and reactions of biogenic manganese oxides with heavy metals in environment].

    PubMed

    Meng, You-Ting; Zheng, Yuan-Ming; Zhang, Li-Mei; He, Ji-Zheng

    2009-02-15

    Manganese (Mn) oxides are common minerals in natural environments that may play an important role in the biogeochemical cycles of heavy metals. Increasing evidences have shown that Mn (II) oxidation is a microbially-mediated process, and the Mn oxidizing microorganisms are thus recognized as the major drivers of the global Mn cycle. The major pathway for bacterial Mn (II) oxidation is catalysed by a multicopper oxidizing enzyme family. The primary Mn (IV) biooxides are phyllomanganate-like minerals most similar to delta-MnO2 or acid birnessite. Manganese oxides are known to have high sorption capacities for a wide variety of metal ions and considered to be the important environmental oxidant to many metal ions. This paper reviewed the mechanisms of biogenic manganese oxides formation and their reactions with heavy metal ions in environment.

  19. Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters.

    PubMed

    Yamada, Akira; Miyajima, Ken; Mafuné, Fumitaka

    2012-03-28

    Gas phase catalytic reactions involving the reduction of N(2)O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rh(n) (n = 10-28), using mass spectrometry. Sequential oxygen transfer reactions, Rh(n)O(m-1) + N(2)O → Rh(n)O(m) + N(2) (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, Rh(n)O(m) + CO → Rh(n)O(m-1) + CO(2) (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N(2)O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around Rh(n)O(m) (m ≥ 4) than around bare Rh(n). Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalytic CO oxidation reaction on a rhodium surface.

  20. Constraints in the colonization of natural and engineered subterranean igneous rock aquifers by aerobic methane-oxidizing bacteria inferred by culture analysis.

    PubMed

    Chi Fru, E

    2008-08-01

    The aerobic methane-oxidizing bacteria (MOB) are suggested to be important for the removal of oxygen from subterranean aquifers that become oxygenated by natural and engineering processes. This is primarily because MOB are ubiquitous in the environment and in addition reduce oxygen efficiently. The biogeochemical factors that will control the success of the aerobic MOB in these kinds of underground aquifers remain unknown. In this study, viable and cultivable MOB occurring at natural and engineered deep granitic aquifers targeted for the disposal of spent nuclear fuel (SNF) in the Fennoscandian Shield (approximately 3-1000 m) were enumerated. The numbers were correlated with in situ salinity, methane concentrations, conductivity, pH, and depth. A mixed population habiting freshwater aquifers (approximately 3-20 m), a potential source for the inoculation of MOB into the deeper aquifers was tested for tolerance to NaCl, temperature, pH, and an ability to produce cysts and exospores. Extrapolations show that due to changing in situ parameters (salinity, conductivity, and pH), the numbers of MOB in the aquifers dropped quickly with depth. A positive correlation between the most probable numbers of MOB and methane concentrations was observed. Furthermore, the tolerance-based tests of cultured strains indicated that the MOB in the shallow aquifers thrived best in mesophilic and neutrophilic conditions as opposed to the hyperthermophilic and alkaliphilic conditions expected to develop in an engineered subterranean SNF repository. Overall, the survival of the MOB both quantitatively and physiologically in the granitic aquifers was under the strong influence of biogeochemical factors that are strongly depth-dependent.

  1. Photocatalytic reaction of catechol on rutile titanium oxide

    NASA Astrophysics Data System (ADS)

    Jacobson, Peter; Wang, Chundao; Diebold, Ulrike

    2008-03-01

    In an attempt to understand the fundamental aspects of photocatalysis we have studied the substituted benzene catechol on TiO2(110). Previous studies have given detailed information about the catechol bonding configuration letting our group focus on molecular level interactions with scanning tunneling microscopy and X ray photoelectron spectroscopy. Under UV exposure (248 nm) in an oxygen background, catechol is observed to degrade via oxidation. This oxidation process results in removal of roughly 10% of the initial monolayer. The removal of carbon from the TiO2 surface is shown to depend upon the background gas. Formation of a residual carbon layer is achieved by annealing the catechol monolayer to 600C. This carbon layer is more difficult to remove by photocatalytic oxidation than a pristine catechol monolayer. Work supported by Intel Corporation

  2. Determination of carbon by the oxidation reduction reaction with chromium

    NASA Technical Reports Server (NTRS)

    Mashkovich, L.; Kuteynikov, A. F.

    1978-01-01

    Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

  3. Mutagenicity screening of reaction products from the enzyme-catalyzed oxidation of phenolic pollutants

    SciTech Connect

    Massey, I.J.; Aitken, M.D.; Ball, L.M.; Heck, P.E. . Dept. of Environmental Sciences and Engineering)

    1994-11-01

    Phenol-oxidizing enzymes such as peroxidases, laccases, and mushroom polyphenol oxidase are capable of catalyzing the oxidation of a wide range of phenolic pollutants. Although the use of these enzymes in waste-treatment applications has been proposed by a number of investigators, little information exists on the toxicological characteristics of the oxidation products. The enzymes chloroperoxidase, horseradish peroxidase, lignin peroxidase, and mushroom polyphenol oxidase were used in this study to catalyze the oxidation of phenol, several mono-substituted phenols, and pentachlorophenol. Seventeen reaction mixtures representing selected combinations of enzyme and parent phenol were subjected to mutagenicity screening using the Ames Salmonella typhimurium plate incorporation assay; five selected mixtures were also incubated with the S9 microsomal preparation to detect the possible presence of promutagens. The majority of reaction mixtures tested were not directly mutagenic, and none of those tested with S9 gave a positive response. Such lack of mutagenicity of enzymatic oxidation products provides encouragement for establishing the feasibility of enzyme-catalyzed oxidation as a waste-treatment process. The only positive responses were obtained with reaction products from the lignin peroxidase-catalyzed oxidation of 2-nitrophenol and 4-nitrophenol. Clear positive responses were observed when strain TA100 was incubated with 2-nitrophenol reaction-product mixtures, and when strain TA98 was incubated with the 4-nitrophenol reaction mixture. Additionally, 2,4-dinitrophenol was identified as a reaction product from 4-nitrophenol, and preliminary evidence indicates that both 2,4- and 2,6-dinitrophenol are produced from the oxidation of 2-nitrophenol. Possible mechanism by which these nitration reactions occur are discussed.

  4. Method for catalyzing oxidation/reduction reactions of simple molecules

    SciTech Connect

    Bicker, D.; Bonaventura, J.

    1988-06-14

    A method for oxidizing carbon monoxide to carbon dioxide is described comprising: (1) contacting, together, carbon monoxide, a nitrogen-containing chelating agent and water; wherein the chelating agent is at least one member selected from the group consisting of methmeoglobin bound to a support, ferric hemoglobin bound to a support, iron-containing porphyrins bound to a support, and sperm whale myoglobin bound to a support, wherein the support is glass, a natural fiber, a synthetic fiber, a gel, charcoal, carbon ceramic material, a metal oxide, a synthetic polymer, a zeolite, a silica compound of an alumina compound; and (2) obtaining carbon dioxide.

  5. Nitrogen oxide reactions in the urban plume of Boston.

    PubMed

    Spicer, C W

    1982-02-26

    The rate of removal or conversion of nitrogen oxides has been determined from airborne measurements in the urban plume of Boston. The average pseudo-first-order rate constant for removal was 0.18 per hour, with a range of 0.14 to 0.24 per hour under daylight conditions for four study days. The removal process is dominated by chemical conversion to nitric acid and organic nitrates. The removal rate suggests an atmospheric lifetime for nitrogen oxides of about 5 to 6 hours in urban air.

  6. Copper(II) complex of new non-innocent O-aminophenol-based ligand as biomimetic model for galactose oxidase enzyme in aerobic oxidation of alcohols

    NASA Astrophysics Data System (ADS)

    Safaei, Elham; Bahrami, Hadiseh; Pevec, Andrej; Kozlevčar, Bojan; Jagličić, Zvonko

    2017-04-01

    Mononuclear copper(II) complex of tetra-dentate o-aminophenol-based ligand (H2LBAPP) has been synthesized and characterized. The three dentate precursor (HLBAP) of the final ligand was synthesized first, while the title four-dentate copper bound ligand was synthesized in situ, isolated only in the final copper species [CuLBAPP]. This copper coordination complex reveals a distorted square-planar geometry around the copper(II) centre by one oxygen and three nitrogen atoms from the coordinating ligand. The ligand is thus twice deprotonated via hydroxy and amine groups. The complex is red, non-typical for copper(II), but the effective magnetic moment of 1.86 B M. and a single isotropic symmetry EPR signal with g 2.059 confirm a S = 1/2 diluted spin system, without copper-copper magnetic coupling. Electrochemical oxidation of this complex yields the corresponding Cu(II)-phenyl radical species. Finally, the title complex CuLBAPP has shown good and selective catalytic activity towards alcohol to aldehyde oxidation, at aerobic room temperature conditions, for a set of different alcohols.

  7. Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,β-dehydrogenation of β-heteroatom-substituted ketones.

    PubMed

    Yoshii, Daichi; Jin, Xiongjie; Yatabe, Takafumi; Hasegawa, Jun-Ya; Yamaguchi, Kazuya; Mizuno, Noritaka

    2016-12-06

    In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of β-heteroatom-substituted α,β-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,β-dehydrogenation of the corresponding saturated ketones using O2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.

  8. A comparative theoretical study of CO oxidation reaction by O2 molecule over Al- or Si-decorated graphene oxide.

    PubMed

    Esrafili, Mehdi D; Sharifi, Fahimeh; Nematollahi, Parisa

    2016-09-01

    Using density functional theory calculations, the probable CO oxidation reaction mechanisms are investigated over Al- or Si-decorated graphene oxide (GO). The equilibrium geometry and electronic structure of these metal decorated-GOs along with the O2/CO adsorption configurations are studied in detail. The relatively large adsorption energies reveal that both Al and Si atoms can disperse on GO quite stably without clustering problem. Hence, both Al- and Si-decorated GOs are stable enough to be utilized in catalytic oxidation of CO by molecular O2. The two possible reaction pathways proposed for the oxidation of CO with O2 molecule are as follows: O2+CO→CO2+Oads and CO+Oads→CO2. The estimated energy barriers of the first oxidation reaction on Si-decorated GOs, following the Eley-Rideal (ER) reaction, are lower than that on Al-decorated ones. This is most likely due to the larger atomic charge on the Si atom than the Al one, which tends to stabilize the corresponding transition state structure. The results of this study can be useful for better understanding the chemical properties of Al- and Si-decorated GOs, and are valuable for the development of an automobile catalytic converter in order to remove the toxic CO molecule.

  9. Enhancement of Bacterial Transport in Aerobic and Anaerobic Environments: Assessing the Effect of Metal Oxide Chemical Heterogeneities

    SciTech Connect

    T.C. Onstott

    2005-09-30

    The goal of our research was to understand the fundamental processes that control microbial transport in physically and chemically heterogeneous aquifers and from this enhanced understanding determine the requirements for successful, field-scale delivery of microorganisms to metal contaminated subsurface sites. Our specific research goals were to determine; (1) the circumstances under which the preferential adsorption of bacteria to Fe, Mn, and Al oxyhydroxides influences field-scale bacterial transport, (2) the extent to which the adhesion properties of bacterial cells affect field-scale bacterial transport, (3) whether microbial Fe(III) reduction can enhance field-scale transport of Fe reducing bacteria (IRB) and other microorganisms and (4) the effect of field-scale physical and chemical heterogeneity on all three processes. Some of the spin-offs from this basic research that can improve biostimulation and bioaugmentation remediation efforts at contaminated DOE sites have included; (1) new bacterial tracking tools for viable bacteria; (2) an integrated protocol which combines subsurface characterization, laboratory-scale experimentation, and scale-up techniques to accurately predict field-scale bacterial transport; and (3) innovative and inexpensive field equipment and methods that can be employed to enhance Fe(III) reduction and microbial transport and to target microbial deposition under both aerobic and anaerobic conditions.

  10. The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid.

    PubMed

    Lee, Myungjin; Kim, Kijeong; Lee, Hangil

    2013-09-02

    The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation.

  11. The aniline-to-azobenzene oxidation reaction on monolayer graphene or graphene oxide surfaces fabricated by benzoic acid

    PubMed Central

    2013-01-01

    The oxidation of aniline to azobenzene was conducted in the presence of either monolayer graphene (EG) or graphene-oxide-like surface, such as GOx, under ultra-high vacuum conditions maintaining a 365-nm UV light exposure to enhance the oxidation reaction. The surface-bound products were investigated using micro Raman spectroscopy, high-resolution photoemission spectroscopy, and work function measurements. The oxygen carriers present on the GOx surfaces, but not on the EG surfaces, acted as reaction reagents to facilitate the oxidation reaction from aniline to azobenzene. Increasing the aniline concentration at 300 K confirmed that the exchange ratio from the aniline to the azobenzene was enhanced, as determined by the intensity ratio between the aniline- and azobenzene-induced N 1 s core-level spectra. The work function changed dramatically as the aniline concentration increased, indicating that the aniline on the GOx surface conveyed n-type doping characteristics at a low coverage level. A higher aniline concentration increased the p-type doping character by increasing the azobenzene concentration on the GOx surface. A comparison of the oxidation reactivity of aniline molecules on the EG or GOx surfaces revealed the role of the oxygen carriers on the GOx surfaces in the context of catalytic oxidation. PMID:24229051

  12. REACTION OF BENZENE OXIDE WITH THIOLS INCLUDING GLUTATHIONE

    EPA Science Inventory

    This study accounts for the observations that the metabolism of benzene is dominated by the formation of phenol. As demonstrated here, the pathway leading to S-phenylmercapturic acid is necessarily minor on account of the low efficiency of benzene oxide capture by glutathione at ...

  13. [Study on apparent kinetics of photocatalytic oxidation degradation Rhodamine B by photo-Fenton reaction].

    PubMed

    Li, Hong; Zheng, Huai-Li; Li, Xiao-Hong; Xie, Li-Guo; Tang, Xue

    2008-11-01

    The Fenton process, mixed by hydrogen peroxide and iron salts with highly oxidative effect, is recognized as one of powerful advanced oxidation technologies available and can be used to destroy a variety of persistent organic pollutants. The oxidation power of Fenton reagent is due to the generation of hydroxyl radical (* OH) during the iron catalysed decomposition of hydrogen peroxide in acid medium. The hydroxyl radical with a high oxidation potential (2.8 eV) attacks and completely destroys the pollutants in Fenton process. The degradation of pollutants can be considerably improved by using sunlight radiation, which is due to the generation of additional hydroxyl radicals. This photo-Fenton process had been effectively used to degrade the pollutants. In this paper, the definite quantity of Fenton reagent was added in the definite concentration of Rhodamine B solution. The degradation reaction was carried out at pH 3.5 under natural sunlight. The factors influencing on photocatalytic oxidation degradation rate of Rhodamine B were studied following: the initial concentration of Rhodamine B, initial concentrateions of Fe2+ and H2O2. The orders of degradation reaction were obtained by solving exponential kinetics equations of curve fitting, thereby gaining the kinetic parameters and reaction dynamics equation of the reaction system. The research contents included mainly: the UV-Vis spectra of Rhodamine B solution, the concentration-absorbency work curve of Rhodamine B solution, the analysis of the reaction system at various initial Rhodamine B concentrations, the analysis of the reaction system at various initial Fe2+ concentrateions, the analysis of the reaction system at various initial H2O2 concentrations, and the calculation of the apparent kinetics parameters in reaction dynamics equation. The reaction dynamics equation from experiments was constructed: V = 5 x 10(-9) P1.28 F0.366 E0.920, and overall reaction order was 2.57.

  14. The reactions of imidogen with nitric oxide and molecular oxygen

    SciTech Connect

    Miller, J.A.; Melius, C.F.

    1991-01-01

    Using potential energy surface information from BAC-MP4 calculations and statistical-dynamical methods, we have calculated the branching fraction for the NH + NO reaction, NH + NO {r arrow} N{sub 2} + H (1) NH + NO {r arrow} N{sub 2}O + H (2). We find that reaction (2) dominates over the entire temperature range considered, 300 K < T < 3500 K, with f=k{sub 1}/(k{sub 1} + K{sub 2}) varying from about 0.07 at room temperature to about 0.20 at 3500 K. In addition, we have calculated rate coefficients for the two-channel process, NH + O{sub 2} {r arrow} HNO + O (3) NH + O{sub 2} {r arrow} NO + OH (4). In this case we find that reaction (4) dominates at low temperature, reaction (3) at high temperature. All these results are discussed in terms of the experimental results available and compared with previous theoretical investigations where appropriate. 21 refs., 4 figs., 3 tabs.

  15. The reactions of imidogen with nitric oxide and molecular oxygen

    SciTech Connect

    Miller, J.A.; Melius, C.F.

    1991-12-31

    Using potential energy surface information from BAC-MP4 calculations and statistical-dynamical methods, we have calculated the branching fraction for the NH + NO reaction, NH + NO {r_arrow} N{sub 2} + H (1) NH + NO {r_arrow} N{sub 2}O + H (2). We find that reaction (2) dominates over the entire temperature range considered, 300 K < T < 3500 K, with f=k{sub 1}/(k{sub 1} + K{sub 2}) varying from about 0.07 at room temperature to about 0.20 at 3500 K. In addition, we have calculated rate coefficients for the two-channel process, NH + O{sub 2} {r_arrow} HNO + O (3) NH + O{sub 2} {r_arrow} NO + OH (4). In this case we find that reaction (4) dominates at low temperature, reaction (3) at high temperature. All these results are discussed in terms of the experimental results available and compared with previous theoretical investigations where appropriate. 21 refs., 4 figs., 3 tabs.

  16. Iron oxide mineral-water interface reactions studied by AFM

    SciTech Connect

    Hawley, M.E.; Rogers, P.S.Z.

    1994-07-01

    Natural iron mineral surfaces have been examined in air by atomic force (AFM) and scanning tunneling (STM) microscopies. A number of different surface features were found to be characteristic of the native surface. Even surfaces freshly exposed by crushing larger crystals were found to have a pebbly surface texture caused by the presence of thin coatings of what might be surface precipitates. This finding is interpreted as evidence for previous exposure to water, probably through an extensive network of microfractures. Surface reactions on the goethite crystals were studied by AFM at size resolutions ranging from microns to atomic resolution before, during, and after reaction with distilled water and 0.lN HCl. Immediate and extensive surface reconfiguration occurred on contact with water. In one case, after equilibration with water for 3 days, surface reprecipitation, etching and pitting were observed. Atomic resolution images taken under water were found to be disordered. The result of surface reaction was generally to increase the surface area substantially through the extension of surface platelet arrays, present prior to reaction. This work is being done in support of the site characterization project at Yucca Mountain.

  17. Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications

    NASA Astrophysics Data System (ADS)

    Pilo, Alice L.; Zhao, Feifei; McLuckey, Scott A.

    2017-01-01

    Here, we provide an overview of pathways available upon the gas-phase oxidation of peptides and DNA via ion/ion reactions and explore potential applications of these chemistries. The oxidation of thioethers (i.e., methionine residues and S-alkyl cysteine residues), disulfide bonds, S-nitrosylated cysteine residues, and DNA to the [M+H+O]+ derivative via ion/ion reactions with periodate and peroxymono-sulfate anions is demonstrated. The oxidation of neutral basic sites to various oxidized structures, including the [M+H+O]+, [M-H]+, and [M-H-NH3]+ species, via ion/ion reactions is illustrated and the oxidation characteristics of two different oxidizing reagents, periodate and persulfate anions, are compared. Lastly, the highly efficient generation of molecular radical cations via ion/ion reactions with sulfate radical anion is summarized. Activation of the newly generated molecular radical peptide cations results in losses of various neutral side chains, several of which generate dehydroalanine residues that can be used to localize the amino acid from which the dehydroalanine was generated. The chemistries presented herein result in a diverse range of structures that can be used for a variety of applications, including the identification and localization of S-alkyl cysteine residues, the oxidative cleavage of disulfide bonds, and the generation of molecular radical cations from even-electron doubly protonated peptides.

  18. Bench-scale study of the effect of phosphate on an aerobic iron oxidation plant for mine water treatment.

    PubMed

    Tischler, Judith S; Wiacek, Claudia; Janneck, Eberhard; Schlömann, Michael

    2014-01-01

    At the opencast pit Nochten acidic iron- and sulfate-rich mine waters are treated biotechnologically in a mine-water treatment plant by microbial iron oxidation. Due to the low phosphate concentration in such waters the treatment plant was simulated in bench-scale to investigate the influence of addition of potassium dihydrogen phosphate on chemical and biological parameters of the mine-water treatment. As a result of the phosphate addition the number of cells increased, which resulted in an increase of the iron oxidation rate in the reactor with phosphate addition by a factor of 1.7 compared to a reference approach without phosphate addition. Terminal restriction fragment length polymorphism (T-RFLP) analysis during the cultivation revealed a shift of the microbial community depending on the phosphate addition. While almost exclusively iron-oxidizing bacteria related to "Ferrovum" sp. were detected with phosphate addition, the microbial community was more diverse without phosphate addition. In the latter case, iron-oxidizing bacteria ("Ferrovum" sp., Acidithiobacillus spp.) as well as non-iron-oxidizing bacteria (Acidiphilium sp.) were identified.

  19. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    DOE PAGES

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; ...

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication ofmore » crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.« less

  20. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    SciTech Connect

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication of crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.

  1. Evaluation of Salivary Nitric Oxide Levels in Smokers, Tobacco Chewers and Patients with Oral Lichenoid Reactions

    PubMed Central

    Jose, Joy Idiculla; Sivapathasundharam, B.; Sabarinath, B.

    2016-01-01

    Introduction Nitric oxide (NO), a free radical, acts as a signalling molecule affecting numerous physiological and pathological processes. Role of nitric oxide as a mediator in tobacco related habits and the resultant oral lichenoid reactions was assessed. Aim The aim of the study is to evaluate and compare the salivary nitric oxide levels in normal patients with that of smokers, tobacco chewers and patients with oral lichenoid reactions. Materials and Methods One hundred and twenty patients were enrolled in the study which included 30 healthy patients without any chronic inflammatory lesion and habit as controls (group I), 30 smokers without the habit of tobacco/betel nut chewing and any oral lesion (group II), 30 tobacco chewers without the habit of smoking and any oral lesion (group III) and 30 histologically confirmed cases of oral lichenoid reaction with the habit of tobacco usage (group IV). Saliva from these patients was collected and the nitrite concentration was assessed. Results Our results concluded that there was highly significant increase in the nitric oxide levels in smokers, tobacco chewers and patients with oral lichenoid reactions compared to that of controls. Also, there was a significant increase in nitric oxide levels in patients with smoking associated oral lichenoid reactions in comparison with smokers and in patients with lichenoid reactions associated with tobacco chewing in comparison with tobacco chewers. Conclusion Estimation of salivary nitric oxide levels is a simple, non-invasive procedure and could be analysed to suggest the role of nitric oxide in the pathogenesis of these lesions. The increased activity of the enzyme may indicate that nitric oxide has a pathophysiological role in these lesions. PMID:26894179

  2. The Energetics of Aerobic versus Anaerobic Respiration.

    ERIC Educational Resources Information Center

    Champion, Timothy D.; Schwenz, Richard W.

    1990-01-01

    Background information, laboratory procedures, and a discussion of the results of an experiment designed to investigate the difference in energy gained from the aerobic and anaerobic oxidation of glucose are presented. Sample experimental and calculated data are included. (CW)

  3. Implications of sterically constrained n-butane oxidation reactions on the reaction mechanism and selectivity to 1-butanol

    NASA Astrophysics Data System (ADS)

    Dix, Sean T.; Gómez-Gualdrón, Diego A.; Getman, Rachel B.

    2016-11-01

    Density functional theory (DFT) is used to analyze the reaction network in n-butane oxidation to 1-butanol over a Ag/Pd alloy catalyst under steric constraints, and the implications on the ability to produce 1-butanol selectively using MOF-encapsulated catalysts are discussed. MOFs are porous crystalline solids comprised of metal nodes linked by organic molecules. Recently, they have been successfully grown around metal nanoparticle catalysts. The resulting porous networks have been shown to promote regioselective chemistry, i.e., hydrogenation of trans-1,3-hexadiene to 3-hexene, presumably by forcing the linear alkene to stand "upright" on the catalyst surface and allowing only the terminal C-H bonds to be activated. In this work, we extend this concept to alkane oxidation. Our goal is to determine if a MOF-encapsulated catalyst could be used to selectively produce 1-butanol. Reaction energies and activation barriers are presented for more than 40 reactions in the pathway for n-butane oxidation. We find that C-H bond activation proceeds through an oxygen-assisted pathway and that butanal and 1-butanol are some of the possible products.

  4. High Temperature Reactions of Uranium Dioxide with Various Metal Oxides

    DTIC Science & Technology

    1956-02-20

    less oxygen than that in U308, even at low tem- peratures; (b) reduction of oxides such as U205 , U30,, and UO3 at temperatures above 1,450’ C to a...Corporation. Thorium dioxide (ThO2). Lindsay Light & Power Co. low-tem- perature, calcined material of 99.99-percent purity. Vanadium pentoxide (V2O6

  5. Application of hydrogen peroxide encapsulated in silica xerogels to oxidation reactions.

    PubMed

    Bednarz, Szczepan; Ryś, Barbara; Bogdał, Dariusz

    2012-07-04

    Hydrogen peroxide was encapsulated into a silica xerogel matrix by the sol-gel technique. The composite was tested as an oxidizing agent both under conventional and microwave conditions in a few model reactions: Noyori's method of octanal and 2-octanol oxidation and cycloctene epoxidation in a 1,1,1-trifluoroethanol/Na2WO4 system. The results were compared with yields obtained for reactions with 30% H2O2 and urea-hydrogen peroxide (UHP) as oxidizing agents. It was found that the composite has activity similar to 30% H2O2 and has a several advantages over UHP such as the fact that silica and H2O are the only products of the composite decomposition or no contamination by urea or its derivatives occurs; the xerogel is easier to heated by microwave irradiation than UHP and could be used as both an oxidizing agent and as solid support for microwave assisted solvent-free oxidations.

  6. Reduction reaction analysis of nanoparticle copper oxide for copper direct bonding using formic acid

    NASA Astrophysics Data System (ADS)

    Fujino, Masahisa; Akaike, Masatake; Matsuoka, Naoya; Suga, Tadatomo

    2017-04-01

    Copper direct bonding is required for electronics devices, especially power devices, and copper direct bonding using formic acid is expected to lower the bonding temperature. In this research, we analyzed the reduction reaction of copper oxide using formic acid with a Pt catalyst by electron spin resonance analysis and thermal gravimetry analysis. It was found that formic acid was decomposed and radicals were generated under 200 °C. The amount of radicals generated was increased by adding the Pt catalyst. Because of these radicals, both copper(I) oxide and copper(II) oxide start to be decomposed below 200 °C, and the reduction of copper oxide is accelerated by reactants such as H2 and CO from the decomposition of formic acid above 200 °C. The Pt catalyst also accelerates the reaction of copper oxide reduction. Herewith, it is considered that the copper surface can be controlled more precisely by using formic acid to induce direct bonding.

  7. Effects of aerobic exercise training on metabolism of nitric oxide and endothelin-1 in lung parenchyma of rats with pulmonary arterial hypertension.

    PubMed

    Zimmer, A; Teixeira, R B; Bonetto, J H P; Siqueira, R; Carraro, C C; Donatti, L M; Hickmann, A; Litvin, I E; Godoy, A E G; Araujo, A S; Colombo, R; Belló-Klein, Adriane

    2017-05-01

    Pulmonary arterial hypertension (PAH) is characterized by vasoconstriction and proliferative obstruction of pulmonary vessels, which promotes a progressive increase in pulmonary vascular resistance (PVR). The effect of exercise training on oxidative stress, metabolism, and markers of nitric oxide (NO) and endothelin-1 (ET-1) was analyzed in the lung tissue of rats with PAH induced by monocrotaline (MCT).Twenty-four Wistar rats were divided into four groups (5-7 animals): sedentary control (SC), sedentary MCT (SM), trained control (TC), and trained MCT (TM). The TC and TM groups participated in a treadmill training protocol (60% VO2 max) for 5 weeks, 3 weeks of which were performed after the injection of MCT (60 mg/kg i.p.) or saline. MCT administration promoted an increase in PVR and right ventricle hypertrophy, and reduction of right ventricle systolic function assessed by echocardiography. These changes were not improved by exercise training. The activity of NO synthase was reduced in the animals of the TC, TM, and SM groups. No significant differences were found in total nitrite concentration and expression of endothelial NO synthase. Moreover, the TM group showed strong staining for iNOS and nitrotyrosine, suggesting an increase in oxidative stress in these animals. In parallel, reduced expression of type B ET-1 receptors was noticed in the SM and TM groups in comparison to controls. In conclusion, the aerobic training protocol was unable to mitigate changes in the metabolism of NO and ET-1, probably because of the disease severity in these animals, especially in the TM group.

  8. Boundary effects in a surface reaction model for CO oxidation

    NASA Astrophysics Data System (ADS)

    Brosilow, Benjamin J.; Gulari, Erdogan; Ziff, Robert M.

    1993-01-01

    The surface reaction model of Ziff, Gulari, and Barshad (ZGB) is investigated on finite systems with ``hard'' oxygen boundary conditions. The rate of production of CO2 is calculated as a function of y and system size. When the rate of CO adsorption y is above the first-order transition value y2, the reactive region is found to extend into the system a distance ξ which scales as (y-y2)-0.40 when y→y2.

  9. Theoretical study of reactions of HO{sub 2} in low-temperature oxidation of benzene

    SciTech Connect

    Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; Mackie, John C.

    2010-07-15

    We have generated a set of thermodynamic and kinetic parameters for the reactions involving HO{sub 2} in the very early stages of benzene oxidation at low temperatures using density functional theory (DFT). In particular, we report the rate constants for the reactions of HO{sub 2} with benzene and phenyl. The calculated reaction rate constant for the abstraction of H-C{sub 6}H{sub 5} by HO{sub 2} is found to be in good agreement with the limited experimental values. HO{sub 2} addition to benzene is found to be more important than direct abstraction. We show that the reactions of HO{sub 2} with the phenyl radical generate the propagating radical OH in a highly exoergic reaction. The results presented herein should be useful in modeling the oxidation of aromatic compounds at low temperatures. (author)

  10. Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

    NASA Astrophysics Data System (ADS)

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-05-01

    Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene.

  11. Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

    PubMed Central

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-01-01

    Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene. PMID:27181191

  12. Effects of aerobic exercise on the blood pressure, oxidative stress and eNOS gene polymorphism in pre-hypertensive older people.

    PubMed

    Zago, Anderson Saranz; Park, Joon-Young; Fenty-Stewart, Nicola; Silveira, Leonardo Reis; Kokubun, Eduardo; Brown, Michael D

    2010-11-01

    The polymorphisms of endothelial nitric oxide synthase (eNOS) are associated with reduced eNOS activity. Aerobic exercise training (AEX) may influence resting nitric oxide (NO) production, oxidative stress and blood pressure. The purpose of this study was to investigate the effect of AEX on the relationship among blood pressure, eNOS gene polymorphism and oxidative stress in pre-hypertensive older people. 118 pre-hypertensive subjects (59 ± 6 years) had blood samples collected after a 12 h overnight fast for assessing plasma NO metabolites (NOx) assays, thiobarbituric acid reactive substances (T-BARS) and superoxide dismutase activity (ecSOD). eNOS polymorphism (T-786C and G-894T) was done by standard PCR methods. All people were divided according to the genotype results (G1: TT/GG, G2: TT/GT + TT, G3: TC + CC/GG, G4: TC + CC/GT + TT). All parameters were measured before and after 6 months of AEX (70% of VO(2 max)). At baseline, no difference was found in systolic and diastolic blood pressure, ecSOD and T-BARS activity. Plasma NOx levels were significantly different between G1 (19 ± 1 μM) and G4 (14.2 ± 0.6 μM) and between G2 (20.1 ± 1.7 μM) and G4 (14.2 ± 0.6 μM). Therefore, reduced NOx concentration in G4 group occurred only when the polymorphisms were associated, suggesting that these results are more related to genetic factors than NO-scavenging effect. After AEX, the G4 increased NOx values (17.2 ± 1.2 μM) and decreased blood pressure. G1, G3 and G4 decreased T-BARS levels. These results suggest the AEX can modulate the NOx concentration, eNOS activity and the relationship among eNOS gene polymorphism, oxidative stress and blood pressure especially in C (T-786C) and T (G-894T) allele carriers.

  13. Extensive Bone Reaction From Catastrophic Oxidized Zirconium Wear.

    PubMed

    Cassar-Gheiti, Adrian J; Collins, Dennis; McCarthy, Tom

    2016-01-01

    The use of alternative bearing surfaces for total hip arthroplasty has become popular to minimize wear and increase longevity, especially in young patients. Oxidized zirconium (Oxinium; Smith & Nephew, Memphis, Tennessee) femoral heads were introduced in the past decade for use in total hip arthroplasty. The advantages of oxidized zirconium include less risk of fracture compared with traditional ceramic heads. This case report describes a patient with a history of bilateral avascular necrosis of the femoral head after chemotherapy for acute lymphoblastic leukemia. Nonoperative management of avascular necrosis failed, and the patient was treated with bilateral total hip arthroplasty. The patient was followed at regular intervals and had slow eccentric polyethylene wear during a 10-year period. After 10 years, the patient had accelerated wear, with femoral and acetabular bone changes as a result of Oxinium and ultrahigh-molecular-weight polyethylene wear during a 6-month period. This article highlights the unusual accelerated bone changes that occurred as a result of Oxinium wear particles.

  14. Evaluation of reaction mechanism of coal-metal oxide interactions in chemical-looping combustion

    SciTech Connect

    Siriwardane, Ranjani; Richards, George; Poston, James; Tian, Hanjing; Miller, Duane; Simonyi, Thomas

    2010-11-15

    The knowledge of reaction mechanism is very important in designing reactors for chemical-looping combustion (CLC) of coal. Recent CLC studies have considered the more technically difficult problem of reactions between abundant solid fuels (i.e. coal and waste streams) and solid metal oxides. A definitive reaction mechanism has not been reported for CLC reaction of solid fuels. It has often been assumed that the solid/solid reaction is slow and therefore requires that reactions be conducted at temperatures high enough to gasify the solid fuel, or decompose the metal oxide. In contrast, data presented in this paper demonstrates that solid/solid reactions can be completed at much lower temperatures, with rates that are technically useful as long as adequate fuel/metal oxide contact is achieved. Density functional theory (DFT) simulations as well as experimental techniques such as thermo-gravimetric analysis (TGA), flow reactor studies, in situ X-ray photo electron spectroscopy (XPS), in situ X-ray diffraction (XRD) and scanning electron microscopy (SEM) are used to evaluate how the proximal interaction between solid phases proceeds. The data indicate that carbon induces the Cu-O bond breaking process to initiate the combustion of carbon at temperatures significantly lower than the spontaneous decomposition temperature of CuO, and the type of reducing medium in the vicinity of the metal oxide influences the temperature at which the oxygen release from the metal oxide takes place. Surface melting of Cu and wetting of carbon may contribute to the solid-solid contacts necessary for the reaction. (author)

  15. Oxidative catalysis using the stoichiometric oxidant as a reagent: an efficient strategy for single-electron-transfer-induced tandem anion-radical reactions.

    PubMed

    Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císařová, Ivana; Klepetářová, Blanka; Jahn, Ullrich

    2014-09-08

    Oxidative single-electron transfer-catalyzed tandem reactions consisting of a conjugate addition and a radical cyclization are reported, which incorporate the mandatory terminal oxidant as a functionality into the product.

  16. Photocatalytic activity of layered perovskite-like oxides in practically valuable chemical reactions

    NASA Astrophysics Data System (ADS)

    Rodionov, I. A.; Zvereva, I. A.

    2016-03-01

    The photocatalytic properties of layered perovskite-like oxides corresponding to the Ruddlesen-Popper, Dion-Jacobson and Aurivillius phases are considered. Of the photocatalytic reactions, the focus is on the reactions of water splitting, hydrogen evolution from aqueous solutions of organic substances and degradation of model organic pollutants. Possibilities to conduct these reactions under UV and visible light in the presence of layered perovskite-like oxides and composite photocatalysts based on them are shown. The specific surface area, band gap energy, particle morphology, cation and anion doping and surface modification are considered as factors that affect the photocatalytic activity. Special attention is paid to the possibilities to enhance the photocatalytic activity by intercalation, ion exchange and exfoliation, which are inherent in this class of compounds. Conclusions are made about the prospects for the use of layered perovskite-like oxides in photocatalysis. The bibliography includes 253 references.

  17. Saccharomyces cerevisiae engineered for xylose metabolism requires gluconeogenesis and the oxidative branch of the pentose phosphate pathway for aerobic xylose assimilation.

    PubMed

    Hector, Ronald E; Mertens, Jeffrey A; Bowman, Michael J; Nichols, Nancy N; Cotta, Michael A; Hughes, Stephen R

    2011-09-01

    Saccharomyces strains engineered to ferment xylose using Scheffersomyces stipitis xylose reductase (XR) and xylitol dehydrogenase (XDH) genes appear to be limited by metabolic imbalances, due to differing cofactor specificities of XR and XDH. The S. stipitis XR, which uses both NADH and NADPH, is hypothesized to reduce the cofactor imbalance, allowing xylose fermentation in this yeast. However, unadapted S. cerevisiae strains expressing this XR grow poorly on xylose, suggesting that metabolism is still imbalanced, even under aerobic conditions. In this study, we investigated the possible reasons for this imbalance by deleting genes required for NADPH production and gluconeogenesis in S. cerevisiae. S. cerevisiae cells expressing the XR-XDH, but not a xylose isomerase, pathway required the oxidative branch of the pentose phosphate pathway (PPP) and gluconeogenic production of glucose-6-P for xylose assimilation. The requirement for generating glucose-6-P from xylose was also shown for Kluyveromyces lactis. When grown in xylose medium, both K. lactis and S. stipitis showed increases in enzyme activity required for producing glucose-6-P. Thus, natural xylose-assimilating yeast respond to xylose, in part, by upregulating enzymes required for recycling xylose back to glucose-6-P for the production of NADPH via the oxidative branch of the PPP. Finally, we show that induction of these enzymes correlated with increased tolerance to the NADPH-depleting compound diamide and the fermentation inhibitors furfural and hydroxymethyl furfural; S. cerevisiae was not able to increase enzyme activity for glucose-6-P production when grown in xylose medium and was more sensitive to these inhibitors in xylose medium compared to glucose.

  18. Attenuation of Ca2+ homeostasis, oxidative stress, and mitochondrial dysfunctions in diabetic rat heart: insulin therapy or aerobic exercise?

    PubMed

    da Silva, Márcia F; Natali, Antônio J; da Silva, Edson; Gomes, Gilton J; Teodoro, Bruno G; Cunha, Daise N Q; Drummond, Lucas R; Drummond, Filipe R; Moura, Anselmo G; Belfort, Felipe G; de Oliveira, Alessandro; Maldonado, Izabel R S C; Alberici, Luciane C

    2015-07-15

    We tested the effects of swimming training and insulin therapy, either alone or in combination, on the intracellular calcium ([Ca(2+)]i) homeostasis, oxidative stress, and mitochondrial functions in diabetic rat hearts. Male Wistar rats were separated into control, diabetic, or diabetic plus insulin groups. Type 1 diabetes mellitus was induced by streptozotocin (STZ). Insulin-treated groups received 1 to 4 UI of insulin daily for 8 wk. Each group was divided into sedentary or exercised rats. Trained groups were submitted to swimming (90 min/day, 5 days/wk, 8 wk). [Ca(2+)]i transient in left ventricular myocytes (LVM), oxidative stress in LV tissue, and mitochondrial functions in the heart were assessed. Diabetes reduced the amplitude and prolonged the times to peak and to half decay of the [Ca(2+)]i transient in LVM, increased NADPH oxidase-4 (Nox-4) expression, decreased superoxide dismutase (SOD), and increased carbonyl protein contents in LV tissue. In isolated mitochondria, diabetes increased Ca(2+) uptake, susceptibility to permeability transition pore (MPTP) opening, uncoupling protein-2 (UCP-2) expression, and oxygen consumption but reduced H2O2 release. Swimming training corrected the time course of the [Ca(2+)]i transient, UCP-2 expression, and mitochondrial Ca(2+) uptake. Insulin replacement further normalized [Ca(2+)]i transient amplitude, Nox-4 expression, and carbonyl content. Alongside these benefits, the combination of both therapies restored the LV tissue SOD and mitochondrial O2 consumption, H2O2 release, and MPTP opening. In conclusion, the combination of swimming training with insulin replacement was more effective in attenuating intracellular Ca(2+) disruptions, oxidative stress, and mitochondrial dysfunctions in STZ-induced diabetic rat hearts.

  19. Surface-catalyzed air oxidation reactions of hydrazines: Tubular reactor studies

    NASA Technical Reports Server (NTRS)

    Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

    1988-01-01

    The surface-catalyzed air oxidation reactions of hydrazine, monomethylhydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine and tetramethylhydrazine were investigated in a metal-powder packed turbular flow reactor at 55 plus or minus 3 C. Hydrazine was completely reacted on all surfaces studied. The major products of monomethylhydrazine (MMH) oxidation were methanol, methane and methyldiazene. The di-, tri- and tetra-methyl hydrazines were essentially unreactive under these conditions. The relative catalytic reactivities toward MMH are: Fe greater than Al2O3 greater than Ti greater than Zn greater than 316 SS greater than Cr greater than Ni greater than Al greater than 304L SS. A kinetic scheme and mechanism involving adsorption, oxidative dehydrogenation and reductive elimination reactions on a metal oxide surface are proposed.

  20. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  1. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    DOE PAGES

    Senanayake, S. D.; Pappoe, N. A.; Nguyen-Phan, T. -D.; ...

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface statesmore » or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.« less

  2. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    NASA Astrophysics Data System (ADS)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  3. Effects of high-intensity interval versus continuous moderate-intensity aerobic exercise on apoptosis, oxidative stress and metabolism of the infarcted myocardium in a rat model.

    PubMed

    Lu, Kai; Wang, Li; Wang, Changying; Yang, Yuan; Hu, Dayi; Ding, Rongjing

    2015-08-01

    The optimal aerobic exercise training (AET) protocol for patients following myocardial infarction (MI) has remained under debate. The present study therefore aimed to compare the effects of continuous moderate-intensity training (CMT) and high-intensity interval training (HIT) on cardiac functional recovery, and to investigate the potential associated mechanisms in a post-MI rat model. Female Sprague Dawley rats (8-10 weeks old) undergoing MI or sham surgery were subsequently submitted to CMT or HIT, or kept sedentary for eight weeks. Prior to and following AET, echocardiographic parameters and exercise capacity of the rats were measured. Western blotting was used to evaluate the levels of apoptosis and associated signaling pathway protein expression. The concentrations of biomarkers of oxidative stress were also determined by ELISA assay. Messenger (m)RNA levels and activity of the key enzymes for glycolysis and fatty acid oxidation, as well as the rate of adenosine triphosphate (ATP) synthesis, were also measured. Compared with the MI group, exercise capacity and cardiac function were significantly improved following AET, particularly following HIT. Left ventricular ejection fraction and fraction shortening were further improved in the MI-HIT group in comparison to that of the MI-CMT group. The two forms of AET almost equally attenuated apoptosis of the post-infarction myocardium. CMT and HIT also alleviated oxidative stress by decreasing the concentration of malondialdehyde and increasing the concentration of superoxide dismutase and glutathione peroxidase (GPx). In particular, HIT induced a greater increase in the concentration of GPx than that of CMT. AET, and HIT in particular, significantly increased the levels of mRNA and the maximal activity of phosphofructokinase-1 and carnitine palmitoyl transferase-1, as well as the maximal ratio of ATP synthesis. In addition, compared with the MI group, the expression of signaling proteins PI3K, Akt, p38mapk and AMPK

  4. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    SciTech Connect

    Bartling, Stephan Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

    2015-09-21

    Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology.

  5. "Click" reaction in conjunction with diazeniumdiolate chemistry: developing high-load nitric oxide donors.

    PubMed

    Oladeinde, Oyebola A; Hong, Sam Y; Holland, Ryan J; Maciag, Anna E; Keefer, Larry K; Saavedra, Joseph E; Nandurdikar, Rahul S

    2010-10-01

    The use of Cu(I)-catalyzed "click" reactions of alkyne-substituted diazeniumdiolate prodrugs with bis- and tetrakis-azido compounds is described. The "click" reaction for the bis-azide using CuSO(4)/Na-ascorbate predominantly gave the expected bis-triazole. However, CuI/diisopropylethylamine predominantly gave uncommon triazolo-triazole products as a result of oxidative coupling. Neither set of "click" conditions showed evidence of compromising the integrity of the diazeniumdiolate groups. The chemistry developed has applications in the synthesis of polyvalent and dendritic nitric oxide donors.

  6. Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol

    PubMed Central

    Cui, Yubo; Villafane, Louis A.; Clausen, Dane J.

    2013-01-01

    Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon–hydrogen bond cleavage. PMID:23913987

  7. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    PubMed Central

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

    2017-01-01

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level. PMID:28327642

  8. Reaction Mechanism for m-Xylene Oxidation in the Claus Process by Sulfur Dioxide.

    PubMed

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S; Chung, Suk Ho

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation.

  9. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    PubMed

    Ding, Liangbing; Xiong, Feng; Jin, Yuekang; Wang, Zhengming; Sun, Guanghui; Huang, Weixin

    2016-11-30

    CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

  10. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

    PubMed

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-22

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  11. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    NASA Astrophysics Data System (ADS)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-01

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  12. Proteomic analysis reveals perturbed energy metabolism and elevated oxidative stress in hearts of rats with inborn low aerobic capacity

    PubMed Central

    Burniston, Jatin G.; Kenyani, Jenna; Wastling, Jonathan M.; Burant, Charles F.; Qi, Nathan R.; Koch, Lauren G.; Britton, Steven L.

    2012-01-01

    Selection on running capacity has created rat phenotypes of high capacity runners (HCR) that have enhanced cardiac function and low capacity runners (LCR) that exhibit risk factors of metabolic syndrome. We analysed hearts of HCR and LCR from generation 22 of selection using DIGE and identified proteins from MS database searches. The running capacity of HCR was 6-fold greater than LCR. DIGE resolved 957 spots and proteins were unambiguously identified in 369 spots. Protein expression profiling detected 67 statistically significant (P<0.05; false discovery rate <10 %, calculated using q-values) differences between HCR and LCR. Hearts of HCR rats exhibited robust increases in the abundance of each enzyme of the beta-oxidation pathway. In contrast, LCR hearts were characterised by the modulation of enzymes associated with ketone body or amino acid metabolism. LCR also exhibited enhanced expression of antioxidant enzymes such as catalase and greater phosphorylation of alpha B-crystallin at serine 59, which is a common point of convergence in cardiac stress signalling. Thus proteomic analysis revealed selection on low running capacity is associated with perturbations in cardiac energy metabolism and provided the first evidence that the LCR cardiac proteome is exposed to greater oxidative stress. PMID:21751351

  13. Oxidative C-H/C-H Coupling Reactions between Two (Hetero)arenes.

    PubMed

    Yang, Yudong; Lan, Jingbo; You, Jingsong

    2017-01-13

    Transition metal-mediated C-H bond activation and functionalization represent one of the most straightforward and powerful tools in modern organic synthetic chemistry. Bi(hetero)aryls are privileged π-conjugated structural cores in biologically active molecules, organic functional materials, ligands, and organic synthetic intermediates. The oxidative C-H/C-H coupling reactions between two (hetero)arenes through 2-fold C-H activation offer a valuable opportunity for rapid assembly of diverse bi(hetero)aryls and further exploitation of their applications in pharmaceutical and material sciences. This review provides a comprehensive overview of the fundamentals and applications of transition metal-mediated/catalyzed oxidative C-H/C-H coupling reactions between two (hetero)arenes. The substrate scope, limitation, reaction mechanism, regioselectivity, and chemoselectivity, as well as related control strategies of these reactions are discussed. Additionally, the applications of these established methods in the synthesis of natural products and exploitation of new organic functional materials are exemplified. In the last section, a short introduction on oxidant- or Lewis acid-mediated oxidative Ar-H/Ar-H coupling reactions is presented, considering that it is a very powerful method for the construction of biaryl units and polycylic arenes.

  14. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    PubMed

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

    2014-08-01

    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  15. Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

    NASA Technical Reports Server (NTRS)

    Hampson, R. F., Jr.

    1980-01-01

    Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

  16. Proton Coupled Electron Transfer Reactions at the Surface of Metal Oxide Nanomaterials

    NASA Astrophysics Data System (ADS)

    Braten, Miles N.

    Nanostructured metal oxide materials are found in many products and processes in our society today, but they play a particularly important role in the conversion and storage of energy. The materials are used as catalysts and redox active supports in devices such as dye sensitized solar cells, solid oxide fuel cells, and flow batteries, where they transfer and store electrons and charge balancing cations. Oftentimes electron transfer is modulated by the cations and when the cation is a proton, these redox reactions are known as proton coupled electron transfer (PCET) reactions. The work described in this dissertation focuses on understanding the PCET reactivity of nanocrystalline metal oxide materials. Chapter 1 introduces the concept of PCET and provides background information on the zinc oxide (ZnO) nanocrystals (NCs) which the majority of the research is focused on. Chapter 2 examines the chemistry that occurs during the photoreduction of ZnO NCs. Chapter 3 describes experiments probing how ZnO NC capping ligand concentration and NC size modulate PCET reaction rates. Chapter 4 describes experiments that compare the PCET reactivity of ZnO NCs with different numbers of electrons and protons stored on them. Chapter 5 describes attempts to observe the electrochemical reduction of ZnO NCs attached to gold electrodes. Finally, Chapter 6 contains attempts to identify a nanostructured metal oxide alkane oxidation catalyst for use in fuel cell.

  17. Nonenzymatic Reactions above Phospholipid Surfaces of Biological Membranes: Reactivity of Phospholipids and Their Oxidation Derivatives

    PubMed Central

    Solís-Calero, Christian; Ortega-Castro, Joaquín; Frau, Juan; Muñoz, Francisco

    2015-01-01

    Phospholipids play multiple and essential roles in cells, as components of biological membranes. Although phospholipid bilayers provide the supporting matrix and surface for many enzymatic reactions, their inherent reactivity and possible catalytic role have not been highlighted. As other biomolecules, phospholipids are frequent targets of nonenzymatic modifications by reactive substances including oxidants and glycating agents which conduct to the formation of advanced lipoxidation end products (ALEs) and advanced glycation end products (AGEs). There are some theoretical studies about the mechanisms of reactions related to these processes on phosphatidylethanolamine surfaces, which hypothesize that cell membrane phospholipids surface environment could enhance some reactions through a catalyst effect. On the other hand, the phospholipid bilayers are susceptible to oxidative damage by oxidant agents as reactive oxygen species (ROS). Molecular dynamics simulations performed on phospholipid bilayers models, which include modified phospholipids by these reactions and subsequent reactions that conduct to formation of ALEs and AGEs, have revealed changes in the molecular interactions and biophysical properties of these bilayers as consequence of these reactions. Then, more studies are desirable which could correlate the biophysics of modified phospholipids with metabolism in processes such as aging and diseases such as diabetes, atherosclerosis, and Alzheimer's disease. PMID:25977746

  18. Secondary Organic Aerosol Formation by Molecular-Weight Building Reactions of Biogenic Oxidation Products

    NASA Astrophysics Data System (ADS)

    Barsanti, K.; Guenther, A.; Matsunaga, S.; Smith, J.

    2006-12-01

    Understanding the chemical composition of atmospheric organic aerosols (OA) remains one of the significant challenges to accurately representing OA in air quality and climate models. Meeting this challenge will require further understanding of secondary organic aerosols (SOA), of which biogenic emissions are thought to be major precursors. Of recent interest is the significance of higher-molecular weight (MW) compounds (i.e., "oligomers"). Theoretical, laboratory, and field study results suggest that relatively volatile oxidation products may contribute to SOA formation through multi-phase MW- building reactions. The significance of such reactions for biogenic SOA formation, including for newly considered precursors such as isoprene, is explored in this work. Theoretical and field studies are employed to: 1) identify MW-building reactions that may contribute to SOA formation in the atmosphere, 2) identify MW-building reaction products in ambient samples, and 3) parameterize atmospheric SOA formation by MW-building reactions of biogenic oxidation products. Likely reactions of biogenic oxidation products include ester, amide, and peroxyhemiacetal formation. Each of the proposed reactions involves known oxidation productions of biogenic precursors (e.g., carboxylic acids and aldehydes) reacting with one another and/or other atmospheric constituents (e.g., sulfuric acid and ammonia) to form higher-MW/lower-volatility products that can condense to form SOA. It has been suggested that products of MW-building reactions can revert to the parent reactants during sampling and analysis. Thus, relatively volatile compounds detected in ambient particle samples in fact may be decomposition products of higher-MW products. The contribution of relatively volatile biogenic oxidation products to SOA via ester, amide, and peroxyhemiacetal formation, as determined by studies based on fundamental thermodynamics and gas/particle partitioning theory, will be discussed; in addition to

  19. Relating Carbon and Nitrogen Isotope Effects to Reaction Mechanisms during Aerobic or Anaerobic Degradation of RDX (Hexahydro-1,3,5-Trinitro-1,3,5-Triazine) by Pure Bacterial Cultures

    PubMed Central

    Heraty, Linnea; Condee, Charles W.; Vainberg, Simon; Sturchio, Neil C.; Böhlke, J. K.; Hatzinger, Paul B.

    2016-01-01

    ABSTRACT Kinetic isotopic fractionation of carbon and nitrogen during RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) biodegradation was investigated with pure bacterial cultures under aerobic and anaerobic conditions. Relatively large bulk enrichments in 15N were observed during biodegradation of RDX via anaerobic ring cleavage (ε15N = −12.7‰ ± 0.8‰) and anaerobic nitro reduction (ε15N = −9.9‰ ± 0.7‰), in comparison to smaller effects during biodegradation via aerobic denitration (ε15N = −2.4‰ ± 0.2‰). 13C enrichment was negligible during aerobic RDX biodegradation (ε13C = −0.8‰ ± 0.5‰) but larger during anaerobic degradation (ε13C = −4.0‰ ± 0.8‰), with modest variability among genera. Dual-isotope ε13C/ε15N analyses indicated that the three biodegradation pathways could be distinguished isotopically from each other and from abiotic degradation mechanisms. Compared to the initial RDX bulk δ15N value of +9‰, δ15N values of the NO2− released from RDX ranged from −7‰ to +2‰ during aerobic biodegradation and from −42‰ to −24‰ during anaerobic biodegradation. Numerical reaction models indicated that N isotope effects of NO2− production were much larger than, but systematically related to, the bulk RDX N isotope effects with different bacteria. Apparent intrinsic ε15N-NO2− values were consistent with an initial denitration pathway in the aerobic experiments and more complex processes of NO2− formation associated with anaerobic ring cleavage. These results indicate the potential for isotopic analysis of residual RDX for the differentiation of degradation pathways and indicate that further efforts to examine the isotopic composition of potential RDX degradation products (e.g., NOx) in the environment are warranted. IMPORTANCE This work provides the first systematic evaluation of the isotopic fractionation of carbon and nitrogen in the organic explosive RDX during degradation by different pathways. It also

  20. Reaction pattern and mechanism of light induced oxidative water splitting in photosynthesis.

    PubMed

    Renger, Gernot; Kühn, Philipp

    2007-06-01

    This mini review is an attempt to briefly summarize our current knowledge on light driven oxidative water splitting in photosynthesis. The reaction leading to molecular oxygen and four protons via photosynthesis comprises thermodynamic and kinetic constraints that require a balanced fine tuning of the reaction coordinates. The mode of coupling between electron (ET) and proton transfer (PT) reactions is shown to be of key mechanistic relevance for the redox turnover of Y(Z) and the reactions within the WOC. The WOC is characterized by peculiar energetics of its oxidation steps in the WOC. In all oxygen evolving photosynthetic organisms the redox state S(1) is thermodynamically most stable and therefore this general feature is assumed to be of physiological relevance. Available information on the Gibbs energy differences between the individual redox states S(i+1) and S(i) and on the activation energies of their oxidative transitions are used to construct a general reaction coordinate of oxidative water splitting in photosystem II (PS II). Finally, an attempt is presented to cast our current state of knowledge into a mechanism of oxidative water splitting with special emphasis on the formation of the essential O-O bond and the active role of the protein environment in tuning the local proton activity that depends on time and redox state S(i). The O-O linkage is assumed to take place within a multistate equilibrium at the redox level of S(3), comprising both redox isomerism and proton tautomerism. It is proposed that one state, S(3)(P), attains an electronic configuration and nuclear geometry that corresponds with a hydrogen bonded peroxide which acts as the entatic state for the generation of complexed molecular oxygen through S(3)(P) oxidation by Y(Z)(ox).

  1. Catalytic Reaction Synthesis for the Partial Oxidation of Methane to Formaldehyde.

    NASA Astrophysics Data System (ADS)

    Cardenas-Galindo, Maria-Guadalupe

    Catalytic reaction synthesis for the partial oxidation of methane to formaldehyde has been studied by combining microkinetic analysis with molecular orbital calculations. This strategy is used to establish microscopic correlations between the structure and composition of the active site and the kinetic parameters of the reaction mechanism. Using atom clusters to represent the active site of transition metal oxide catalysts, the relationship was probed between coordination number, oxidation state, and ionization potential of the active cation and the reaction steps of methane activation and surface reactions leading to formaldehyde formation. The analysis suggests that in transition metal oxide catalysts, the d-band orbitals of the metal cation should be empty, since otherwise CO_2 formation from CO oxidation will be excessive. Furthermore, the transition metal oxide d-band must be located at sufficiently low energy that it may accept electrons during methane activation. Oxygen O- species, representing vacancies in the 2p cluster band, will favor methane activation. However, clusters with fully occupied 2p bands (O^ {2-}^ecies) will favor formaldehyde production. Such inferences illustrate how experimental and theoretical information already incorporated into an existing microkinetic model for the reaction over V _2O_5 and MoO _3 catalysts can be extended to describe the reaction over new materials in the search for more active and selective catalysts. Using parameters estimated from the molecular orbital calculations, microkinetic reaction simulations were also shown to be useful to identify reactor operating conditions that may favor the production of formaldehyde. The simulation can be used to identify key experiments necessary to test the performance of postulated catalytic materials. The economic evaluation of the process design sets important target goals for methane conversion and formaldehyde selectivity that a catalytic material must satisfy to create a new

  2. The reaction mechanism of catalytic oxidation with hydrogen peroxide and ozone in aqueous solution.

    PubMed

    Park, J S; Choi, H; Ahn, K H

    2003-01-01

    The sorption and catalytic oxidation of model compounds (pCBA and phenanthrene) and NOM on FeOOH were investigated using hydrogen peroxide and ozone, respectively. After oxidation with ozone, the hydrophobic, transphilic, and hydrophilic NOM fractions were isolated using XAD-8 and -4 resins to analyze the reaction characteristics. The sorption of pCBA was strongly dependent upon the pH, but phenanthrene exhibited a sorption behavior that was independent of the pH. In the case of NOM, the hydrophobic portion showed higher sorption affinity than hydrophilic and transphilic at pH 7.2. The concentrations of model compounds and oxidants were measured during the oxidations and the efficiency was compared for tests done with ozone alone and those using catalytic ozonation. Through the comparison of the sorption and decomposition of the model compounds, along with the effects of bicarbonate addition, mechanisms for catalytic oxidation with hydrogen peroxide or ozone were proposed, respectively.

  3. The reactions of O(ID) and OH with CH3OH, oxidation of the HCO radial, and the photochemical oxidation of formaldehyde. [photochemical reactions in stratosphere

    NASA Technical Reports Server (NTRS)

    Osif, T. L.

    1976-01-01

    An experimental, laboratory study of the various photochemical reactions that can occur in the mesosphere and stratosphere is presented. N2O was photolyzed at 2139 A in the presence of CH3OH and CO. The O(id) produced in the photolysis reacted with CH3OH to produce OH radicals, and thus the reactions of both O(id) and OH were able to be studied. Also considered was the oxidation of the HCO radical. Mixtures of Cl2, O2, H2CO, and sometimes N2 or He were irradiated at 3660 A at several temperatures to photodecompose the Cl2. The photochemical oxidation of formaldehyde was studied as follows: formaldehyde in the presence of N2 and/or O2 (usually dry air) was photolyzed with a medium pressure Hg lamp used in conjunction with various filters which transmit different relative amounts of Hg lines from 2894 A to 3660 A. Results are presented and discussed, along with a description of experimental procedures and apparatus, and chemical reaction kinetics.

  4. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    SciTech Connect

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  5. Efficient synthesis of oxygenated terphenyls and other oligomers: sequential arylation reactions through phenol oxidation-rearomatization.

    PubMed

    Dohi, Toshifumi; Kamitanaka, Tohru; Watanabe, Shohei; Hu, Yinjun; Washimi, Naohiko; Kita, Yasuyuki

    2012-10-22

    One by one: starting from simple phenols, a diverse series of oxygenated terphenyl compounds can be prepared in a concise and practical manner using sequential arylation reactions involving phenol oxidation/rearomatization and quinone monoacetal intermediates. Many of the terphenyl products can be used for preparing well-defined oligomers and, furthermore, contain valuable functional groups that can be transformed for further diversification.

  6. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    ERIC Educational Resources Information Center

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  7. Surface electronic structure and isomerization reactions of alkanes on some transition metal oxides

    NASA Astrophysics Data System (ADS)

    Katrib, A.; Logie, V.; Saurel, N.; Wehrer, P.; Hilaire, L.; Maire, G.

    1997-04-01

    XP spectra of some reduced transition metal oxides are presented. Different number of free nd,( n + 1)s valence electrons in each case could be observed by the presence of a certain density of states (DOS) at the Fermi-level in the valence band (VB) energy region of the XP spectrum. Catalytic isomerization reactions of 2-methylpentane yielding 3-methylpentane and n-hexane at 350°C have been observed on these reduced valence surface states. The bifunctionel mechanism in terms of metallic and acidic sites required for such reactions is proposed by considering the metallic properties of the rutile deformed structure through the C-axis in the case of MoO 2 and WO 2, while the oxygen atom(s) in the lattice structure exhibit Brönsted acidic properties. On the other hand, highly reduced or clean surfaces of these transition metals yield hydrogenolysis catalytic reactions for the same reactant with methane as the major product. In all cases, the exposure of the lower valence oxidation states of bulk transition metal oxides to air results in the surface partial oxidation to the stable oxides such as MoO 3, WO 3, V 2O 5 and Nb 2O 5.

  8. Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

    PubMed

    Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

    2016-04-12

    Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

  9. Methanol oxidation and hydrogen reactions on NiZr in acid solution

    NASA Astrophysics Data System (ADS)

    Hays, C. C.; Manoharan, R.; Goodenough, J. B.

    The electrochemical properties of a Ni 50Zr 50 (at.%) alloy have been investigated by cyclic voltammetry and steady-state polarization measurements. The alloy forms a passivating oxyhydroxide film that makes it electrochemically stable in an acid solution. The oxyhydroxide film is shown to be an electrocatalyst for the methanol oxidation reaction (MOR). The reaction proceeds at surface O 2- ions neighboring a Ni 3+ ion of a thicker passivating film; electron transfer from the surface to the electrode occurs diffusively by the nickel atoms of the film. A reaction pathway is presented that accounts for the observation of an optimum thickness for the passivating film. The NiZr alloy was also found to catalyze both hydrogen-oxidation and proton-reduction reactions (HOR and PRR) if it has a thinner surface oxyhydroxide film. The alloy appears to form mixed NiZrH and NiZrH 3- x hydrides on cycling negative of the normal hydrogen potential. The activity of the hydrogen-oxidation reaction on a hydride surface was found to increase in the presence of streaming hydrogen gas and also with increasing negative initial potential. Although the hydride is unstable in acid, it may be an attractive candidate for use as a rechargeable negative electrode in an alkaline metal/air or nickel-metal hydride secondary battery.

  10. Surface grafting of reduced graphene oxide using nanocrystalline cellulose via click reaction

    NASA Astrophysics Data System (ADS)

    Kabiri, Roya; Namazi, Hassan

    2014-07-01

    Reduced graphene oxide (RGO) sheet was functionalized with nanocrystalline cellulose (NCC) via click coupling between azide-functionalized graphene oxide (GO-N3) and terminal propargyl-functionalized nanocrystalline cellulose (PG-NCC). First, the reactive azide groups were introduced on the surface of GO with azidation of 2-chloroethyl isocyanate-treated graphene oxide (GO-Cl). Then, the resulted compounds were reacted with PG-NCC utilizing copper-catalyzed azide-alkyne cycloaddition. During the click reaction, GO was simultaneously reduced to graphene. The coupling was confirmed by Fourier transform infrared, Raman, DEPT135, and 13C NMR spectroscopy, and the complete exfoliation of graphene in the NCC matrix was confirmed with X-ray diffraction measurement. The degree of functionalization from the gradual mass loss of RGO-NCC suggests that around 23 mass % has been functionalized covalently. The size of both NCC and GO was found to be in nanometric range, which decreased after click reaction.

  11. Modelling of silicon oxynitridation by nitrous oxide using the reaction rate approach

    SciTech Connect

    Dominique Krzeminski, Christophe

    2013-12-14

    Large technological progress in oxynitridation processing leads to the introduction of silicon oxynitride as ultra-thin gate oxide. On the theoretical side, few studies have been dedicated to the process modelling of oxynitridation. Such an objective is a considerable challenge regarding the various atomistic mechanisms occurring during this fabrication step. In this article, some progress performed to adapt the reaction rate approach for the modelling of oxynitride growth by a nitrous ambient are reported. The Ellis and Buhrman's approach is used for the gas phase decomposition modelling. Taking into account the mass balance of the species at the interface between the oxynitride and silicon, a minimal kinetic model describing the oxide growth has been calibrated and implemented. The influence of nitrogen on the reaction rate has been introduced in an empirical way. The oxidation kinetics predicted with this minimal model compares well with several experiments.

  12. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    PubMed

    Poux, T; Bonnefont, A; Ryabova, A; Kéranguéven, G; Tsirlina, G A; Savinova, E R

    2014-07-21

    Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.

  13. Inhibition of nitric oxide and prostaglandins, but not endothelial-derived hyperpolarizing factors, reduces blood flow and aerobic energy turnover in the exercising human leg.

    PubMed

    Mortensen, Stefan P; González-Alonso, José; Damsgaard, Rasmus; Saltin, Bengt; Hellsten, Ylva

    2007-06-01

    Prostaglandins, nitric oxide (NO) and endothelial-derived hyperpolarizing factors (EDHFs) are substances that have been proposed to be involved in the regulation of skeletal muscle blood flow during physical activity. We measured haemodynamics, plasma ATP at rest and during one-legged knee-extensor exercise (19 +/- 1 W) in nine healthy subjects with and without intra-arterial infusion of indomethacin (Indo; 621 +/- 17 microg min(-1)), Indo + N(G)-monomethyl-L-arginine (L-NMMA; 12.4 +/- 0.3 mg min(-1)) (double blockade) and Indo + L-NMMA + tetraethylammonium chloride (TEA; 12.4 +/- 0.3 mg min(-1)) (triple blockade). Double and triple blockade lowered leg blood flow (LBF) at rest (P<0.05), while it remained unchanged with Indo. During exercise, LBF and vascular conductance were 2.54 +/- 0.10 l min(-1) and 25 +/- 1 mmHg, respectively, in control and they were lower with double (33 +/- 3 and 36 +/- 4%, respectively) and triple (26 +/- 4 and 28 +/- 3%, respectively) blockade (P<0.05), while there was no difference with Indo. The lower LBF and vascular conductance with double and triple blockade occurred in parallel with a lower O(2) delivery, cardiac output, heart rate and plasma [noradrenaline] (P<0.05), while blood pressure remained unchanged and O(2) extraction and femoral venous plasma [ATP] increased. Despite the increased O(2) extraction, leg was 13 and 17% (triple and double blockade, respectively) lower than control in parallel to a lower femoral venous temperature and lactate release (P<0.05). These results suggest that NO and prostaglandins play important roles in skeletal muscle blood flow regulation during moderate intensity exercise and that EDHFs do not compensate for the impaired formation of NO and prostaglandins. Moreover, inhibition of NO and prostaglandin formation is associated with a lower aerobic energy turnover and increased concentration of vasoactive ATP in plasma.

  14. Zircon coronas around Fe-Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

    NASA Astrophysics Data System (ADS)

    Austrheim, Håkon; Putnis, Christine V.; Engvik, Ane K.; Putnis, Andrew

    2008-10-01

    Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite-prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution-reprecipitation. Zircon coronas on Fe-Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.

  15. Mass transfer model for two-layer TBP oxidation reactions: Revision 1

    SciTech Connect

    Laurinat, J.E.

    1994-11-04

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments.

  16. Electrochemical reaction and oxidation of lecithin under pulsed electric fields (PEF) processing.

    PubMed

    Zhao, Wei; Yang, Ruijin; Liang, Qi; Zhang, Wenbin; Hua, Xiao; Tang, Yali

    2012-12-12

    Pulsed electric fields (PEF) processing is a promising nonthermal food preservation technology, which is ongoing from laboratory and pilot plant scale levels to the industrial level. Currently, greater attention has been paid to side effects occurring during PEF treatment and the influences on food qualities and food components. The present study investigated the electrochemical reaction and oxidation of lecithin under PEF processing. Results showed that electrochemical reaction of NaCl solutions at different pH values occurred during PEF processing. Active chlorine, reactive oxygen, and free radicals were detected, which were related to the PEF parameters and pH values of the solution. Lecithin extracted from yolk was further selected to investigate the oxidation of food lipids under PEF processing, confirming the occurrence of oxidation of lecithin under PEF treatment. The oxidative agents induced by PEF might be responsible for the oxidation of extracted yolk lecithin. Moreover, this study found that vitamin C as a natural antioxidant could effectively quench free radicals and inhibit the oxidation of lipid in NaCl and lecithin solutions as model systems under PEF processing, representing a way to minimize the impact of PEF treatment on food qualities.

  17. Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction

    USGS Publications Warehouse

    Heard, I.; Senftle, F.E.

    1984-01-01

    Solutions of 30% H2O2 ranging from pH = 0 to pH = 11.5 have been used to oxidize anthracite at room temperature. The inorganic impurities, primarily pyrite, catalysed the oxidation and reduction of H2O2 (the Fenton reaction) to form the hydroxyl radical; the oxidation of the organic matter was minimal and was observed only in strong acidic solutions (pH < 1.5). After acid demineralization, samples of the same anthracite underwent a significant enhancement of oxidation in both acid and alkaline solutions (pH = 0.4-11.5). As all the iron had been removed from the surface and the reactions were completed in a much shorter time, the oxidation mechanism must have been of a different nature than that for the untreated anthracite. A qualitative model based on the catalytic decomposition of H2O2 by activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite. ?? 1984.

  18. Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride.

    PubMed

    Raff, Jonathan D; Njegic, Bosiljka; Chang, Wayne L; Gordon, Mark S; Dabdub, Donald; Gerber, R Benny; Finlayson-Pitts, Barbara J

    2009-08-18

    Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO(y)) are also globally distributed, because NO formed in combustion processes is oxidized to NO(2), HNO(3), N(2)O(5) and a variety of other nitrogen oxides during transport. Deposition of HCl and NO(y) onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO(2) or N(2)O(5) on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO(2)), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO(2) in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

  19. Nitrous Oxide-dependent Iron-catalyzed Coupling Reactions of Grignard Reagents.

    PubMed

    Döhlert, Peter; Weidauer, Maik; Enthaler, Stephan

    2015-01-01

    The formation of carbon-carbon bonds is one of the fundamental transformations in chemistry. In this regard the application of palladium-based catalysts has been extensively investigated during recent years, but nowadays research focuses on iron catalysis, due to sustainability, costs and toxicity issues; hence numerous examples for iron-catalyzed cross-coupling reactions have been established, based on the coupling of electrophiles (R(1)-X, X = halide) with nucleophiles (R(2)-MgX). Only a small number of protocols deals with the iron-catalyzed oxidative coupling of nucleophiles (R(1)-MgX + R(2)-MgX) with the aid of oxidants (1,2-dihaloethanes). However, some issues arise with these oxidants; hence more recently the potential of the industrial waste product nitrous oxide (N(2)O) was investigated, because the unproblematic side product N(2) is formed. Based on that, we demonstrate the catalytic potential of easily accessible iron complexes in the oxidative coupling of Grignard reagents. Importantly, nitrous oxide was essential to obtain yields up to >99% at mild conditions (e.g. 1 atm, ambient temperature) and low catalyst loadings (0.1 mol%) Excellent catalyst performance is realized with turnover numbers of up to 1000 and turnover frequencies of up to 12000 h(-1). Moreover, a good functional group tolerance is observed (e.g. amide, ester, nitrile, alkene, alkyne). Afterwards the reaction of different Grignard reagents revealed interesting results with respect to the selectivity of cross-coupling product formation.

  20. Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst.

    PubMed

    Xu, Lingshun; Wu, Zongfang; Jin, Yuekang; Ma, Yunsheng; Huang, Weixin

    2013-08-07

    We have employed XPS and TDS to study the adsorption and surface reactions of H2O, CO and HCOOH on an FeO(111)/Pt(111) inverse model catalyst. The FeO(111)-Pt(111) interface of the FeO(111)/Pt(111) inverse model catalyst exposes coordination-unsaturated Fe(II) cations (Fe(II)CUS) and the Fe(II)CUS cations are capable of modifying the reactivity of neighbouring Pt sites. Water facilely dissociates on the Fe(II)CUS cations at the FeO(111)-Pt(111) interface to form hydroxyls that react to form both water and H2 upon heating. Hydroxyls on the Fe(II)CUS cations can react with CO(a) on the neighbouring Pt(111) sites to produce CO2 at low temperatures. Hydroxyls act as the co-catalyst in the CO oxidation by hydroxyls to CO2 (PROX reaction), while they act as one of the reactants in the CO oxidation by hydroxyls to CO2 and H2 (WGS reaction), and the recombinative reaction of hydroxyls to produce H2 is the rate-limiting step in the WGS reaction. A comparison of reaction behaviors between the interfacial CO(a) + OH reaction and the formate decomposition reaction suggest that formate is the likely surface intermediate of the CO(a) + OH reaction. These results provide some solid experimental evidence for the associative reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts.

  1. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    NASA Astrophysics Data System (ADS)

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  2. Mathematical modeling of an exothermic leaching reaction system: pressure oxidation of wide size arsenopyrite participates

    NASA Astrophysics Data System (ADS)

    Papangelakis, V. G.; Berk, D.; Demopoulos, G. P.

    1990-10-01

    In the design of processes involving exothermic reactions, as is the case of several sulfide leaching systems, it is desirable to utilize the energy liberated by the reaction to drive the reactor toward autogenous operation. For optimal reactor design, models which couple leaching kinetics and heat effects are needed. In this paper, the principles of modeling exothermic leaching reactions are outlined. The system investigated is the high-temperature (160 °C to 200 °C) pressure (O2) oxidation of arsenopyrite (FeAsS). The reaction system is characterized by three consecutive reactions: (1) heterogeneous dissolution of arsenopyrite particles, (2) homogeneous oxidation of iron(II) to iron(III), and (3) precipitation of scorodite (FeAsO4-2H2O). The overall kinetics is controlled by the arsenopyrite surface reaction. There was good agreement between laboratory-scale batch tests and model predictions. The model was expanded to simulate the performance of large-scale batch and single-stage continuous stirred tank reactor (CSTR) for the same rate-limiting regime. Emphasis is given to the identification of steady-state temperatures for autogenous processing. The effects of operating variables, such as feed temperature, slurry density, and retention time, on reactor operation and yield of leaching products are discussed.

  3. Variability in aerobic methane oxidation over the past 1.2 Myrs recorded in microbial biomarker signatures from Congo fan sediments

    NASA Astrophysics Data System (ADS)

    Talbot, Helen M.; Handley, Luke; Spencer-Jones, Charlotte L.; Dinga, Bienvenu Jean; Schefuß, Enno; Mann, Paul J.; Poulsen, John R.; Spencer, Robert G. M.; Wabakanghanzi, Jose N.; Wagner, Thomas

    2014-05-01

    Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30‰ to -40‰ for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential

  4. Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory

    SciTech Connect

    Liu, P.

    2010-11-28

    Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO{sub 2}/Cu(111), ZrO{sub 2}/Cu(111) < MoO{sub 3}/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.

  5. Oxidation of aqueous Cr(III) at birnessite surfaces: Constraints on reaction mechanism

    SciTech Connect

    Banerjee, D.; Nesbitt, H.W.

    1999-06-01

    X-ray Photoelectron Spectroscopy (XPS) was used to investigate oxidation of aqueous Cr(III) at the surface of 7 {angstrom}-birnessite [MnO{sub 1.75}(OH){sub 0.25}]. Special emphasis was placed on detection of intermediate oxidation states of chromium due to their critical environmental significance. No previous studies have been able to identify these intermediate oxidation states of chromium (namely, Cr[IV], and Cr[V]) on mineral surfaces or in natural solutions. Mn(2p{sub 3/2}), Cr(2p{sub 3/2}) and O(1s) spectra of the reacted surfaces reveal that Mn(IV) of synthetic birnessite undergoes reductive dissolution in two steps. The first step involves Mn(IV) reduction to Mn(III), that forms at the oxide surface probably as an oxyhydroxide (MnOOH), and in the second step Mn(III) is reduced to Mn(II) that is subsequently taken into solution. Each reductive reaction step involves transfer of only one electron to the Mn ion. After Cr(III){sub aq} is adsorbed onto the MnO{sub 2} surface, it undergoes oxidation in three separate steps, each involving the loss of one electron to Mn ions, so that Cr(IV), Cr(V) and Cr(VI) are produced. The intermediate reaction products, namely Mn(III), and Cr(V) were positively identified by XPS spectral analyses. Similarity in XPS binding energy values of Cr(III) and Cr(IV) as well as that of Cr(V) and Cr(VI), however, preclude separate identification of Cr(III) from Cr(IV) and Cr(VI) from Cr(V) multiplets on the near-surface of the solid. A parallel reaction scheme (exclusive of sorption reactions) best describes the birnessite-Cr(III){sub aq} redox reactions. The two parallel reactions proceed by separate mechanisms with a monodentate complex formed in one mechanism and a bidentate complex in another. The bulk of Cr(IV) probably is formed via the monodentate complex and Cr(V) via the bidentate complex. The rate expressions associated with these reactions display near-perfect correlation with changing surface abundances of Cr(IV) and Cr

  6. Teaching Aerobic Fitness Concepts.

    ERIC Educational Resources Information Center

    Sander, Allan N.; Ratliffe, Tom

    2002-01-01

    Discusses how to teach aerobic fitness concepts to elementary students. Some of the K-2 activities include location, size, and purpose of the heart and lungs; the exercise pulse; respiration rate; and activities to measure aerobic endurance. Some of the 3-6 activities include: definition of aerobic endurance; heart disease risk factors;…

  7. Elucidation of the reaction mechanism during the removal of copper oxide by halogen surfactant at the surface of copper plate

    NASA Astrophysics Data System (ADS)

    Yokoyama, Shun; Takahashi, Hideyuki; Itoh, Takashi; Motomiya, Kenichi; Tohji, Kazuyuki

    2013-01-01

    Although copper nanoparticles have various attractive properties, electrical applications of these was not achieved because of its surface oxide layer which prohibited electrical conduction. Thus, it can be considered that a new elimination method of the oxide on Cu surface, which simultaneously provide the resistance to re-oxidized, should be developed. In this study, the reaction between the metal oxide on Cu plate surface and halogen surfactant was introduced into development as a new elimination method of surface oxide layer. Since electrochemical and surface analysis are effective for analyzing the reaction mechanism which expected to be the reduction reaction of the oxide on metal surface, Cu electrode, which represented material of Cu nanoparticles surface, was used for the reaction mechanism analysis. The oxide is removed by controlling the temperature and selecting the optimal combination of solvents and the halogen surfactant (TIC). Results of electrochemical measurements strongly suggest that the chemical reaction between the oxides on the surface with the halogen surfactant is a substitution reaction which converts Cu oxide to Cu bromide, and continuously formed Cu bromide was dissolved into solvent. Totally, the oxide on the Cu surface was successfully eliminated.

  8. Enhancement Effect of Noble Metals on Manganese Oxide for the Oxygen Evolution Reaction.

    PubMed

    Seitz, Linsey C; Hersbach, Thomas J P; Nordlund, Dennis; Jaramillo, Thomas F

    2015-10-15

    Developing improved catalysts for the oxygen evolution reaction (OER) is key to the advancement of a number of renewable energy technologies, including solar fuels production and metal air batteries. In this study, we employ electrochemical methods and synchrotron techniques to systematically investigate interactions between metal oxides and noble metals that lead to enhanced OER catalysis for water oxidation. In particular, we synthesize porous MnOx films together with nanoparticles of Au, Pd, Pt, or Ag and observe significant improvement in activity for the combined catalysts. Soft X-ray absorption spectroscopy (XAS) shows that increased activity correlates with increased Mn oxidation states to 4+ under OER conditions compared to bare MnOx, which exhibits minimal OER current and remains in a 3+ oxidation state. Thickness studies of bare MnOx films and of MnOx films deposited on Au nanoparticles reveal trends suggesting that the enhancement in activity arises from interfacial sites between Au and MnOx.

  9. Online Monitoring of Methanol Electro-Oxidation Reactions by Ambient Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Cheng, Si; Wu, Qiuhua; Dewald, Howard D.; Chen, Hao

    2016-08-01

    Online detection of methanol electro-oxidation reaction products [e.g., formaldehyde (HCHO)] by mass spectrometry (MS) is challenging, owing to the high salt content and extreme pH of the electrolyte solution as well as the difficulty in ionizing the reaction products. Herein we present an online ambient mass spectrometric approach for analyzing HCHO generated from methanol electro-oxidation, taking the advantage of high salt tolerance of desorption electrospray ionization mass spectrometry (DESI-MS). It was found that HCHO can be detected as PhNHNH+=CH2 (m/z 121) by DESI after online derivatization with PhNHNH2. With this approach, the analysis of HCHO from methanol electro-oxidation by MS was carried out not only in acidic condition but also in alkaline media for the first time. Efficiencies of different electrodes for methanol oxidation at different pHs were also evaluated. Our results show that Au electrode produces more HCHO than Pt-based electrodes at alkaline pH, while the latter have higher yields at acidic solution. The presented methodology would be of great value for elucidating fuel cell reaction mechanisms and for screening ideal fuel cell electrode materials.

  10. Supercritical water oxidation of Quinazoline: Effects of conversion parameters and reaction mechanism.

    PubMed

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan

    2016-09-01

    The supercritical water oxidation reaction of quinazoline and a set of related reaction products were investigated in batch reactors by varying the temperature (T, 400-600 °C), time (t, 0-400 s), water density (ρ, 70.79-166.28  kg m(-3)) and oxidation coefficient (OC, 0-4.0). The TOC removal efficiency (CRE) increased significantly as the OC increased, whereas this effect was very limited at high OC (>2.0). Lack of oxygen resulted in low CRE and TN removal efficiency (NRE), also cause coke-formation, and giving high yield of NH3 and nitrogenous organic intermediates. Prolonging reaction time did not provide an appreciable improvement on CRE but remarkably increased NRE at temperature higher than 500 °C. Pyrimidines and pyridines as the nitrogenous intermediates were largely found in GC-MS spectrum. Polymerization among benzene, phenyl radical and benzyl radical played important roles in the formation of PAHs, such as naphthalene, biphenyl, phenanthrene. These collective results showed how the yield of intermediate products responded to changes in the process variables, which permitted the development of a potential reaction network for supercritical water oxidation of quinazoline.

  11. Water Oxidation by a Cytochrome P450: Mechanism and Function of the Reaction

    PubMed Central

    Prasad, Brinda; Mah, Derrick J.; Lewis, Andrew R.; Plettner, Erika

    2013-01-01

    P450cam (CYP101A1) is a bacterial monooxygenase that is known to catalyze the oxidation of camphor, the first committed step in camphor degradation, with simultaneous reduction of oxygen (O2). We report that P450cam catalysis is controlled by oxygen levels: at high O2 concentration, P450cam catalyzes the known oxidation reaction, whereas at low O2 concentration the enzyme catalyzes the reduction of camphor to borneol. We confirmed, using 17O and 2H NMR, that the hydrogen atom added to camphor comes from water, which is oxidized to hydrogen peroxide (H2O2). This is the first time a cytochrome P450 has been observed to catalyze oxidation of water to H2O2, a difficult reaction to catalyze due to its high barrier. The reduction of camphor and simultaneous oxidation of water are likely catalyzed by the iron-oxo intermediate of P450cam, and we present a plausible mechanism that accounts for the 1∶1 borneol:H2O2 stoichiometry we observed. This reaction has an adaptive value to bacteria that express this camphor catabolism pathway, which requires O2, for two reasons: 1) the borneol and H2O2 mixture generated is toxic to other bacteria and 2) borneol down-regulates the expression of P450cam and its electron transfer partners. Since the reaction described here only occurs under low O2 conditions, the down-regulation only occurs when O2 is scarce. PMID:23634216

  12. Permanganate oxidation of arsenic(III): Reaction stoichiometry and the characterization of solid product

    NASA Astrophysics Data System (ADS)

    Lee, Giehyeon; Song, Kyungsun; Bae, Jongseong

    2011-09-01

    Permanganate (MnO 4-) has widely been used as an effective oxidant for drinking water treatment systems, as well as for in situ treatment of groundwater impacted by various organic contaminants. The reaction stoichiometry of As(III) oxidation by permanganate has been assumed to be 1.5, based on the formation of solid product, which is putatively considered to be MnO 2(s). This study determined the stoichiometric ratio (SR) of the oxidation reaction with varying doses of As(III) (3-300 μM) and MnO 4- (0.5 or 300 μM) under circumneutral pH conditions (pH 4.5-7.5). We also characterized the solid product that was recovered ˜1 min after the oxidation of 2.16 mM As(III) by 0.97 mM MnO 4- at pH 6.9 and examined the feasibility of secondary heterogeneous As(III) oxidation by the solid product. When permanganate was in excess of As(III), the SR of As(III) to Mn(VII) was 2.07 ± 0.07, regardless of the solution pH; however, it increased to 2.49 ± 0.09 when As(III) was in excess. The solid product was analogous to vernadite, a poorly crystalline manganese oxide based on XRD analysis. The average valence of structural Mn in the solid product corresponded to +III according to the splitting interval of the Mn3s peaks (5.5 eV), determined using X-ray photoelectron spectroscopy (XPS). The relative proportions of the structural Mn(IV):Mn(III):Mn(II) were quantified as 19:62:19 by fitting the Mn2p 3/2 spectrum of the solid with the five multiplet binding energy spectra for each Mn valence. Additionally, the O1s spectrum of the solid was comparable to that of Mn-oxide but not of Mn-hydroxide. These results suggest that the solid product resembled a poorly crystalline hydrous Mn-oxide such as (Mn II0.19Mn III0.62Mn IV0.19) 2O 3· nH 2O, in which Mn(II) and Mn(IV) were presumably produced from the disproportionation of aqueous phase Mn(III). Thermodynamic calculations also show that the formation of Mn(III) oxide is more favorable than that of Mn(IV) oxide from As(III) oxidation

  13. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    PubMed

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5%) in α-MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2.

  14. Recovery after aerobic exercise is manipulated by tempo change in a rhythmic sound pattern, as indicated by autonomic reaction on heart functioning

    PubMed Central

    Wallert, John; Madison, Guy

    2014-01-01

    Physical prowess is associated with rapid recovery from exhaustion. Here we examined whether recovery from aerobic exercise could be manipulated with a rhythmic sound pattern that either decreased or increased in tempo. Six men and six women exercised repeatedly for six minutes on a cycle ergometer at 60 percent of their individual maximal oxygen consumption, and then relaxed for six minutes while listening to one of two sound pattern conditions, which seemed to infinitely either decrease or increase in tempo, during which heart and breathing activity was measured. Participants exhibited more high-frequent heart rate variability when listening to decreasing tempo than when listening to increasing tempo, accompanied by a non-significant trend towards lower heart rate. The results show that neuropsychological entrainment to a sound pattern may directly affect the autonomic nervous system, which in turn may facilitate physiological recovery after exercise. Applications using rhythmic entrainment to aid physical recovery are discussed. PMID:25285076

  15. Oxidative Degradation of Nadic-End-Capped Polyimides. 2; Evidence for Reactions Occurring at High Temperatures

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Johnston, J. Christopher; Cavano, Paul J.; Frimer, Aryeh A.

    1997-01-01

    The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (Cp-MAS) NMR. C-13 labeling of selected sites in the polymers allowed for direct observation of the transformations arising from oxidation processes. As opposed to model compound studies, the reactions were followed directly in the polymer. The labeling experiments confirm the previously reported oxidation of the methylene carbon to ketone in the methylenedianiline portion of the polymer chain. They also show the formation of two other oxidized species, acid and ester, from this same carbon. In addition, the technique provides the first evidence of the kind of degradation reactions that are occurring in the nadic end caps. Several PMR formulations containing moieties determined to be present after oxidation, as suggested by the labeling study, were synthesized. Weight loss, FTIR, and natural abundance NMR of these derivatives were followed during aging. In this way, weight loss could be related to the observed transformations.

  16. Pd(Quinox)-Catalyzed Allylic Relay Suzuki Reactions of Secondary Homostyrenyl Tosylates via Alkene-Assisted Oxidative Addition.

    PubMed

    Stokes, Benjamin J; Bischoff, Amanda J; Sigman, Matthew S

    2014-06-01

    Pd-catalyzed allylic relay Suzuki cross-coupling reactions of secondary alkyl tosylates, featuring a sterically-hindered oxidative addition and precise control of β-hydride elimination, are reported. The identification of a linear free energy relationship between the relative rates of substrate consumption and the electronic nature of the substrate alkene suggests that the oxidative addition requires direct alkene involvement. A study of the effect of chain length on the reaction outcome supports a chelation-controlled oxidative addition.

  17. Solid-gas reactions of complex oxides inside an environmental high-resolution transmission electron microscope.

    PubMed

    Sayagués, M J; Krumeich, F; Hutchison, J L

    2001-07-01

    In a gas reaction cell (GRC), installed in a high-resolution transmission electron microscope (HRTEM) (JEOL 4000EX), samples can be manipulated in an ambient atmosphere (p<50mbar). This experimental setup permits not only the observation of solid-gas reactions in situ at close to the atomic level but also the induction of structural modifications under the influence of a plasma, generated by the ionization of gas particles by an intense electron beam. Solid state reactions of non-stoichiometric niobium oxides and niobium tungsten oxides with different gases (O2, H2 and He) have been carried out inside this controlled environment transmission electron microscope (CETEM), and this has led to reaction products with novel structures which are not accessible by conventional solid state synthesis methods. Monoclinic and orthorhombic Nb(12)O(29) crystallize in block structures comprising [3x4] blocks. The oxidation of the monoclinic phase occurs via a three step mechanism: firstly, a lamellar defect of composition Nb(11)O(27) is formed. Empty rectangular channels in this defect provide the diffusion paths in the subsequent oxidation. In the second step, microdomains of the Nb(22)O(54) phase are generated as an intermediate state of the oxidation process. The structure of the final product Nb(10)O(25), which consists of [3x3] blocks and tetrahedral coordinated sites, is isostructural to PNb(9)O(25). Microdomains of this apparently metastable phase appear as a product of the Nb(22)O(54) oxidation. The oxidation reaction of Nb(12)O(29) was found to be a reversible process: the reduction of the oxidation product with H(2) results in the formation of the starting Nb(12)O(29) structure. On the other hand, the block structure of Nb(12)O(29) has been destroyed by a direct treatment of the sample with H(2) while NbO in a cubic rock salt structure is produced. This in situ technique has also been applied to niobium tungsten oxides which constitute the solid solution series Nb(8-n

  18. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    PubMed

    Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

    2016-12-01

    Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

  19. Metal-Organic Frameworks derivatives for improving the catalytic activity of CO oxidation reaction.

    PubMed

    Ji, Wenlan; Xu, Zhiling; Liu, Pengfei; Zhang, Suoying; Zhou, Weiqiang; Li, Hongfeng; Zhang, Tao; Li, Linjie; Lu, Xiaohua; Wu, Jiansheng; Zhang, Weina; Huo, Fengwei

    2017-03-15

    Metal-Organic Frameworks (MOFs) based derivatives have attracted an increasing interest in various research fields. However, most of reported papers mainly focused on the pristine MOFs-based derivatives, and researches on the functional MOFs-based derivatives composites are rare. Here, a simple strategy was reported to design the functional MOFs based derivatives composites by the encapsulation of the metal nanoparticles (MNPs) in MOFs matrixes (MNPs@MOFs) and the high-temperature calcination of MNPs@MOFs composites. The as-prepared MNPs@metal oxide composites with the hierarchical pore structure exhibited excellent catalytic activity and high stability for CO oxidation reaction.

  20. Substrate activation for O2 reactions by oxidized metal centers in biology.

    PubMed

    Pau, Monita Y M; Lipscomb, John D; Solomon, Edward I

    2007-11-20

    The uncatalyzed reactions of O(2) (S = 1) with organic substrates (S = 0) are thermodynamically favorable but kinetically slow because they are spin-forbidden and the one-electron reduction potential of O(2) is unfavorable. In nature, many of these important O(2) reactions are catalyzed by metalloenzymes. In the case of mononuclear non-heme iron enzymes, either Fe(II) or Fe(III) can play the catalytic role in these spin-forbidden reactions. Whereas the ferrous enzymes activate O(2) directly for reaction, the ferric enzymes activate the substrate for O(2) attack. The enzyme-substrate complex of the ferric intradiol dioxygenases exhibits a low-energy catecholate to Fe(III) charge transfer transition that provides a mechanism by which both the Fe center and the catecholic substrate are activated for the reaction with O(2). In this Perspective, we evaluate how the coupling between this experimentally observed charge transfer and the change in geometry and ligand field of the oxidized metal center along the reaction coordinate can overcome the spin-forbidden nature of the O(2) reaction.

  1. Nitrile Oxide-Norbornene Cycloaddition as a Bioorthogonal Crosslinking Reaction for the Preparation of Hydrogels.

    PubMed

    Truong, Vinh X; Zhou, Kun; Simon, George P; Forsythe, John S

    2015-10-01

    This communication describes the first application of cycloaddition between an in situ generated nitrile oxide with norbornene leading to a polymer crosslinking reaction for the preparation of poly(ethylene glycol) hydrogels under physiological conditions. Hydrogels with high water content and robust physical strength are readily formed within 2-5 min by a simple two-solution mixing method which allows 3D encapsulation of neuronal cells. This bioorthogonal crosslinking reaction provides a simple yet highly effective method for preparation of hydrogels to be used in bioengineering.

  2. Variation of the oxidation state of verdoheme in the heme oxygenase reaction

    SciTech Connect

    Gohya, Tomohiko; Sato, Michihiko; Zhang Xuhong; Migita, Catharina T.

    2008-11-14

    Heme oxygenase (HO) converts hemin to biliverdin, CO, and iron applying molecular oxygen and electrons. During successive HO reactions, two intermediates, {alpha}-hydroxyhemin and verdoheme, have been generated. Here, oxidation state of the verdoheme-HO complexes is controversial. To clarify this, the heme conversion by soybean and rat HO isoform-1 (GmHO-1 and rHO-1, respectively) was compared both under physiological conditions, with oxygen and NADPH coupled with ferredoxin reductase/ferredoxin for GmHO-1 or with cytochrome P450 reductase for rHO-1, and under a non-physiological condition with hydrogen peroxide. EPR measurements on the hemin-GmHO-1 reaction with oxygen detected a low-spin ferric intermediate, which was undetectable in the rHO-1 reaction, suggesting the verdoheme in the six-coordinate ferric state in GmHO-1. Optical absorption measurements on this reaction indicated that the heme degradation was extremely retarded at verdoheme though this reaction was not inhibited under high-CO concentrations, unlike the rHO-1 reaction. On the contrary, the Gm and rHO-1 reactions with hydrogen peroxide both provided ferric low-spin intermediates though their yields were different. The optical absorption spectra suggested that the ferric and ferrous verdoheme coexisted in reaction mixtures and were slowly converted to the ferric biliverdin complex. Consequently, in the physiological oxygen reactions, the verdoheme is found to be stabilized in the ferric state in GmHO-1 probably guided by protein distal residues and in the ferrous state in rHO-1, whereas in the hydrogen peroxide reactions, hydrogen peroxide or hydroxide coordination stabilizes the ferric state of verdoheme in both HOs.

  3. A flexible modeling framework for gas transport and reaction: Applied to oxide removal from non-oxide porous media

    NASA Astrophysics Data System (ADS)

    Pantina, Joseph Albert

    Many non-oxide ceramics are produced through the densification of a non-oxide powder compact by sintering. A pervasive problem when processing non-oxide powders is the growth of a native oxide layer on the powder surface due to oxidation. Non-oxide powders sinter poorly without the addition of sintering additives to aid in the removal of surface oxide and lower grain boundary energies. Reducing agents, such as C, remove the oxide layer at hold temperatures much below the sintering temperature, forming a significant amount of gas (mainly CO(g)) to be removed. However, sintering additives to enhance densification at the sintering temperature can also form gas at the lower temperature, depleting the additive before reaching the sintering temperature. In this work, we have developed an analytical modeling framework to simulate gas transport and reaction in a porous medium comprised of an arbitrary collection of chemical species. This modeling framework automatically generates the necessary conditions to calculate the thermodynamic equilibrium composition at a given temperature and uses the Dusty Gas Model (DGM) to predict the gas transport. This model accounts for processing parameters including the initial powder composition, sample thickness, porosity, pore radius, and tortuosity of the powder compact, plus the furnace pressure and heating cycle. This model was used to predict the time for complete oxide removal ( tc) and residual composition for three material systems. The C/SiC/SiO2 and B4C/B2O3/C systems were studied to identify the functional dependence of t c with respect to each processing parameter. Additionally, the C/SiC/SiO2 system was studied to determine optimal heating cycles to control the rate of CO(g) effusion into the furnace while reduce heating times. The C/SiC/SiO2/B4C system was studied to quantify the amount B4C depleted and redistributed during SiO 2 removal for samples of varying thicknesses, initial SiO2 content, and holding temperature. B4C

  4. Reactions of calcium orthosilicate and barium zirconate with oxides and sulfates of various elements

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1979-01-01

    Calcium orthosilicate and barium zirconate were evaluated as the insulation layer of thermal barrier coatings for air cooled gas turbine components. Their reactions with various oxides and sulfates were studied at 1100 C and 1300 C for times ranging up to 400 and 200 hours, respectively. These oxides and sulfates represent potential impurities or additives in gas turbine fuels and in turbine combustion air, as well as elements of potential bond coat alloys. The phase compositions of the reaction products were determined by X-ray diffraction analysis. BaZrO3 and 2CaO-SiO2 both reacted with P2O5, V2O5, Cr2O3, Al2O3, and SiO2. In addition, 2CaO-SiO2 reacted with Na2O, BaO, MgO, and CoO and BaZrO3 reacted with Fe2O3.

  5. Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts.

    PubMed

    Cao, Shaowen; Tao, Franklin Feng; Tang, Yu; Li, Yuting; Yu, Jiaguo

    2016-08-22

    Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes. In the past two decades, the catalytic performances of different catalytic reactions on nanoparticles of metals and oxides with well controlled sizes or shapes have been extensively studied thanks to the spectacular advances in syntheses of nanomaterials of metals and oxides. This review discussed the size and shape effects of catalyst particles on catalytic activity and selectivity of reactions performed at solid-gas or solid-liquid interfaces with a purpose of establishing correlations of size- and shape-dependent chemical and structural factors of surface of a catalyst with the corresponding catalytic performances toward understanding of catalysis at a molecular level.

  6. Theoretical study of the dark-oxidation reaction mechanisms for organic polymers

    NASA Astrophysics Data System (ADS)

    Wang, Guixiu; Zhu, Rongxiu; Zhang, Dongju; Liu, Chengbu

    2006-08-01

    To model the dark-oxidation mechanism of organic polymers, the reactions of the corresponding model compounds, including cumene, methyl 2-methylbutyrate, methyl methacrylate and methylacrylic acid, with triplet O 2 molecule, have been studied by performing density functional theory calculations at the UB3LYP/6-31G(d) level. The calculated results show that these model compounds can be oxygenated by O 2 via an H-abstract mechanism. The structures of initial contact charge transfer complexes, transition states, intermediates of cage-like pairs of radicals, and final hydro-peroxides involved in the reactions have been shown in details. The present results are expected to provide a general guidance for understanding the dark-oxidation mechanism of organic polymers.

  7. Aerobic Microbial Respiration In Oceanic Oxygen Minimum Zones

    PubMed Central

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene M.; Revsbech, Niels Peter; Löscher, Carolin; Schunck, Harald; Desai, Dhwani K.; Hauss, Helena; Kiko, Rainer; Holtappels, Moritz; LaRoche, Julie; Schmitz, Ruth A.; Graco, Michelle I.; Kuypers, Marcel M. M.

    2015-01-01

    Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic denitrification and alternative anaerobic pathways of organic matter remineralization cannot account for the ammonium requirements of reported anammox rates. Here, we explore the significance of microaerobic respiration as a source of ammonium during organic matter degradation in the oxygen-deficient waters off Namibia and Peru. Experiments with additions of double-labelled oxygen revealed high aerobic activity in the upper OMZs, likely controlled by surface organic matter export. Consistently observed oxygen consumption in samples retrieved throughout the lower OMZs hints at efficient exploitation of vertically and laterally advected, oxygenated waters in this zone by aerobic microorganisms. In accordance, metagenomic and metatranscriptomic analyses identified genes encoding for aerobic terminal oxidases and demonstrated their expression by diverse microbial communities, even in virtually anoxic waters. Our results suggest that microaerobic respiration is a major mode of organic matter remineralization and source of ammonium (~45-100%) in the upper oxygen minimum zones, and reconcile hitherto observed mismatches between ammonium producing and consuming processes therein. PMID:26192623

  8. Aerobic Microbial Respiration In Oceanic Oxygen Minimum Zones.

    PubMed

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene M; Revsbech, Niels Peter; Löscher, Carolin; Schunck, Harald; Desai, Dhwani K; Hauss, Helena; Kiko, Rainer; Holtappels, Moritz; LaRoche, Julie; Schmitz, Ruth A; Graco, Michelle I; Kuypers, Marcel M M

    2015-01-01

    Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic denitrification and alternative anaerobic pathways of organic matter remineralization cannot account for the ammonium requirements of reported anammox rates. Here, we explore the significance of microaerobic respiration as a source of ammonium during organic matter degradation in the oxygen-deficient waters off Namibia and Peru. Experiments with additions of double-labelled oxygen revealed high aerobic activity in the upper OMZs, likely controlled by surface organic matter export. Consistently observed oxygen consumption in samples retrieved throughout the lower OMZs hints at efficient exploitation of vertically and laterally advected, oxygenated waters in this zone by aerobic microorganisms. In accordance, metagenomic and metatranscriptomic analyses identified genes encoding for aerobic terminal oxidases and demonstrated their expression by diverse microbial communities, even in virtually anoxic waters. Our results suggest that microaerobic respiration is a major mode of organic matter remineralization and source of ammonium (~45-100%) in the upper oxygen minimum zones, and reconcile hitherto observed mismatches between ammonium producing and consuming processes therein.

  9. Theoretical evaluation of isotopic fractionation factors in oxidation reactions of benzene, phenol and chlorophenols.

    PubMed

    Adamczyk, Paweł; Paneth, Piotr

    2011-09-01

    We have studied theoretically the rate determining steps of reactions of benzene with permanganate, perchlorate, ozone and dioxygen in the gas phase and aqueous solution as well as phenol and dichlorophenol in protonated and unprotonated forms in aqueous solution. Kinetic isotope effects were then calculated for all carbon atoms and based on their values isotopic fractionation factors corresponding to compound specific isotopic analysis have been evaluated. The influence of the oxidant, substituents, environment and protonation on the isotopic fractionation factors has been analyzed.

  10. Preparation and characterization TiO(x)-Pt/C catalyst for hydrogen oxidation reaction.

    PubMed

    Elezović, N R; Babić, B M; Vracar, Lj M; Radmilović, V R; Krstajić, N V

    2009-07-07

    The hydrogen oxidation reaction (HOR) was studied at the home made TiO(x)-Pt/C nanocatalysts in 0.5 mol dm(-3) HClO(4) at 25 degrees C. Pt/C catalyst was first synthesized by modified ethylene glycol method (EG) on commercially used carbon support (Vulcan XC-72). Then TiO(x)-Pt/C catalyst was prepared by the polyole method followed by TiO(x) post-deposition. The synthesized catalyst was characterized by XRD, TEM and EDX techniques. It was found that Pt/C catalyst nanoparticles were homogenously distributed over carbon support with the mean particle size of about 2.4 nm. The quite similar, homogenous distribution and particle size were obtained for Pt/C doped by TiO(x) catalyst which was the confirmation that TiO(x) post-deposition did not lead to significant growth of the Pt nanoparticles. The electrochemically active surface area of the catalyst was determined by using the cyclic voltammetry technique.The kinetics of hydrogen oxidation was investigated by the linear sweep voltammetry technique at the rotating disc electrode (RDE). The kinetic equations used for the analysis were derived considering the reversible or irreversible nature of the kinetics of the HOR. It was found that the hydrogen oxidation reaction for an investigated catalyst proceeded as an electrochemically reversible reaction. The values determined for the kinetic parameters-Tafel slope of 28 mV dec(-1) and exchange current density about 0.4 mA cm(-2)(Pt) are in good agreement with usually reported values for a hydrogen oxidation reaction with platinum catalysts in acid solutions.

  11. Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways

    SciTech Connect

    Yan, Nai-Qiang; Liu, Shou-Heng; Chang, Shih-Ger

    2004-10-22

    Accurate oxidation rate constants of mercury gas are needed for determining its dispersion and lifetime in the atmosphere. They would also help in developing a technology for the control of mercury emissions from coal-fired power plants. However, it is difficult to establish the accurate rate constants primarily due to the fact that mercury easily adsorbs on solid surface and its reactions can be catalyzed by the surface. We have demonstrated a procedure that allows the determination of gas phase, surface-induced, and photo-induced contributions in the kinetic study of the oxidation of mercury by chlorine gas. The kinetics was studied using reactors with various surface to volume ratios. The effect of the surface and the photo irradiation on the reaction was taken into consideration. The pressure dependent study revealed that the gas phase oxidation was a three-body collision process. The third order rate constant was determined to be 7.5({+-}0.2) x 10{sup -39} mL{sup 2} molecules{sup -2}s{sup -1} with N{sub 2} as the third body at 297 {+-} 1 K. The surface induced reaction on quartz window was second order and the rate constant was 2.7 x 10{sup -17} mL{sup 2} molecules{sup -1} cm{sup -2} sec. Meanwhile, the 253.7 nm photon employed for mercury detection was found to accelerate the reaction. The utilization efficiency of 253.7 nm photon for Hg{sup 0} oxidation was 6.7 x 10{sup -4} molecules photon{sup -1} under the conditions employed in this study.

  12. Hypochlorous acid-mediated protein oxidation: how important are chloramine transfer reactions and protein tertiary structure?

    PubMed

    Pattison, David I; Hawkins, Clare L; Davies, Michael J

    2007-08-28

    Hypochlorous acid (HOCl) is a powerful oxidant generated from H2O2 and Cl- by the heme enzyme myeloperoxidase, which is released from activated leukocytes. HOCl possesses potent antibacterial properties, but excessive production can lead to host tissue damage that occurs in numerous human pathologies. As proteins and amino acids are highly abundant in vivo and react rapidly with HOCl, they are likely to be major targets for HOCl. In this study, two small globular proteins, lysozyme and insulin, have been oxidized with increasing excesses of HOCl to determine whether the pattern of HOCl-mediated amino acid consumption is consistent with reported kinetic data for isolated amino acids and model compounds. Identical experiments have been carried out with mixtures of N-acetyl amino acids (to prevent reaction at the alpha-amino groups) that mimic the protein composition to examine the role of protein structure on reactivity. The results indicate that tertiary structure facilitates secondary chlorine transfer reactions of chloramines formed on His and Lys side chains. In light of these data, second-order rate constants for reactions of Lys side chain and Gly chloramines with Trp side chains and disulfide bonds have been determined, together with those for further oxidation of Met sulfoxide by HOCl and His side chain chloramines. Computational kinetic models incorporating these additional rate constants closely predict the experimentally observed amino acid consumption. These studies provide insight into the roles of chloramine formation and three-dimensional structure on the reactions of HOCl with isolated proteins and demonstrate that kinetic models can predict the outcome of HOCl-mediated protein oxidation.

  13. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    PubMed

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs.

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

    PubMed

    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.

  15. Biotransformations Utilizing β-Oxidation Cycle Reactions in the Synthesis of Natural Compounds and Medicines

    PubMed Central

    Œwizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Kołek, Teresa

    2012-01-01

    β-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the β-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via β-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

  16. Adsorption and Reaction of Methanethiol on Thin-Film Cerium Oxide

    SciTech Connect

    Mullins, David R; McDonald, Tom S

    2008-01-01

    The adsorption and reaction of methanethiol, CH{sub 3}SH, have been studied on cerium oxide thin films that were vapor deposited on Ru(0 0 0 1). The behavior of the CH{sub 3}SH was examined as a function of the Ce oxidation state. CH{sub 3}SH weakly interacts with fully oxidized CeO{sub 2}(1 1 1) forming both chemisorbed CH{sub 3}SH and CH{sub 3}S + OH. OH forms through the reaction of the sulfhydrol H with the surface O. These species recombine and desorb near 180 K leaving the surface virtually clean. When the ceria is ca. 50% reduced, the chemisorbed CH{sub 3}SH desorbs near 150 K while the CH{sub 3}S + OH are stable to 400 K. These species react above 450 K to produce predominantly CH{sub 4} and CH{sub 3}SH. A small amount of CH{sub 2}O and water are also formed through reaction with the O in the ceria. Atomic S is left on the surface. S 2p, C 1s and O 1s soft X-ray photoelectron spectroscopy were used to identify the nature of the chemisorbed species and the adsorption site of the CH{sub 3}S or S.

  17. Adsorption and reaction of methanethiol on thin-film cerium oxide

    NASA Astrophysics Data System (ADS)

    Mullins, D. R.; McDonald, T. S.

    2008-03-01

    The adsorption and reaction of methanethiol, CH 3SH, have been studied on cerium oxide thin films that were vapor deposited on Ru(0 0 0 1). The behavior of the CH 3SH was examined as a function of the Ce oxidation state. CH 3SH weakly interacts with fully oxidized CeO 2(1 1 1) forming both chemisorbed CH 3SH and CH 3S + OH. OH forms through the reaction of the sulfhydrol H with the surface O. These species recombine and desorb near 180 K leaving the surface virtually clean. When the ceria is ca. 50% reduced, the chemisorbed CH 3SH desorbs near 150 K while the CH 3S + OH are stable to 400 K. These species react above 450 K to produce predominantly CH 4 and CH 3SH. A small amount of CH 2O and water are also formed through reaction with the O in the ceria. Atomic S is left on the surface. S 2p, C 1s and O 1s soft X-ray photoelectron spectroscopy were used to identify the nature of the chemisorbed species and the adsorption site of the CH 3S or S.

  18. Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction

    NASA Astrophysics Data System (ADS)

    Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

    2013-03-01

    Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize

  19. Oxygenated monoterpenes citral and carvacrol cause oxidative damage in Escherichia coli without the involvement of tricarboxylic acid cycle and Fenton reaction.

    PubMed

    Chueca, Beatriz; Pagán, Rafael; García-Gonzalo, Diego

    2014-10-17

    Oxygenated monoterpenes citral and carvacrol are common constituents of many essential oils (EOs) that have been extensively studied as antimicrobial agents but whose mechanisms of microbial inactivation have not been totally elucidated. A recent study described a mechanism of Escherichia coli death for (+)-limonene, a hydrocarbon monoterpene also frequently present in EOs, similar to the common mechanism proposed for bactericidal antibiotics. This mechanism involves the formation of Fenton-mediated hydroxyl radical, a reactive oxygen species (ROS), via tricarboxylic acid (TCA) cycle, which would ultimately inactivate cells. Our objective was to determine whether E. coli MG1655 inactivation by citral and carvacrol follows a similar mechanism of cell death. Challenging experiments with 300μL/L citral and 100μL/L carvacrol inactivated at least 2.5log10cycles of exponentially growing cells in 3h under aerobic conditions. The presence of thiourea (an ROS scavenger) reduced cell inactivation in 2log10cycles, demonstrating the role of ROS in cell death. Decreased resistance of a ΔrecA mutant (deficient in an enzyme involved in SOS response to DNA damage) indicated that citral and carvacrol caused oxidative damage to DNA. Although the mechanism of E. coli inactivation by carvacrol and citral was similarly mediated by ROS, their formation did not follow the same pathways described for (+)-limonene and bactericidal drugs because neither Fenton reaction nor NADH production via the TCA cycle was involved in cell death. Moreover, further experiments demonstrated antimicrobial activity of citral and carvacrol in anaerobic environments without the involvement of ROS. As a consequence, cell death by carvacrol and citral in anaerobiosis follows a different mechanism than that observed under aerobic conditions. These results demonstrated a different mechanism of inactivation by citral and carvacrol with regard to (+)-limonene and bactericidal antibiotics, indicating the

  20. Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage.

    PubMed

    Lu, F S H; Bruheim, I; Haugsgjerd, B O; Jacobsen, C

    2014-08-15

    The main objective of this study was to investigate the effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage. Krill oil was incubated at two different temperatures (20 and 40 °C) for 28 or 42 days. The oxidative stability of krill oil was assessed by peroxide value and anisidine value, measurement of lipid derived volatiles, lipid classes and antioxidants. The non-enzymatic browning reactions were assessed through the measurement of pyrroles, free amino acids content and Strecker-derived volatiles. The increase of incubation temperature firstly increased the lipid oxidation in krill oil and subsequently the non-enzymatic browning reactions. The occurrence of these reactions was most likely due to the reaction between α-dicarbonyl or carbonyl compounds with amino acids or ammonia. In addition to tocopherol and astaxanthin esters, the formation of pyrroles might help to protect the krill oil against lipid oxidation.

  1. A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

    NASA Astrophysics Data System (ADS)

    Conte, Marco; Wilson, Karen; Chechik, Victor

    2010-10-01

    A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X-band electron paramagnetic resonance spectroscopy.

  2. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    SciTech Connect

    Pizarro, C.; Escudey, M.; Moya, S.A.; Fabris, J.D.

    2005-04-26

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124 deg. C to 500 deg. C. The room temperature Moessbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 deg. C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  3. Construction materials for reaction unit in the liquid-phase synthesis of propylene oxide

    SciTech Connect

    Zaritskii, V.I.D.

    1987-09-01

    The main components of the reaction medium in equipment for the synthesis of propylene oxide by liquid-phase oxidation of gaseous propylene with peracetic acid are propylene, peracetic acid, ethyl acetate, acetic acid, propylene oxide, carbon dioxide, oxygen, methane, and propylene glycol acetates. The operating conditions of the equipment and content of the main components of the medium are shown. Results are given for the investigation of the corrosion behavior of 12Kh18N10T, 10Kh17N13M2T, 08Kh22N6T, and 08Kh21N6M2T steels, AD0 and AD1 aluminum, and VT1-0 titanium. VSt3 carbon steel was tested for comparison.

  4. Aerobic Metabolism of Streptococcus agalactiae

    PubMed Central

    Mickelson, M. N.

    1967-01-01

    Streptococcus agalactiae cultures possess an aerobic pathway for glucose oxidation that is strongly inhibited by cyanide. The products of glucose oxidation by aerobically grown cells of S. agalactiae 50 are lactic and acetic acids, acetylmethylcarbinol, and carbon dioxide. Glucose degradation products by aerobically grown cells, as percentage of glucose carbon, were 52 to 61% lactic acid, 20 to 23% acetic acid, 5.5 to 6.5% acetylmethylcarbinol, and 14 to 16% carbon dioxide. There was no evidence for a pentose cycle or a tricarboxylic acid cycle. Crude cell-free extracts of S. agalactiae 50 possessed a strong reduced nicotinamide adenine dinucleotide (NADH2) oxidase that is also cyanide-sensitive. Dialysis or ultrafiltration of the crude, cell-free extract resulted in loss of NADH2 oxidase activity. Oxidase activity was restored to the inactive extract by addition of the ultrafiltrate or by addition of menadione or K3Fe(CN)6. Noncytochrome iron-containing pigments were present in cell-free extracts of S. agalactiae. The possible participation of these pigments in the respiration of S. agalactiae is presently being studied. PMID:4291090

  5. Insight into the Mechanism of Graphene Oxide Degradation via the Photo-Fenton Reaction.

    PubMed

    Bai, Hao; Jiang, Wentao; Kotchey, Gregg P; Saidi, Wissam A; Bythell, Benjamin J; Jarvis, Jacqueline M; Marshall, Alan G; Robinson, Renã A S; Star, Alexander

    2014-05-15

    Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150-1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed.

  6. Facile synthesis of PdSx/C porous nanospheres and their applications for ethanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Qiang; Zhang, Fuhua; Ma, Xuemei; Zheng, Yiqun; Hou, Shifeng

    2016-12-01

    We report a facile approach for the synthesis of carbon-supported palladium polysulphide porous nanospheres (PdSx/C) and their applications for ethanol oxidation reaction. Typical synthesis started with generation of palladium/poly (3,4-ethylenedioxythiophene)(Pd/PEDOT) nanospheres, followed by a calcination process at an optimized temperature to form PdSx/C, with an average size of 2.47 ± 0.60 and 50 nm of PdSx nanoparticles and carbon porous nanospheres, respectively. Various techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques were performed to characterize their morphologies, compositions and structures. In contrary to most Pd-based electrochemical catalysts that could be easily poised with trace sulfur during the catalytic oxidation process, the as-prepared PdSx/C porous nanospheres exhibited high electrocatalytic activities and stabilities for the electrochemical catalytic oxidation of ethanol in alkaline medium. In particular, the forward peak current intensity achieved 162.1 mA mg-1 and still maintained at 46.7 mA mg-1 even after 1000 cycles. This current work not only offers a novel type of fuel-cell catalyst for ethanol oxidation reaction, but also provides a possible route for solving the sulfur-poisoning problem in catalysis.

  7. Insight into the Mechanism of Graphene Oxide Degradation via the Photo-Fenton Reaction

    PubMed Central

    2015-01-01

    Graphene represents an attractive two-dimensional carbon-based nanomaterial that holds great promise for applications such as electronics, batteries, sensors, and composite materials. Recent work has demonstrated that carbon-based nanomaterials are degradable/biodegradable, but little work has been expended to identify products formed during the degradation process. As these products may have toxicological implications that could leach into the environment or the human body, insight into the mechanism and structural elucidation remain important as carbon-based nanomaterials become commercialized. We provide insight into a potential mechanism of graphene oxide degradation via the photo-Fenton reaction. We have determined that after 1 day of treatment intermediate oxidation products (with MW 150–1000 Da) were generated. Upon longer reaction times (i.e., days 2 and 3), these products were no longer present in high abundance, and the system was dominated by graphene quantum dots (GQDs). On the basis of FTIR, MS, and NMR data, potential structures for these oxidation products, which consist of oxidized polycyclic aromatic hydrocarbons, are proposed. PMID:24860637

  8. The Effect of Anodic Oxide Films on the Nickel-Aluminum Reaction in Aluminum Braze Sheet

    NASA Astrophysics Data System (ADS)

    Tadgell, Colin A.; Wells, Mary A.; Corbin, Stephen F.; Colley, Leo; Cheadle, Brian; Winkler, Sooky

    2017-01-01

    The influence of an anodic oxide surface film on the nickel-aluminum reaction at the surface of aluminum brazing sheet has been investigated. Samples were anodized in a barrier-type solution and subsequently sputtered with nickel. Differential scanning calorimetry (DSC) and metallography were used as the main investigative techniques. The thickness of the anodic film was found to control the reaction between the aluminum substrate and nickel coating. Solid-state formation of nickel-aluminum intermetallic phases occurred readily when a relatively thin oxide film (13 to 25 nm) was present, whereas intermetallic formation was suppressed in the presence of thicker oxides ( 60 nm). At an intermediate oxide film thickness of 35 nm, the Al3Ni phase formed shortly after the initiation of melting in the aluminum substrate. Analysis of DSC traces showed that formation of nickel-aluminum intermetallic phases changed the melting characteristics of the aluminum substrate, and that the extent of this change can be used as an indirect measure of the amount of nickel incorporated into the intermetallic phases.

  9. Surface reaction mechanisms during ozone and oxygen plasma assisted atomic layer deposition of aluminum oxide.

    PubMed

    Rai, Vikrant R; Vandalon, Vincent; Agarwal, Sumit

    2010-09-07

    We have elucidated the reaction mechanism and the role of the reactive intermediates in the atomic layer deposition (ALD) of aluminum oxide from trimethyl aluminum in conjunction with O(3) and an O(2) plasma. In situ attenuated total reflection Fourier transform infrared spectroscopy data show that both -OH groups and carbonates are formed on the surface during the oxidation cycle. These carbonates, once formed on the surface, are stable to prolonged O(3) exposure in the same cycle. However, in the case of plasma-assisted ALD, the carbonates decompose upon prolonged O(2) plasma exposure via a series reaction kinetics of the type, A (CH(3)) --> B (carbonates) --> C (Al(2)O(3)). The ratio of -OH groups to carbonates on the surface strongly depends on the oxidizing agent, and also the duration of the oxidation cycle in plasma-assisted ALD. However, in both O(3) and O(2) plasma cycles, carbonates are a small fraction of the total number of reactive sites compared to the hydroxyl groups.

  10. Substrate Oxidation by Indoleamine 2,3-Dioxygenase: EVIDENCE FOR A COMMON REACTION MECHANISM.

    PubMed

    Booth, Elizabeth S; Basran, Jaswir; Lee, Michael; Handa, Sandeep; Raven, Emma L

    2015-12-25

    The kynurenine pathway is the major route of L-tryptophan (L-Trp) catabolism in biology, leading ultimately to the formation of NAD(+). The initial and rate-limiting step of the kynurenine pathway involves oxidation of L-Trp to N-formylkynurenine. This is an O2-dependent process and catalyzed by indoleamine 2,3-dioxygenase and tryptophan 2,3-dioxygenase. More than 60 years after these dioxygenase enzymes were first isolated (Kotake, Y., and Masayama, I. (1936) Z. Physiol. Chem. 243, 237-244), the mechanism of the reaction is not established. We examined the mechanism of substrate oxidation for a series of substituted tryptophan analogues by indoleamine 2,3-dioxygenase. We observed formation of a transient intermediate, assigned as a Compound II (ferryl) species, during oxidation of L-Trp, 1-methyl-L-Trp, and a number of other substrate analogues. The data are consistent with a common reaction mechanism for indoleamine 2,3-dioxygenase-catalyzed oxidation of tryptophan and other tryptophan analogues.

  11. The Effect of Anodic Oxide Films on the Nickel-Aluminum Reaction in Aluminum Braze Sheet

    NASA Astrophysics Data System (ADS)

    Tadgell, Colin A.; Wells, Mary A.; Corbin, Stephen F.; Colley, Leo; Cheadle, Brian; Winkler, Sooky

    2017-03-01

    The influence of an anodic oxide surface film on the nickel-aluminum reaction at the surface of aluminum brazing sheet has been investigated. Samples were anodized in a barrier-type solution and subsequently sputtered with nickel. Differential scanning calorimetry (DSC) and metallography were used as the main investigative techniques. The thickness of the anodic film was found to control the reaction between the aluminum substrate and nickel coating. Solid-state formation of nickel-aluminum intermetallic phases occurred readily when a relatively thin oxide film (13 to 25 nm) was present, whereas intermetallic formation was suppressed in the presence of thicker oxides ( 60 nm). At an intermediate oxide film thickness of 35 nm, the Al3Ni phase formed shortly after the initiation of melting in the aluminum substrate. Analysis of DSC traces showed that formation of nickel-aluminum intermetallic phases changed the melting characteristics of the aluminum substrate, and that the extent of this change can be used as an indirect measure of the amount of nickel incorporated into the intermetallic phases.

  12. Effects of aluminum and zirconia contents on the reaction bonded aluminum oxide process

    NASA Astrophysics Data System (ADS)

    Sheedy, Paul Martin

    The effects of aluminum and ZrO2 contents on the reaction and sintering of reaction bonded aluminum oxide (RBAO) were investigated. It was apparent that ZrO2-containing RBAO powders with higher initial aluminum contents (>45 vol%) were increasingly more difficult to react and sinter. During oxidation in air, samples often underwent a self-propagating high-temperature synthesis (SHS) reaction which led to catastrophic failure. This reaction and cracking behavior was more pronounced with increasing aluminum and ZrO2 contents of the powders. Subsequently, it was shown that the SHS reaction was actually two combustion phenomena: a thermal explosion reaction on the surface of the sample between aluminum and oxygen, which (in ZrO2-containing samples) triggered a self propagating aluminothermic reduction of ZrO2, forming Al2O3 and Al 3Zr. Therefore, methods for controlling the rate of the initial oxidation reaction were effective since both SHS reactions were prevented. Despite the use of controlled firing, initial samples with increasing aluminum contents proved difficult to densify. It was found that in all RBAO samples (regardless of ZrO2 content), the reactively formed Al 2O3 underwent the gamma to alpha-Al2O 3 transformation, which resulted in the development of a vermicular microstructure. In ZrO2-containing RBAO samples, this transformation was inhibited and occurred concurrently with the start of densification. In addition, the start of bulk shrinkage in these samples was delayed and the densification rates were decreased in comparison to samples without ZrO 2. This ultimately resulted in a decrease in the limiting density to which ZrO2-containing RBAO samples could be sintered. Surprisingly, in samples without ZrO2, increasing the aluminum content did not appear to have any effects upon the densification behavior of RBAO. In examining RBAO samples with similar aluminum contents but increasing ZrO2 contents, it became apparent that the grain growth inhibiting

  13. Citric Acid-Modified Fenton's Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems

    SciTech Connect

    Seol, Yongkoo; Javandel, Iraj

    2008-03-15

    Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H{sub 2}O{sub 2} concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H{sub 2}O{sub 2} relative to iron catalysts (Fe{sup 2+}/H{sub 2}O{sub 2} < 1/330) would result in lowering the efficiency of contaminant removal by iron chelations in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

  14. Sub-micrometer sized yttrium oxide fibers prepared through hydrothermal reaction

    SciTech Connect

    Li, Nan; Yanagisawa, Kazumichi

    2011-03-15

    Research highlights: {yields} Y{sub 2}O{sub 3} fibers were synthesized by hydrothermal reaction followed by calcination. {yields} Y(OH){sub x}Cl{sub 3-x}.yH{sub 2}O was received from hydrothermal reaction. {yields} Y{sub 2}O{sub 3} fibers showed outstanding high-temperature stability. -- Abstract: Yttrium oxide fibers have been synthesized via hydrothermal reaction and subsequent thermal treatment using yttrium chloride as precursor. The products before and after the thermal treatment were characterized by powder X-ray diffractions (XRD), scanning electron microscopy (SEM), ion-chromatograph analysis, and thermogravimetry and differential thermal analysis (TG-DTA). The fiber diameter ranged from 100 to 300 nm, while the length was up to tens of microns. It was found that the chemical composition and morphology of the products were closely related to the pH value of reaction solution, and fibrous products could be obtained at pH 9.5-10.25. These oxide fibers exhibited outstanding high-temperature stability, which maintained their morphology at temperature up to 1400 {sup o}C.

  15. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    NASA Astrophysics Data System (ADS)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-04-01

    The electro-catalytic behavior of Pt-CoOx/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH4 as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoOx, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of COads on Pt active sites by the participation of CoOx. Compared to Pt/MWCNTs, Pt-CoOx/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoOx/MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups controls the total rate of MOR process.

  16. Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

    NASA Technical Reports Server (NTRS)

    Collins, J.; Rosner, D. E.; Castillo, J.

    1992-01-01

    A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

  17. Characterizing Pyroxene Reaction Space in Calcium-Aluminum Rich Inclusions: Oxidation During CAI Rim Formation

    NASA Astrophysics Data System (ADS)

    Dyl, K. A.; Young, E. D.

    2009-12-01

    We define the reaction space that controls changes in pyroxene composition in CAIs and Wark-Lovering (WL) rims in an oxidizing solar nebula. Ti-rich pyroxenes in CAIs record a sub-solar oxygen fugacity (Ti3+/Ti4+~1.5). WL rim pyroxenes in the CAI Leoville 144A have a distinctly lower oxidation state.This difference supports WL rim condensation in an environment of increasing O2(g) and Mg(g) (Simon et al. 2005). We used the following phase components to identify four linearly independent reactions (Thompson 1982): diopside, CaTs (Al2Mg-1Si-1), T3 (Ti3+AlMg-1Si-1), T4 (Ti4+Al2Mg-1Si-2), En (MgCa-1), perovskite, O(g), Mg(g), SiO(g), and Ca(g). Compositional variation in this system is dominated by two reactions. The first is oxidation of Ti3+ via reaction with O and Mg in the gas phase: 1.5 O(g) + Mg(g) → ¼ Di + [Ti4+Mg3/4Ti3+-1Ca-1/4Si-1/2] (1). Pyroxene is produced and En is introduced. The second reaction (2) is perovskite formation. It is observed in the WL rim of Leoville 144A, and experiments confirm that an elevated Ti component converts pyroxene to perovskite(Gupta et al. 1973). MgCa-1 is the third linearly independent reaction (3). They combine to give: ½ Di + x Ca(g)→ x Mg(g)+ Pv + [Mg1/2-xSiTi4+-1Ca-1/2+x](2,3). Unlike (1), pyroxene is consumed in this reaction. The parameter x defines the extent of Mg-Ca exchange. When x > 0.5, WL rim formation occurs in an environment where Mg is volatile and Ca condenses. The reaction space defined by reactions (1) and (2,3) describes the transition from CAI interior to WL rims. WL rim pyroxene Ti contents, [CaTs], and Ca < 1 pfu are all explained in this space. The fourth linearly independent reaction is SiO(g):1/8 Di + ¼ Mg(g)→ ¾ SiO(g) + [Mg3/8Ca1/8Ti4+Ti3+-1Si-1/2](4). Silica reduction forms Ti4+, releasing SiO(g). (4) does not describe the oxidation of Ti3+ in WL rim pyroxene, but (1) - (4) results in En formation directly from the gas phase. This may explain WL rim analyses that have Si contents in excess

  18. Effect of atmospheric oxidative plasma treatments on polypropylenic fibers surface: Characterization and reaction mechanisms

    NASA Astrophysics Data System (ADS)

    Nisticò, Roberto; Magnacca, Giuliana; Faga, Maria Giulia; Gautier, Giovanna; D'Angelo, Domenico; Ciancio, Emanuele; Lamberti, Roberta; Martorana, Selanna

    2013-08-01

    Atmospheric pressure plasma-dielectric barrier discharge (APP-DBD, open chamber configuration) was used to functionalize polypropylene (PP) fibers surface in order to generate oxidized-reactive groups such as hydroperoxides, alcohols and carbonyl species (i.e. ketones and others). Such a species increased the surface polarity, without causing material degradation. Three different types of plasma mixture (He, He/O2, He/O2/H2O) under three different values of applied power (750, 1050, 1400 W) were investigated. The formed plasma species (O2+, O single atom and OH radical) and their distribution were monitored via optical emission spectrometry (OES) measurements, and the plasma effects on PP surface species formation were followed by X-ray photoemission spectroscopy (XPS). Results allowed to better understand the reaction pathways between plasma phase and PP fibers. In fact, two reaction mechanisms were proposed, the first one concerning the plasma phase reactions and the second one involving material surface modifications.

  19. Guanine Oxidation in Double-stranded DNA by MnTMPyP/KHSO(5): At Least Three Independent Reaction Pathways.

    PubMed

    Lapi, A; Pratviel, G; Meunier, B

    2001-01-01

    In order to better define the mechanism and the products of guanine oxidation within DNA, we investigated the details of the mechanism of guanine oxidation by a metalloporphyrin, Mn-TMPyP, associated to KHSO(5) on oligonucleotides. We found that the three major products of guanine oxidation are formed by independent reaction routes. The oxidized guanidinohydantoin (1) and the proposed spiro compound 3 derivatives are not precursors of imidazolone lesion (Iz). These guanine lesions as well as their degradation products, may account for non-detected guanine oxidation products on oxidatively damaged DNA.

  20. Water oxidation catalysis: an amorphous quaternary Ba-Sr-Co-Fe oxide as a promising electrocatalyst for the oxygen-evolution reaction.

    PubMed

    Zhang, Cuijuan; Berlinguette, Curtis P; Trudel, Simon

    2016-01-25

    We present an amorphous quaternary Ba-Sr-Co-Fe oxide (a-BSCF) with a specific stoichiometry, readily fabricated via a photochemical decomposition method. a-BSCF demonstrates high catalytic activity towards the oxygen-evolution reaction (OER).

  1. Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: a facile synthesis of β-ketophosphine oxides.

    PubMed

    Zhang, Pengbo; Zhang, Liangliang; Gao, Yuzhen; Xu, Jian; Fang, Hua; Tang, Guo; Zhao, Yufen

    2015-05-07

    The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.

  2. Reactions between Grignard reagents and heterocyclic N-oxides: stereoselective synthesis of substituted pyridines, piperidines, and piperazines.

    PubMed

    Andersson, Hans; Olsson, Roger; Almqvist, Fredrik

    2011-01-21

    In this perspective we discuss the recent developments of stereoselective synthesis of substituted pyridines, piperidines, and piperazines from cheap and commercially readily available starting materials. Pyridine N-oxides and pyrazine N-oxides are reacted with alkyl, aryl, alkynyl and vinyl Grignard reagents to give a diverse set of heterocycles in high yields. Optically active substituted piperazines are obtained by an asymmetric reaction from pyrazine N-oxides using sparteine as chiral ligand. In addition, a stereoselective synthesis of dienal-oximes from the reaction between pyridine N-oxides and Grignard reagents is presented, which results in a useful intermediate for the synthesis of a diverse set of compounds.

  3. Human 2-Oxoglutarate Dehydrogenase Complex E1 Component Forms a Thiamin-derived Radical by Aerobic Oxidation of the Enamine Intermediate*

    PubMed Central

    Nemeria, Natalia S.; Ambrus, Attila; Patel, Hetalben; Gerfen, Gary; Adam-Vizi, Vera; Tretter, Laszlo; Zhou, Jieyu; Wang, Junjie; Jordan, Frank

    2014-01-01

    Herein are reported unique properties of the human 2-oxoglutarate dehydrogenase multienzyme complex (OGDHc), a rate-limiting enzyme in the Krebs (citric acid) cycle. (a) Functionally competent 2-oxoglutarate dehydrogenase (E1o-h) and dihydrolipoyl succinyltransferase components have been expressed according to kinetic and spectroscopic evidence. (b) A stable free radical, consistent with the C2-(C2α-hydroxy)-γ-carboxypropylidene thiamin diphosphate (ThDP) cation radical was detected by electron spin resonance upon reaction of the E1o-h with 2-oxoglutarate (OG) by itself or when assembled from individual components into OGDHc. (c) An unusual stability of the E1o-h-bound C2-(2α-hydroxy)-γ-carboxypropylidene thiamin diphosphate (the “ThDP-enamine”/C2α-carbanion, the first postdecarboxylation intermediate) was observed, probably stabilized by the 5-carboxyl group of OG, not reported before. (d) The reaction of OG with the E1o-h gave rise to superoxide anion and hydrogen peroxide (reactive oxygen species (ROS)). (e) The relatively stable enzyme-bound enamine is the likely substrate for oxidation by O2, leading to the superoxide anion radical (in d) and the radical (in b). (f) The specific activity assessed for ROS formation compared with the NADH (overall complex) activity, as well as the fraction of radical intermediate occupying active centers of E1o-h are consistent with each other and indicate that radical/ROS formation is an “off-pathway” side reaction comprising less than 1% of the “on-pathway” reactivity. However, the nearly ubiquitous presence of OGDHc in human tissues, including the brain, makes these findings of considerable importance in human metabolism and perhaps disease. PMID:25210035

  4. Effect of long term anaerobic and intermittent anaerobic/aerobic starvation on aerobic granules.

    PubMed

    Pijuan, Maite; Werner, Ursula; Yuan, Zhiguo

    2009-08-01

    The effect of long term anaerobic and intermittent anaerobic/aerobic starvation on the structure and activity of aerobic granules was studied. Aerobic granular sludge treating abattoir wastewater and achieving high levels of nutrient removal was subjected to 4-5 week starvation under anaerobic and intermittent anaerobic/aerobic conditions. Microscopic pictures of granules at the beginning of the starvation period presented a round and compact surface morphology with a much defined external perimeter. Under both starvation conditions, the morphology changed at the end of starvation with the external border of the granules surrounded by floppy materials. The loss of granular compactness was faster and more pronounced under anaerobic/aerobic starvation conditions. The release of Ca(2+) at the onset of anaerobic/aerobic starvation suggests a degradation of extracellular polymeric substances. The activity of ammonia oxidizing bacteria was reduced by 20 and 36% during anaerobic and intermittent anaerobic/aerobic starvation, respectively. When fresh wastewater was reintroduced, the granules recovered their initial morphology within 1 week of normal operation and the nutrient removal activity recovered fully in 3 weeks. The results show that both anaerobic and intermittent anaerobic/aerobic conditions are suitable for maintaining granule structure and activity during starvation.

  5. Oxidation of microcystins by permanganate: reaction kinetics and implications for water treatment.

    PubMed

    Rodríguez, Eva; Majado, María E; Meriluoto, Jussi; Acero, Juan L

    2007-01-01

    A few genera of cyanobacteria produce toxins which contaminate drinking water resources. Microcystins (MC), widely reported cyanotoxins, cause acute and chronic toxicity effects in living beings including humans and warrant removal from drinking water. In the present study, unknown second-order rate constants for the reactions of microcystin-LR (MC-LR), -RR and -YR with potassium permanganate were determined at pH 6.2-8.2 and temperature 10-25 degrees C. The reaction of permanganate with MCs is second-order overall and first-order with respect to both permanganate and toxin. The second-order rate constant for the reaction of MC-LR with permanganate at pH 7 and 20 degrees C was 357.2+/-17.5M(-1)s(-1). The influence of pH on the oxidation process was not appreciable and the activation energy was 28.8 kJ mol(-1). Slightly higher reactivity with permanganate was found for MC-RR (418.0M(-1)s(-1)) and MC-YR (405.9M(-1)s(-1)). According to the results obtained, permanganate likely attacks the Adda moiety of the MC molecule. The oxidation of MCs in a natural surface water was also investigated. A permanganate dose of 1-1.25mgL(-1) was enough to reduce MCs concentration below the guideline value of 1microgL(-1). Permanganate oxidation is therefore a feasible option for microcystin removal during preoxidation processes. However, the oxidant dose must be carefully optimized in order to remove extracellular MCs without causing cell lysis (due to chemical stress) and further release of MCs.

  6. The Photochemical Oxidation of Siderite That Drove Hydrogen Based Microbial Redox Reactions in The Archean Biosphere

    NASA Astrophysics Data System (ADS)

    Kim, J. D.; Yee, N.; Falkowski, P. G.

    2012-12-01

    Hydrogen is the most abundant element in the universe and molecular hydrogen (H2) is a rich source of electron in a mildly reducing environment for microbial redox reactions, such as anoxygenic photosynthesis and methanogenesis. Subaerial volcanoes, ocean crust serpentinization and mid-ocean ridge volcanoes have been believed to be the major source of the hydrogen flux to the atmosphere. Although ferrous ion (Fe2+) photooxidation has been proposed as an alternative mechanism by which hydrogen gas was produced, ferruginous water in contact with a CO2-bearing atmosphere is supersaturated with respect to FeCO3 (siderite), thus the precipitation of siderite would have been thermodynamically favored in the Archean environment. Siderite is the critical mineral component of the oldest fossilized microbial mat. It has also been inferred as a component of chemical sedimentary protolith in the >3750 Ma Nuvvuagittuq supracrustal belt, Canada and the presence of siderite in the protolith suggests the occurrence of siderite extends to Hadean time. Analyses of photooxidation of siderite suggest a significant flux of hydrogen in the early atmosphere. Our estimate of the hydrogen production rate under Archean solar flux is approximately 50 times greater than the estimated hydrogen production rate by the volcanic activity based on a previous report (Tian et al. Science 2005). Our analyses on siderite photooxidation also suggest a mechanism by which banded iron formation (BIF) was formed. The photooxidation transforms siderite to magnetite/maghemite (spinnel iron oxide), while oxygenic oxidation of siderite leads to goethite, and subsequently to hematite (Fe3+2O3) upon dehydration. We will discuss the photochemical reaction, which was once one of the most ubiquitous photochemical reactions before the rise of oxygen in the atmosphere. Photooxidation of siderite over time by UV light From left to right: UV oxidized siderite, pristine siderite, oxidized siderite by oxygen

  7. 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.

  8. Design of heterogeneous photocatalysts based on metal oxides to control the selectivity of chemical reactions.

    PubMed

    Maldotti, Andrea; Molinari, Alessandra

    2011-01-01

    Photocatalysis is particularly relevant in order to realize chemical transformations of interest in synthesis and, at the same time, to move towards a "sustainable chemistry" with a minimal environmental impact. Heterogeneous systems with well-defined textural characteristics represent a suitable means to tailor the selectivity of photocatalytic processes. Here, we summarize and classify the significant features of photocatalysts consisting of photoactive metal oxides dispersed on high-surface-area solid supports, or constrained inside their porous network. These systems are based on the use of titanium dioxide, highly dispersed oxides of titanium, chromium, vanadium, and polyoxotungstates. They share similar primary photoprocesses: light absorption induces a charge separation process with formation of positive holes able to oxidize organic substrates. A great number of the papers discussed here concern oxidation reactions carried out in the presence of O₂ for inducing partial oxidation of alcohols and monooxygenation of hydrocarbons. We also devote some attention to photocatalysis in the absence of O₂. In these conditions, the photogenerated charge separation offers the possibility to induce the formation of C-C and C-N bonds. We emphasize that the optimal tailoring of photoactive materials for synthetic purposes can be achieved by combining recent advances in the preparation of nanostructured materials with mechanistic knowledge derived from surface science and molecular level investigations.

  9. Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields

    NASA Astrophysics Data System (ADS)

    Ham, Jason E.; Harrison, Joel C.; Jackson, Stephen R.; Wells, J. R.

    2016-05-01

    The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OHrad) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OHrad generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OHrad was removed. This suggests that OHrad radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures.

  10. Reactions of Propylene Oxide on Supported Silver Catalysts: Insights into Pathways Limiting Epoxidation Selectivity

    SciTech Connect

    Kulkarni, Apoorva; Bedolla-Pantoja, Marco; Singh, Suyash; Lobo, Raul F.; Mavrikakis, Manos; Barteau, Mark A.

    2012-02-04

    The reactions of propylene oxide (PO) on silver catalysts were studied to understand the network of parallel and sequential reactions that may limit the selectivity of propylene epoxidation by these catalysts. The products of the anaerobic reaction of PO on Ag/a-Al2O3 were propanal, acetone and allyl alcohol for PO conversions below 2–3%. As the conversion of PO was increased either by increasing the temperature or the contact time, acrolein was formed at the expense of propanal, indicating that acrolein is a secondary reaction product in PO decomposition. With addition of oxygen to the feedstream the conversion of PO increased moderately. In contrast to the experiments in absence of oxygen, CO2 was a significant product while the selectivity to propanal decreased as soon as oxygen was introduced in the system. Allyl alcohol disappeared completely from the product stream in the presence of oxygen, reacting to form acrolein and CO2. The product distribution may be explained by a network of reactions involving two types of oxametallacycles formed by ring opening of PO: one with the oxygen bonded to C1 (OMC1, linear) and the other with oxygen bonded to C2 (OMC2, branched). OMC1 reacts to form PO, propanal, and allyl alcohol.

  11. Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields

    PubMed Central

    Ham, Jason E.; Harrison, Joel C.; Jackson, Stephen R.; Wells, J.R.

    2016-01-01

    The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OH•) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OH• generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OH• was removed. This suggests that OH• radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures. PMID:27346977

  12. Dechlorination reaction of hexachlorobenzene with calcium oxide at 300-400 degrees C.

    PubMed

    Gao, Xingbao; Wang, Wei; Liu, Xiao

    2009-09-30

    Hexachlorobenzene (HCB) was thermally treated with calcium oxide (CaO) at 300-400 degrees C. Analyses of chloride ions and residual HCB confirmed that a dechlorination reaction had occurred. The dechlorination mechanism was investigated with a series of analytical methods including X-ray fluorescence (XRF), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The final products detected were CaCO(3) by XRD and Raman spectroscopy, amorphous carbon by Raman spectroscopy, and CaCl(2) by XPS. The newly produced species of CaCO(3) and amorphous carbon were thought to be the ultimate fate of the C element of HCB. After identification of the final dechlorination products, we can conclude that the reaction of HCB with CaO at 300-400 degrees C is through a dechlorination/polymerization pathway, which is induced by electron transfer. An overall reaction formula for HCB reaction with CaO was proposed and was energetically quite favorable. The results are helpful for the further comprehension of the reaction mechanism for thermal dechlorination of PCDD/Fs in CaO rich matrices.

  13. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

    PubMed

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan; Xu, Donghai

    2017-03-01

    This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO2 formation. Low sensitivity of NH3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process.

  14. Effects of oxidative stress reaction for the Eisenia fetida with exposure in Cd(2).

    PubMed

    Dongxing, Zhou; Yucui, Ning; Jiabin, Liu; Jie, Deng; Guohua, Rong; Bilige, Siqin; Yijun, Liu

    2016-11-01

    Earthworms are widely used in all kinds of pollutants as sensitive bio-indicator organisms because of their immediately oxidative stress response under the stress of heavy metal. However, there are a large number of indexes associated with the oxidative stress response. Finding out the key monitoring indexes in the stress process becomes a practical demand of the pollution monitoring and warning process. We studied two groups, the short-term test and the long-term test. The former one is for 10 days, taking out an earthworm every day. The latter test lasted 30 days, taking out an earthworm every 10 days. The Cd(2+) concentration was set at 50, 100, 125, 250, and 500 mg kg(-1). Post-clitellum segments of earthworms were chosen to determine superoxide enzyme (SOD), peroxidase (POD), glutathione peroxidase (GSH-Px), glutathione-S transferase (GST), catalase (CAT), vitamin E (VE), malondialdehyde (MDA), and acetylcholinesterase (AChE). The results showed that the main bio-indicators associating with oxidative stress reaction in short-term group were CAT, SOD, and POD. MDA could be used as a bio-indicator in the early and mid-term. VE was only the bio-indicator in the mid-term stress. While with the long-term test, the main bio-indicators associated with oxidative stress reaction were GSH-Px and MDA. The AChE activity was only suitable for oxidative stress response caused by heavy metal stress more than 30 days.

  15. Immunological reaction and oxidative stress after light or heavy polypropylene mesh implantation in inguinal hernioplasty

    PubMed Central

    Donati, Marcello; Brancato, Giovanna; Grosso, Giuseppe; Li Volti, Giovanni; La Camera, Giuseppina; Cardì, Francesco; Basile, Francesco; Donati, Angelo

    2016-01-01

    Abstract The relationship between mesh weight and host tissue reaction has, so far, not been fully investigated. Lightweight meshes (LWM) are thought to give less inflammatory response compared with heavyweight meshes (HWM). The present study is a randomized, controlled, double-blind clinical trial performed in 61 patients who underwent an elective inguinal hernioplasty. The primary outcome of the study was to investigate the relationship between total amount of prosthetic material (polypropylene), immunological reaction, and oxidative stress. The study was double-blinded. Sixty-one patients were recruited for the study and randomly assigned to 2 groups (groups A and B). Levels of inflammation markers (interleukin-6 [IL-6] and tumor necrosis factor-α [TNF-α]) and oxidative stress markers (reduced glutathione [GSH] and lipid hydroperoxides [LOOH]) were determined preoperatively and after undergoing inguinal hernioplasty (after 6, 72, and 288 hours), respectively, with LWM and HWM. There was no significant difference in IL-6 levels between HWM and LWM (P = 0.3, 0.7, 0.8 after 6, 72, and 288 hours, respectively). A statistically significant difference was found after 72 hours for TNF-α (P = 0.01), for GSH after 6 hours (P < 0.01), and after 6 and 72 hours for LOOH (P = 0.05, 0.01, respectively). Oxidative stress occurred at earlier time points and was pore accentuated HWM versus LWM and prodromal to TNF-α increase. Also, in randomized clinical trial, the use of LWM gives advantages in terms of less inflammatory response when compared with HWM. Moreover, there is a significant higher oxidative stress after implantation of HWM. The intensity of oxidative stress seems to be strongly related to the amount of implanted polypropylene. (Trial registration number: NCT01090284). PMID:27310955

  16. IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

    PubMed

    de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

    2015-10-28

    The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

  17. Enzyme-catalysed synthesis and reactions of benzene oxide/oxepine derivatives of methyl benzoates.

    PubMed

    Boyd, Derek R; Sharma, Narain D; Harrison, John S; Malone, John F; McRoberts, W Colin; Hamilton, John T G; Harper, David B

    2008-04-07

    A series of twelve benzoate esters was metabolised, by species of the Phellinus genus of wood-rotting fungi, to yield the corresponding benzyl alcohol derivatives and eight salicylates. The isolation of a stable oxepine metabolite, from methyl benzoate, allied to evidence of the migration and retention of a carbomethoxy group (the NIH Shift), during enzyme-catalysed ortho-hydroxylation of alkyl benzoates to form salicylates, is consistent with a mechanism involving an initial arene epoxidation step. This mechanism was confirmed by the isolation of a remarkably stable, optically active, substituted benzene oxide metabolite of methyl 2-(trifluoromethyl)benzoate, which slowly converted into the racemic form. The arene oxide was found to undergo a cycloaddition reaction with 4-phenyl-1,2,4-triazoline-3,5-dione to yield a crystalline cycloadduct whose structure and racemic nature was established by X-ray crystallography. The metabolite was also found to undergo some novel benzene oxide reactions, including epoxidation to give an anti-diepoxide, base-catalysed hydrolysis to form a trans-dihydrodiol and acid-catalysed aromatisation to yield a salicylate derivative via the NIH Shift of a carbomethoxy group.

  18. The analysis of magnesium oxide hydration in three-phase reaction system

    SciTech Connect

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  19. Theoretical study of structure, stability, and the hydrolysis reactions of small iridium oxide nanoclusters.

    PubMed

    Zhou, Xin; Yang, Jingxiu; Li, Can

    2012-10-11

    The geometric structures and relative stabilities of small iridium oxide nanoclusters, Ir(m)O(n) (m = 1-5 and n = 1-2m), have been systematically investigated using density functional theory (DFT) calculations at the B3LYP level. Our results show that the lowest-energy structures of these clusters can be obtained by the sequential oxidation of small "core" iridium clusters. The iridium-monoxide-like clusters have relatively higher stability because of their relatively high binding energy and second difference in energies. On the basis of the optimized lowest-energy structures of neutral and cationic (IrO(2))(n) (n = 1-5), DFT has been used to study the hydrolysis reaction of these clusters with water molecules. The calculated results show that the addition of water molecules to the cationic species is much easier than the neutral ones. The overall hydrolysis reaction energies are more exothermic for the cationic clusters than for the neutral clusters. Our calculations indicate that H(2)O can be more easily split on the cationic iridium oxide clusters than on the neutral clusters.

  20. Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions.

    PubMed

    Mueller, David N; Machala, Michael L; Bluhm, Hendrik; Chueh, William C

    2015-01-19

    Surface redox-active centres in transition-metal oxides play a key role in determining the efficacy of electrocatalysts. The extreme sensitivity of surface redox states to temperatures, to gas pressures and to electrochemical reaction conditions renders them difficult to investigate by conventional surface-science techniques. Here we report the direct observation of surface redox processes by surface-sensitive, operando X-ray absorption spectroscopy using thin-film iron and cobalt perovskite oxides as model electrodes for elevated-temperature oxygen incorporation and evolution reactions. In contrast to the conventional view that the transition metal cations are the dominant redox-active centres, we find that the oxygen anions near the surface are a significant redox partner to molecular oxygen due to the strong hybridization between oxygen 2p and transition metal 3d electronic states. We propose that a narrow electronic state of significant oxygen 2p character near the Fermi level exchanges electrons with the oxygen adsorbates. This result highlights the importance of surface anion-redox chemistry in oxygen-deficient transition-metal oxides.

  1. Confining a bi-enzyme inside the nanochannels of a porous aluminum oxide membrane for accelerating the enzymatic reactions.

    PubMed

    Shangguan, Li; Wei, Yuanqing; Liu, Xu; Yu, Jiachao; Liu, Songqin

    2017-02-28

    An artificial metabolon with high conversion efficiency was constructed by confining a bi-enzyme into porous aluminum oxide nanochannels, which accelerated enzymatic reactions by minimizing the diffusion loss of intermediate species.

  2. Diffusion-reaction of aluminum and oxygen in thermally grown Al2O3 oxide layers

    NASA Astrophysics Data System (ADS)

    Osorio, Julián D.; Giraldo, Juliana; Hernández, Juan C.; Toro, Alejandro; Hernández-Ortiz, Juan P.

    2014-04-01

    The diffusion-reaction of aluminum (Al) and oxygen (O), to form thermally grown oxide (TGO) layers in thermal barrier coatings (TBCs), is studied through an analytical model. A nonsymmetrical radial basis function approach is used to numerically solve the mass balance equations that predict the TGO growth. Correct boundary conditions for the Al and O reactions are laid out using scaling arguments. The Damköhler number shows that the O-Al reaction is several orders of magnitude faster than diffusion. In addition, a comparison between aluminum and oxygen diffusivities indicates that TGO growth is governed by aluminum diffusion. The results are compared with experimental measurements on air plasma spray-deposited TBCs treated at 1,373 K with exposure times ranging from 1 to 1700 hours. We found that, for several time decades, the thickness of the thermally grown layer has power law dependence of time with an exponent of ½, following the diffusion control mechanism. At later times, however, the presence of other oxides and additional kinetics modify the diffusive exponent.

  3. Behavior of Supported Palladium Oxide Nanoparticles under Reaction Conditions, Studied with near Ambient Pressure XPS.

    PubMed

    Jürgensen, Astrid; Heutz, Niels; Raschke, Hannes; Merz, Klaus; Hergenröder, Roland

    2015-08-04

    Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is a promising method to close the "pressure gap", and thus, study the surface composition during heterogeneous reactions in situ. The specialized spectrometers necessary for this analytical technique have recently been adapted to operate with a conventional X-ray source, making it available for routine quantitative analysis in the laboratory. This is shown in the present in situ study of the partial oxidation of 2-propanol catalyzed with PdO nanoparticles supported on TiO2, which was investigated under reaction conditions as a function of gas composition (alcohol-to-oxygen ratio) and temperature. Exposure of the nanoparticles to 2-propanol at 30 °C leads to immediate partial reduction of the PdO, followed by a continuous reduction of the remaining PdO during heating. However, gaseous oxygen inhibits the reduction of PdO below 90 °C, and the oxidation of 2-propanol to carboxylates only occurs in the presence of oxygen above 90 °C. These results support the theory that metallic palladium is the active catalyst material, and they show that environmental conditions affect the nanoparticles and the reaction process significantly. The study also revealed challenges and limitations of this analytical method. Specifically, the intensity and fixed photon energy of a conventional X-ray source limit the spectral resolution and surface sensitivity of lab-based NAP-XPS, which affect precision and accuracy of the quantitative analysis.

  4. Iridium−Ruthenium Alloyed Nanoparticles for the Ethanol Oxidation Fuel Cell Reactions

    SciTech Connect

    Su D.; Du, W.; Deskins, N.A.; Teng, X.

    2012-06-01

    In this study, carbon supported Ir-Ru nanoparticles with average sizes ranging from 2.9 to 3.7 nm were prepared using a polyol method. The combined characterization techniques, that is, scanning transmission electron microscopy equipped with electron energy loss spectroscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, were used to determine an Ir-Ru alloy nanostructure. Both cyclic voltammetry and chronoamperometry (CA) results demonstrate that Ir{sub 77}Ru{sub 23}/C bears superior catalytic activities for the ethanol oxidation reaction compared to Ir/C and commercial Pt/C catalysts. In particular, the Ir{sub 77}Ru{sub 23}/C catalyst shows more than 21 times higher mass current density than that of Pt/C after 2 h reaction at a potential of 0.2 V vs Ag/AgCl in CA measurement. Density functional theory simulations also demonstrate the superiority of Ir-Ru alloys compared to Ir for the ethanol oxidation reaction.

  5. Gold-TiO2-Nickel catalysts for low temperature-driven CO oxidation reaction

    NASA Astrophysics Data System (ADS)

    Hinojosa-Reyes, Mariana; Zanella, Rodolfo; Maturano-Rojas, Viridiana; Rodríguez-González, Vicente

    2016-04-01

    Nickel-doped-TiO2 catalysts were prepared by the sol-gel method and surface modified with gold nanoparticles (AuNPs) by the urea-deposition-precipitation technique. The as-synthesized catalysts were characterized by X-ray diffraction, Raman and XPS spectroscopies, N2 physisorption, STEM-HAADF microscopy and TPR hydrogen consumption. The Au/TiO2-Ni catalysts were evaluated catalytically performing CO oxidation reactions. The catalyst with nickel content of 1 wt. % (Au/TiO2-Ni 1) showed the highest CO conversion with respect to the high-nickel-content or bare/commercial TiO2 at 0 °C. In situ DRIFTS showed a strong participation of both nickel due to the presence of surface-nickel-metallic nanoparticles formed during the CO adsorption process at reaction temperatures above 200 °C, and surface-bridged-nickel-CO species. A minor deactivation rate was observed for the Au/TiO2-Ni 1 catalyst in comparison with the Au/TiO2 one. The oxygen vacancies that were created on the sol-gel-doped TiO2 improved the catalytic behavior during the performance of CO oxidation reactions, and inhibited the AuNP sintering.

  6. Effect of hydrothermal reaction time and alkaline conditions on the electrochemical properties of reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Giannouri, M.; Boukos, N.; Lei, C.; Lekakou, C.; Trapalis, C.

    2015-12-01

    Reduced graphene oxide sheets (rGO) were prepared by hydrothermal treatment of aqueous dispersions of graphite oxide (GtO) applied for short (4 h) and prolonged reaction times (19-24 h). The effect of process duration as well as the alkaline conditions (pH ∼10) by addition of K2CO3 on the quality characteristics of the produced rGO materials was investigated. Both reduction and exfoliation occurred during this process as it was evidenced by FTIR and XRD data. SEM, TEM and HRTEM microscopy displayed highly exfoliated rGO materials. XPS verified that the re-establishment of the conjugated graphene network is more extensive for prolonged times of hydrothermal processing in accordance to Raman spectroscopy measurements. The sample produced under alkaline conditions bore fewer defects and almost 5 times higher BET surface area (∼181 m2/g) than the sample with no pH adjustment (∼34 m2/g) for the same hydrothermal reaction time (19 h), attributed to the developed microporosity. The specific capacitance of this material estimated by electrochemical impedance using three-electrode cell and KCl aqueous solution as an electrolyte was ∼400-500 F/g. When EDLC capacitors were fabricated from rGO materials the electrochemical testing in organic electrolyte i.e. TEABF4 in PC, revealed that the shortest hydrothermal reaction time (4 h) was more efficient resulting in capacitance around 60 F/g.

  7. Palladium networks decorated by cuprous oxide for remarkably enhanced electrocatalytic activity of methanol oxidation reaction with high CO-tolerance

    NASA Astrophysics Data System (ADS)

    Ji, Yuanyuan; Ying, Ye; Pan, Yuxia; Li, Mengzhu; Guo, Xiaoyu; Wu, Yiping; Wen, Ying; Yang, Haifeng

    2016-10-01

    The CuO nanorods (NRs) are prepared with the help of inositol hexakisphosphate which serves as a binding agent and stabilizer. We have successfully fabricated Cu2O-decorated palladium networks (Cu2O/Pd Networks) by using such CuO NRs as reaction beds. Transmission electron microscopy images show that Cu2O/Pd network is composed of small and irregular fused nanoparticles with an average size of about 10 nm. Electrochemical results depict that the as-synthesized catalyst exhibits 2-fold higher activity for methanol oxidation than the commercially available 20% Pd/C catalyst and Pd black catalyst. Furthermore, CO-tolerance is also remarkably enhanced due to the presence of Cu2O. Such highly active, low-cost, and superiorly CO-tolerant catalysts of Cu2O/Pd Networks will open up a new avenue for direct methanol fuel cells.

  8. Destruction efficiencies and dynamics of reaction fronts associated with the permanganate oxidation of trichloroethylene.

    PubMed

    Lee, Eung Seok; Seol, Yongkoo; Fang, Y C; Schwartz, Franklin W

    2003-06-01

    Although potassium permanganate (KMnO4) flushing is commonly used to destroy chlorinated solvents in groundwater, many of the problems associated with this treatment scheme have not been examined in detail. We conducted a KMnO4 flushing experiment in a large sand-filled flow tank (L x W x D = 180 cm x 60 cm x 90 cm) to remove TCE emplaced as a DNAPL in a source zone. The study was specifically designed to investigate cleanup progress and problems of pore plugging associated with the dynamics of the solid-phase reaction front (i.e., MnO2) using chemical and optical monitoring techniques. Ambient flow through the source zone formed a plume of dissolved TCE across the flow tank. The volume and concentration of TCE plume diminished with time because of the in situ oxidation of the DNAPL source. The migration velocity of the MnO2 reaction front decreased with time, suggesting that the kinetics of the DNAPL oxidation process became diffusion-controlled because of the pore plugging. A mass balance calculation indicated that only approximately 18% of the total applied KMnO4 (MnO4- = 1250 mg/ L) participated in the oxidation reaction to destroy approximately 41% of emplaced TCE. Evidently, the efficiency of KMnO4 flushing scheme diminished with time due to pore plugging by MnO2 and likely CO2, particularly in the TCE source zone. In addition, the excess KMnO4 used for flushing may cause secondary aquifer contamination. One needs to be concerned about the efficacy of KMnO4 flushing in the field applications. Development of a new approach that can provide both contaminant destruction and plugging/ MnO4- control is required.

  9. Oxidation of Annelated Diarylamines: Analysis of Reaction Pathways to Nitroxide Diradical and Spirocyclic Products

    SciTech Connect

    Rajca, Andrzej; Shiraishi, Kouichi; Boraty; #324; ski, Przemyslaw J.; Pink, Maren; Miyasaka, Makoto; Rajca, Suchada

    2012-02-06

    Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic {sup 1}H NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic {sup 1}H NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as {sup 1}H, {sup 13}C, and {sup 15}N NMR chemical shifts and electronic absorption spectra.

  10. Characteristics of the oxygen evolution reaction on synthetic copper - cobalt - oxide electrodes for water electrolysis

    NASA Astrophysics Data System (ADS)

    Park, Yoo Sei; Park, Chan Su; Kim, Chi Ho; Kim, Yang Do; Park, Sungkyun; Lee, Jae Ho

    2016-10-01

    A nano-sized Cu0.7Co2.3O4 powder was prepared using a thermal decomposition method to achieve an efficient anode catalyst for an economical water electrolysis system for high-purity hydrogen-gas production without using a noble-metal catalyst. This study showed that the calcination temperature should be maintained under 400 °C to obtain a spinel copper - cobalt oxide structure without secondary oxide phases. The powder calcined at 250 °C showed the highest current density at the oxygen evolution reaction. This was due mainly to the increased number of available active sites and the active surface area of the powders. Further systematic analyses of the electrochemical characteristics of Cu x Co3- x O4 synthesized by using the fusion method were performed to assess it as potential anode material for use in alkaline-anion-exchange-membrane water electrolysis.

  11. A sterilization system using ultraviolet photochemical reactions based on nitrous oxide and oxygen gases.

    PubMed

    Ohnishi, Yasutaka; Matsumoto, Hiroyuki; Iwamori, Satoru

    2016-03-01

    Active oxygen species (AOS) generated under ultraviolet (UV) lamps can be applied for various industrial processes owing to extremely strong oxidative abilities. We have already reported on an application of the AOS for a sterilization process of microorganisms. Here, a sterilization method using active oxygen generated under ultraviolet (UV) lamps introducing nitrous oxide (N2O) and oxygen gases into a vacuum chamber was investigated. Nitrogen dioxide (NO2) gas was readily produced from N2O by UV photochemical reactions under the low-pressure mercury lamp and then used to sterilize medical devices. We compared the ability of the N2O gas to sterilize Geobacillus stearothermophilus spores with those of conventional methods. Successful sterilization of spores on various biological indicators was achieved within 60 min, not only in sterilization bags but also in a lumen device.

  12. Reaction kinetics of waste sulfuric acid using H2O2 catalytic oxidation.

    PubMed

    Wang, Jiade; Hong, Binxun; Tong, Xinyang; Qiu, Shufeng

    2016-12-01

    The process of recovering waste sulfuric acids using H2O2 catalytic oxidation is studied in this paper. Activated carbon was used as catalyst. Main operating parameters, such as temperature, feed rate of H2O2, and catalyst dosage, have effects on the removal of impurities from waste sulfuric acids. The reaction kinetics of H2O2 catalytic oxidation on impurities are discussed. At a temperature of 90°C, H2O2 feeding rate of 50 g (kg waste acid)(-1) per hour, and catalyst dosage of 0.2 wt% (waste acid weight), the removal efficiencies of COD and chrominance were both more than 99%, the recovery ratio of sulfuric acid was more than 95%, and the utilization ratio of H2O2 was 88.57%.

  13. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    SciTech Connect

    Sawada, Kayo; Hirabayashi, Daisuke; Enokida, Youichi

    2013-07-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U{sub 3}O{sub 8} without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  14. Oxidation stability of advanced reaction-bonded Si3N4 materials

    NASA Technical Reports Server (NTRS)

    Lindberg, L. J.; Richerson, D. W.; Carruthers, W. D.; Gersch, H. M.

    1982-01-01

    Four slip-cast, injection-molded and isostatically-pressed specimens of reaction-bonded silicon nitride (RBSN) were subjected to static oxidation tests at 900 C for 10 hours. Specimens containing 8-10% interconnected open porosity of size greater than one micron exhibited a 20-30% decrease in average room temperature four-point flexure strength, while those with 10% open porosity of magnitudes much smaller than one micron as well as those with 2-4% interconnected open porosity of about one micron did not decrease in strength after 900 C exposure. It was determined that preoxidation treatment at 1350 C prevents the 20-30% strength degradation due to internal oxidation, and evidence is presented which suggests that surface pit formation in some RBSN may result from contamination by the furnace environment rather than any intrinsic material properties.

  15. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Meng; Liu, Huijuan; Liu, Yang; Qu, Jiuhui; Li, Jinghong

    2015-01-01

    The development of low cost, durable and efficient nanocatalysts to substitute expensive and rare noble metals (e.g. Pt, Au and Pd) in overcoming the sluggish kinetic process of the oxygen reduction reaction (ORR) is essential to satisfy the demand for sustainable energy conversion and storage in the future. Graphene based transition metal oxide nanocomposites have extensively been proven to be a type of promising highly efficient and economic nanocatalyst for optimizing the ORR to solve the world-wide energy crisis. Synthesized nanocomposites exhibit synergetic advantages and avoid the respective disadvantages. In this feature article, we concentrate on the recent leading works of different categories of introduced transition metal oxides on graphene: from the commonly-used classes (FeOx, MnOx, and CoOx) to some rare and heat-studied issues (TiOx, NiCoOx and Co-MnOx). Moreover, the morphologies of the supported oxides on graphene with various dimensional nanostructures, such as one dimensional nanocrystals, two dimensional nanosheets/nanoplates and some special multidimensional frameworks are further reviewed. The strategies used to synthesize and characterize these well-designed nanocomposites and their superior properties for the ORR compared to the traditional catalysts are carefully summarized. This work aims to highlight the meaning of the multiphase establishment of graphene-based transition metal oxide nanocomposites and its structural-dependent ORR performance and mechanisms.

  16. Improved reaction sintered silicon nitride. [protective coatings to improve oxidation resistance

    NASA Technical Reports Server (NTRS)

    Baumgartner, H. R.

    1978-01-01

    Processing treatments were applied to as-nitrided reaction sintered silicon nitride (RSSN) with the purposes of improving strength after processing to above 350 MN/m2 and improving strength after oxidation exposure. The experimental approaches are divided into three broad classifications: sintering of surface-applied powders; impregnation of solution followed by further thermal processing; and infiltration of molten silicon and subsequent carburization or nitridation of the silicon. The impregnation of RSSN with solutions of aluminum nitrate and zirconyl chloride, followed by heating at 1400-1500 C in a nitrogen atmosphere containing silicon monoxide, improved RSSN strength and oxidation resistance. The room temperature bend strength of RSSN was increased nearly fifty percent above the untreated strength with mean absolute strengths up to 420 MN/m2. Strengths of treated samples that were measured after a 12 hour oxidation exposure in air were up to 90 percent of the original as-nitrided strength, as compared to retained strengths in the range of 35 to 60 percent for untreated RSSN after the same oxidation exposure.

  17. Compositional engineering of perovskite oxides for highly efficient oxygen reduction reactions.

    PubMed

    Chen, Dengjie; Chen, Chi; Zhang, Zhenbao; Baiyee, Zarah Medina; Ciucci, Francesco; Shao, Zongping

    2015-04-29

    Mixed conducting perovskite oxides are promising catalysts for high-temperature oxygen reduction reaction. Pristine SrCoO(3-δ) is a widely used parent oxide for the development of highly active mixed conductors. Doping a small amount of redox-inactive cation into the B site (Co site) of SrCoO(3-δ) has been applied as an effective way to improve physicochemical properties and electrochemical performance. Most findings however are obtained only from experimental observations, and no universal guidelines have been proposed. In this article, combined experimental and theoretical studies are conducted to obtain fundamental understanding of the effect of B-site doping concentration with redox-inactive cation (Sc) on the properties and performance of the perovskite oxides. The phase structure, electronic conductivity, defect chemistry, oxygen reduction kinetics, oxygen ion transport, and electrochemical reactivity are experimentally characterized. In-depth analysis of doping level effect is also undertaken by first-principles calculations. Among the compositions, SrCo0.95Sc0.05O(3-δ) shows the best oxygen kinetics and corresponds to the minimum fraction of Sc for stabilization of the oxygen-vacancy-disordered structure. The results strongly support that B-site doping of SrCoO(3-δ) with a small amount of redox-inactive cation is an effective strategy toward the development of highly active mixed conducting perovskites for efficient solid oxide fuel cells and oxygen transport membranes.

  18. Low-temperature oxidation of alkali overlayers: Ionic species and reaction kinetics

    NASA Astrophysics Data System (ADS)

    Krix, David; Nienhaus, Hermann

    2013-04-01

    Clean and oxidized alkali metal films have been studied using X-ray photoelectron spectroscopy (XPS). Thin films, typically 10 nm thick, of lithium, sodium, potassium, rubidium and cesium have been deposited on silicon substrates and oxidized at 120 K. Plasmon losses were found to dress the primary photo emission structures of the metals’ core lines which confirms the metallic, bulk like nature of the films. The emission from the O 1s core levels was used to determine the chemical composition and the reaction kinetics during the exposure to molecular oxygen at low pressures. Molecular oxide ions O2- and O22- as well as atomic oxygen ions O2- were detected in varying amounts depending on the alkali metal used. Diffusive transport of material in the film is shown to greatly determine the composition of the oxides. Especially, the growth of potassium superoxide is explained by the diffusion of potassium atoms to the surface and growth at the surface in a Deal-Grove like model.

  19. Bimetallic oxidative addition involving radical intermediates in nickel-catalyzed alkyl-alkyl Kumada coupling reactions.

    PubMed

    Breitenfeld, Jan; Ruiz, Jesus; Wodrich, Matthew D; Hu, Xile

    2013-08-14

    Many nickel-based catalysts have been reported for cross-coupling reactions of nonactivated alkyl halides. The mechanistic understanding of these reactions is still primitive. Here we report a mechanistic study of alkyl-alkyl Kumada coupling catalyzed by a preformed nickel(II) pincer complex ([(N2N)Ni-Cl]). The coupling proceeds through a radical process, involving two nickel centers for the oxidative addition of alkyl halide. The catalysis is second-order in Grignard reagent, first-order in catalyst, and zero-order in alkyl halide. A transient species, [(N2N)Ni-alkyl(2)](alkyl(2)-MgCl), is identified as the key intermediate responsible for the activation of alkyl halide, the formation of which is the turnover-determining step of the catalysis.

  20. Reaction of nitric oxide with heme proteins and model compounds of hemoglobin

    SciTech Connect

    Sharma, V.S.; Traylor, T.G.; Gardiner, R.; Mizukami, H.

    1987-06-30

    Rates for the reaction of nitric oxide with several ferric heme proteins and model compounds have been measured. The NO combination rates are markedly affected by the presence or absence of distal histidine. Elephant myoglobin in which the E7 distal histidine has been replaced by glutamine reacts with NO 500-1000 times faster than do the native hemoglobins or myoglobins. By contrast, there is not difference in the CO combination rate constants of sperm whale and elephant myoglobins. Studies on ferric model compounds for the R and T states of hemoglobin indicate that their NO combination rate constants are similar to those observed for the combination of CO with the corresponding ferro derivatives. The last observation suggests that the presence of an axial water molecule at the ligand binding site of ferric hemoglobin A prevents it from exhibiting significant cooperativity in its reactions with NO.

  1. Theoretical study of the reaction mechanism of platinum oxide with methane

    NASA Astrophysics Data System (ADS)

    Hwang, Der-Yan; Mebel, Alexander M.

    2002-10-01

    Density functional B3LYP calculations have been employed to investigate the reaction of platinum oxide with methane. PtO is shown to form a molecular complex with CH 4 bound by ˜13 kcal/mol. At elevated temperatures, direct abstraction of a hydrogen atom is possible leading to PtOH and free methyl radical with a barrier of ˜26 kcal/mol. A minor reaction channel is insertion into a C-H bond to produce a CH 3PtOH molecule, which can be also formed by recombination of PtOH and CH 3. CH 3PtOH would preferably dissociates through a mechanism involving 1,2-CH 3 migration to produce a PtCH 3OH complex and eventually Pt+CH 3OH.

  2. Oxidation behavior in reaction-bonded aluminum-silicon alloy/alumina powder compacts

    SciTech Connect

    Yokota, S.H.

    1992-12-01

    Goal of this research is to determine the feasibility of producing low-shrinkage mullite/alumina composites by applying the reaction-bonded alumina (RBAO) process to an aluminum-silicon alloy/alumina system. Mirostructural and compositional changes during heat treatment were studied by removing samples from the furnace at different steps in the heating schedule and then using optical and scanning electron microscopy, EDS and XRD to characterize the powder compacts. Results suggest that the oxidation behavior of the alloy compact is different from the model proposed for the pure Al/alumina system.

  3. Radiolytic reactions of nitro blue tetrazolium under oxidative and reductive conditions: a pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Kovacs, A.; Wojnarovits, L.; Baranyai, M.; Moussa, A.; Othman, I.; McLaughlin, W. L.

    1999-08-01

    The radiolytic reactions of the ditetrazolium salt nitro blue tetrazolium chloride (NBTCl 2) were studied by pulse radiolysis technique in aqueous solution under reducing and oxidising conditions with the aim of potential dosimetry application. Under reducing conditions the fast formation of the tetrazolinyl radical is observed that is followed by the appearance of monoformazan (MF +), i.e. one of the tetrazolium rings is reduced to formazan. The formation of the water-insoluble diformazan, i.e. the result of the second reduction step was not observed in pulse radiolysis. Formazan formation was not found under oxidative conditions.

  4. The direct oxidative diene cyclization and related reactions in natural product synthesis

    PubMed Central

    2016-01-01

    Summary The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed. PMID:27829917

  5. The Role of Metal Oxides in Nanothermite Reactions: Evidence of Condensed Phase Initiation

    DTIC Science & Technology

    2010-01-01

    Al/WO3, and Al/ Bi2O3 were all tested with this system along with 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND SUBTITLE 13. SUPPLEMENTARY NOTES The...Fe2O3, Al/WO3, and Al/ Bi2O3 were all tested with this system along with the neat Al and metal oxide powders. High speed imaging was also used to...visually compare reaction rates of each sample showing that, contradictory to some previous works, Al/ Bi2O3 reacts much faster than the other

  6. Investigation of reaction conditions on morphology and optical properties of Zinc Oxide Nanorods

    NASA Astrophysics Data System (ADS)

    Almodarresiyeh, H. A.; Abakshonok, A. V.; Agabekov, V. E.; Eryomin, A. N.; Shahab, S. N.

    2014-08-01

    Zinc oxide nanoparticles (ZnO NPs) were synthesized by precipitation method in the presence of various polymers. Rod shaped ZnO NPs (length ~ 1 micron) were obtained at 70 °C in a reaction medium containing 10-20 mM of zinc nitrate hexahydrate (Zn(NO3)2·6H2O), 0.05-0.1 mg/ml of polyethylenimine (PEI) and 20 mM of hexamethylenetetramine (HMT). Properties of ZnO NPs were characterized by fluorescence, UV-visible spectroscopy, atomic force and transmission electron microscopy.

  7. Quantitation of four guanine oxidation products from reaction of DNA with varying doses of peroxynitrite.

    PubMed

    Yu, Hongbin; Venkatarangan, Lata; Wishnok, John S; Tannenbaum, Steven R

    2005-12-01

    The oxidation products obtained from the reaction of peroxynitrite (ONOO-) with dG include-among others-8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG), 2,2-diamino-4[(2-deoxy-beta-d-erythro-pentafuranosyl)amino]-5(2H)-oxazolone (oxazolone), spiroiminodihydantoin, and N1-(beta-d-erythro-pentofuranosyl)-5-guanidinohydantoin (guanidinohydantoin). In the present work, the formation of these products from the treatment of calf thymus DNA with varying amounts of ONOO- was studied quantitatively in vitro. 13C-, 15N-labeled standards were synthesized for the nucleosides of interest, and calf thymus DNA was reacted with ONOO- and digested enzymatically down to the nucleoside level. Specific modifications in the DNA were measured by HPLC separation followed by electrospray ionization tandem mass spectrometric analysis in the selected reaction-monitoring mode. Artifacts of the above four oxidation products, arising from oxidation of dG and/or 8-oxodG during DNA digestion and subsequent workup, were evaluated with 7-15N-dG and/or stable-isotope-labeled 8-oxodG as internal standards. Levels of artifactual 8-oxodG were about 5/10(6) nucleosides. The artifacts of spiroiminodihydantoin and guanidinohydantoin, arising from 8-oxodG, were 3.7% and 0.6% of the measured 8-oxodG values, respectively. No artifacts of oxazolone were detected. 8-OxodG and oxazolone were formed dose-dependently in DNA treated with ONOO-, while the levels of spiroiminodihydantoin and guanidinohydantoin increased significantly at low ONOO- doses, and then dropped off at higher ONOO- doses. The complexity of these dose-response relationships is likely due to the dual role of peroxynitrite as both an oxidant and a nucleophile in competition with water.

  8. Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

    NASA Technical Reports Server (NTRS)

    Napier, Mary E.; Stair, Peter C.

    1992-01-01

    Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

  9. Temperature dependence of the heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    PubMed

    Liu, Yongchun; He, Hong; Ma, Qingxin

    2008-04-03

    The experimental determination of rate constants for atmospheric reactions and how these rate constants vary with temperature remain a crucially important part of atmosphere science. In this study, the temperature dependence of the heterogeneous reaction of carbonyl sulfide (COS) on magnesium oxide (MgO) has been investigated using a Knudsen cell reactor and a temperature-programmed reaction apparatus. We found that the adsorption and the heterogeneous reaction are sensitive to temperature. The initial uptake coefficients (gammat(Ini)) of COS on MgO decrease from 1.07 +/- 0.71 x 10-6 to 4.84 +/- 0.60 x 10-7 with the increasing of temperature from 228 to 300 K, and the steady state uptake coefficients (gammat(SS)) increase from 5.31 +/- 0.06 x 10-8 to 1.68 +/- 0.41 x 10-7 with the increasing of temperature from 240 to 300 K. The desorption rate constants (kdes) were also found to increase slightly with the enhancement of temperature. The empirical formula between the uptake coefficients, desorption rate constants and temperature described in the form of Arrhenius expression were obtained. The activation energies for the heterogeneous reaction and desorption of COS on MgO were measured to be 11.02 +/- 0.34 kJ.mol-1 and 6.30 +/- 0.81 kJ.mol-1, respectively. The results demonstrate that the initial uptake of COS on MgO is mainly contributed by an adsorption process and the steady state uptake is due to a catalytic reaction. The environmental implication was also discussed.

  10. Application of Mössbauer Spectroscopy to the Carbon Oxides Hydrogenation Reactions

    NASA Astrophysics Data System (ADS)

    Cubeiro, M. L.; González-Jiménez, F.; Goldwasser, M. R.; Pérez-Zurita, M. J.; Pietri, E.; García, L.

    2001-05-01

    Iron-based catalysts have favorable activity and selectivity properties for the CO and CO2 hydrogenation reactions. Several Fe phases (oxides and carbides) can be present in these catalysts. The interaction of Fe with the other components of the catalyst (support, promoters) can affect the ease of reduction and also its transformation during the reactions. In this work, the relationship between catalytic behavior in the CO and CO2 hydrogenation reactions and the Fe phase composition of fresh and reacted catalysts was studied. Two types of catalysts were tested: a laterite and the other one made of iron supported on alumina, both unpromoted and promoted with K and Mn. Only those Fe species which can be reduced-carburized, by means of a pretreatment or by an in situ transformation under the reaction, seem to be able to perform the CO or CO2 hydrogenation. The reoxidation of the Fe carbide to magnetite was not associated to deactivation. The selectivity seems to be more affected by Fe species difficult to reduce than by magnetite produced by reoxidation.

  11. Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering

    NASA Astrophysics Data System (ADS)

    Rajagopalan, S.; Asthalter, T.; Rabe, V.; Laschat, S.

    2016-12-01

    Nuclear inelastic scattering (NIS) of synchrotron radiation, also known as nuclear resonant vibrational spectroscopy (NRVS), has been shown to provide valuable insights into metal-centered vibrations at Mössbauer-active nuclei. We present a study of the iron-centered vibrational density of states (VDOS) during the first step of the Gif-type oxidation of cyclohexene with a novel trinuclear Fe3(μ 3-O) complex as catalyst precursor. The experiments were carried out on shock-frozen solutions for different combinations of reactants: Fe3(μ 3-O) in pyridine solution, Fe3(μ 3-O) plus Zn/acetic acid in pyridine without and with addition of either oxygen or cyclohexene, and Fe3(μ 3-O)/Zn/acetic acid/pyridine/cyclohexene (reaction mixture) for reaction times of 1 min, 5 min, and 30 min. The projected VDOS of the Fe atoms was calculated on the basis of pseudopotential density functional calculations. Two possible reaction intermediates were identified as [Fe(III)(C5H5N)2(O2CCH3)2]+ and Fe(II)(C5H5N)4(O2CCH3)2, yielding evidence that NIS (NRVS) allows to identify the presence of iron-centered intermediates also in complex reaction mixtures.

  12. Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment

    PubMed Central

    Wang, Xinghao; Huang, Qingguo; Lu, Junhe; Wang, Liansheng; Wang, Zunyao

    2015-01-01

    Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants and has attracted more and more attention. In this work, the parent TBBPA with an initial concentration of 100 mg/L was completely removed after 6 min of ozonation at pH 8.0, and alkaline conditions favored a more rapid removal than acidic and neutral conditions. The presence of typical anions and humic acid did not significantly affect the degradation of TBBPA. The quenching test using isopropanol indicated that direct ozone oxidation played a dominant role during this process. Seventeen reaction intermediates and products were identified using an electrospray time-of-flight mass spectrometer. Notably, the generation of 2,4,6-tribromophenol was first observed in the degradation process of TBBPA. The evolution of reaction products showed that ozonation is an efficient treatment for removal of both TBBPA and intermediates. Sequential transformation of organic bromine to bromide and bromate was confirmed by ion chromatography analysis. Two primary reaction pathways that involve cleavage of central carbon atom and benzene ring cleavage concomitant with debromination were thus proposed and further justified by calculations of frontier electron densities. Furthermore, the total organic carbon data suggested a low mineralization rate, even after the complete removal of TBBPA. Meanwhile, the acute aqueous toxicity of reaction solutions to Photobacterium Phosphoreum and Daphnia magna was rapidly decreased during ozonation. In addition, no obvious difference in the attenuation of TBBPA was found by ozone oxidation using different water matrices, and the effectiveness in natural waters further demonstrates that ozonation can be adopted as a promising technique to treat TBBPA-contaminated waters. PMID:26430733

  13. Ultrasmooth reaction-sintered silicon carbide surface resulting from combination of thermal oxidation and ceria slurry polishing.

    PubMed

    Shen, Xinmin; Dai, Yifan; Deng, Hui; Guan, Chaoliang; Yamamura, Kazuya

    2013-06-17

    An ultrasmooth reaction-sintered silicon carbide surface with an rms roughness of 0.424 nm is obtained after thermal oxidation for 30 min followed by ceria slurry polishing for 30 min. By SEM-EDX analysis, we investigated the thermal oxidation behavior of RS-SiC, in which the main components are Si and SiC. As the oxidation rate is higher in the area with defects, there are no scratches or cracks on the surface after oxidation. However, a bumpy structure is formed after oxidation because the oxidation rates of Si and SiC differ. Through a theoretical analysis of thermal oxidation using the Deal-Grove model and the removal of the oxide layer by ceria slurry polishing in accordance with the Preston equation, a model for obtaining an ultrasmooth surface is proposed and the optimal processing conditions are presented.

  14. pH-Controlled Oxidation of an Aromatic Ketone: Structural Elucidation of the Products of Two Green Chemical Reactions

    ERIC Educational Resources Information Center

    Ballard, C. Eric

    2010-01-01

    A laboratory experiment emphasizing the structural elucidation of organic compounds has been developed as a discovery exercise. The "unknown" compounds are the products of the pH-controlled oxidation of 4'-methoxyacetophenone with bleach. The chemoselectivity of this reaction is highly dependent on the pH of the reaction media: under basic…

  15. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    PubMed

    Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

    2015-11-16

    Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy.

  16. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    NASA Technical Reports Server (NTRS)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  17. Fabrication, strength and oxidation of molybdenum-silicon-boron alloys from reaction synthesis

    NASA Astrophysics Data System (ADS)

    Middlemas, Michael Robert

    Mo-Si-B alloys are a leading candidate for the next generation of jet turbine engine blades and have the potential to raise the operating temperatures by 300-400°C, which would dramatically increase power and efficiency. The alloys of interest are a three-phase mixture of the molybdenum solid solution (Moss) and two intermetallic phases, Mo3Si (A15) and Mo5SiB2 (T2). A novel powder metallurgical method was developed which uses the reaction of molybdenum, silicon nitride (Si3N4) and boron nitride (BN) powders to synthesize a fine dispersion of the intermetallic phases in a Moss matrix. The covalent nitrides are stable in oxidizing environments up to 1000ºC, allowing for fine particle processing without the formation of silicon and boron oxides. The process developed uses standard powder processing techniques to create Mo-Si-B alloys in a less complex and expensive manner than previously demonstrated. The formation of the intermetallic phases was examined by thermo-gravimetric analysis and x-ray diffraction. The start of the reactions to form the T2 and A15 phases were observed at 1140°C and 1193°C and the reactions have been demonstrated to be complete in as little as two hours at 1300°C. This powder metallurgy approach yields a fine dispersion of intermetallics in the Moss matrix, with average grain sizes of 2-4mum. Densities up to 95% of theoretical were attained from pressureless sintering at 1600°C and full theoretical density was achieved by hot-isostatic pressing (HIP). Low temperature sintering and HIPing was attempted to limit grain growth and to reduce the equilibrium silicon concentration in the Moss matrix. Sintering and HIPing at 1300°C reduced the grain sizes of all three phases by over a factor of two. Powder metallurgy provides an opportunity for microstructure control through changes in raw materials and processing parameters. Microstructure examination by electron back-scatter diffraction (EBSD) imaging was used to precisely define the

  18. Type I allergic hypersensitivity reactions due to ethylene oxide sterilised leucocyte filters in patients with thalassaemia: report of four cases

    PubMed Central

    Belen, Burcu; Polat, Meltem

    2015-01-01

    Ethylene oxide (EO) is a highly reactive gas used in sterilisation of heat sensitive medical devices, such as infusion sets, cannulae, intubation materials, ventriculoperitoneal shunts, dialysis catheters and stents. Allergic reactions due to EO have been reported in haemodialysis patients, patients undergoing extracorporeal photopheresis and donors of plasmapheresis. Clinical manifestations vary considerably and generally do not allow differentiation between IgE-mediated anaphylaxis and anaphylactoid reactions. We report four patients with thalassaemia who experienced anaphylaxis during transfusion due to ethylene oxide sterilised leucocyte filters. The aim of this report is to highlight the fact that frequently transfused patients can have allergic reactions due to EO particles left in leucocyte filters. PMID:25725028

  19. Imaging the oxidation effects of the Fenton reaction on phospholipids at the interface between aqueous phase and thermotropic liquid crystals.

    PubMed

    Zhang, Minmin; Jang, Chang-Hyun

    2015-08-01

    The lipid peroxidation process has attracted much attention because of the growing evidence of its involvement in the pathogenesis of age-related diseases. Herein, we report a simple, label-free method to study the oxidation of phospholipids by the Fenton reaction at the interface between an aqueous phase and immiscible liquid crystals (LCs). The different images produced by the orientation of 4-cyano-4'-pentylbiphenyl (5CB) corresponded to the presence or absence of oxidized 1,2-dioleoyl-sn-glycero-3-phospho-rac-(1-glycerol) sodium salt (DOPG). The oxidation effects of the Fenton reaction on DOPG were evaluated by monitoring the orientational response of liquid crystals upon contact with the oxidized DOPG solutions. DOPG was oxidized into chain-changed products containing hydroxy, carbonyl, or aldehyde groups, resulting in the rearrangement of the phospholipid layer. This induced the orientational transition of LCs from homeotropic to planar states; therefore, a dark to bright optical shift was observed. This shift was due to the Fenton reaction preventing DOPG to induce the orientational alignment of LCs at the aqueous/LC interface. We also used an ultraviolet spectrophotometer to confirm the effects of oxidation on phospholipids by the Fenton reaction. Using this simple method, a new approach for investigating phospholipid oxidation was established with high resolution and easy accessibility.

  20. 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