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Sample records for biocatalytic oxidation reactions

  1. Branched zinc oxide nanorods arrays modified paper electrode for electrochemical immunosensing by combining biocatalytic precipitation reaction and competitive immunoassay mode.

    Science.gov (United States)

    Sun, Guoqiang; Yang, Hongmei; Zhang, Yan; Yu, Jinghua; Ge, Shenguang; Yan, Mei; Song, Xianrang

    2015-12-15

    Branched zinc oxide nanorods (BZR) arrays, an array with high charge carries collection efficiency and specific surface area, are grown on the reduced graphene oxide-paper working electrode for the first time to construct a paper-based electrochemical (EC) immunosensor. Typically, the BZR are fabricated via a simple hydrothermal process, which can provide abundant sites for antibodies loading. By combining the large surface area of porous zinc oxide (PZS) and good biocompatibility of gold nanoparticles (AuNPs), PZS-AuNPs (PZS@Au) nanocomposites are designed to label horseradish peroxide (HRP) and antigens. After a competitive reaction between antigens and PZS@Au nanocomposites labeled antigens, the signal labels are introduced into the immunosensor, in which, HRP participate in biocatalytic precipitation process. The produced precipitate reduces the electrode surface area and hinders the electron transfer. With the increase of concentration of antigens, the signal labels introduced into the sensor decrease, thus, a signal-on immunoassay for α-fetoprotein detection is constructed. The proposed paper-based EC immunosensor combines enzymatic biocatalytic precipitation reaction and competitive immunoassay mode for the first time, and possesses a wide linear range from 0.2 pg mL(-1) to 500 ng mL(-1) with a detection limit of 0.08 pg mL(-1). In addition, the proposed method is simple, sensitive and specific and can be a promising platform for other protein detection.

  2. Bioorganometallic chemistry: biocatalytic oxidation reactions with biomimetic nad+/nadh co-factors and [cp*rh(bpy)h]+ for selective organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Lutz, Jochen; Hollman, Frank; Ho, The Vinh; Schnyder, Adrian; Fish, Richard H.; Schmid, Andreas

    2004-03-09

    The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural nicotinamide adenine dinucleotide (NAD{sup +}) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzylnicotinamide bromide, 1a. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfers, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH{sub 2} possibly reacting with the precatalyst, [Cp*Rh(bpy)(H{sub 2}O)](Cl){sub 2}, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH{sub 2} groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H2O)](Cl){sub 2}, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product.

  3. A robust methodology for kinetic model parameter estimation for biocatalytic reactions

    DEFF Research Database (Denmark)

    Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson;

    2012-01-01

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several...

  4. Oxidase-based biocatalytic processes

    DEFF Research Database (Denmark)

    Ramesh, Hemalata; Woodley, John; Krühne, Ulrich

    solvent-resistant oxygen sensors as supporting technology for oxidase-basedreactions using a glucose oxidase reaction system as an example.iiImplementation of biocatalytic oxidation at scale still requires process knowledge which includes thelimitations of the system and the knowledge about the potential......Biocatalytic processes are gaining significant focus in frontiers where they offer unique advantages(selectivity and mild operating conditions) over chemical catalysts. It is therefore not surprising that therehave been many industrial biocatalytic processes implemented.Despite past successes......, the implementation of a new biocatalytic process still presents some challenges (demands placed on the biocatalyst) in terms of the requirements to make a viable industrial process. Inorder for a biocatalytic process to be economically successful, it is necessary that certain a set of targetmetrics (product titre...

  5. Biocatalytic Characterization of Human FMO5: Unearthing Baeyer-Villiger Reactions in Humans.

    Science.gov (United States)

    Fiorentini, Filippo; Geier, Martina; Binda, Claudia; Winkler, Margit; Faber, Kurt; Hall, Mélanie; Mattevi, Andrea

    2016-04-15

    Flavin-containing mono-oxygenases are known as potent drug-metabolizing enzymes, providing complementary functions to the well-investigated cytochrome P450 mono-oxygenases. While human FMO isoforms are typically involved in the oxidation of soft nucleophiles, the biocatalytic activity of human FMO5 (along its physiological role) has long remained unexplored. In this study, we demonstrate the atypical in vitro activity of human FMO5 as a Baeyer-Villiger mono-oxygenase on a broad range of substrates, revealing the first example to date of a human protein catalyzing such reactions. The isolated and purified protein was active on diverse carbonyl compounds, whereas soft nucleophiles were mostly non- or poorly reactive. The absence of the typical characteristic sequence motifs sets human FMO5 apart from all characterized Baeyer-Villiger mono-oxygenases so far. These findings open new perspectives in human oxidative metabolism.

  6. Application of Enzyme Coupling Reactions to Shift Thermodynamically Limited Biocatalytic Reactions

    DEFF Research Database (Denmark)

    Abu, Rohana; Woodley, John M.

    2015-01-01

    shift the equilibrium of otherwise thermodynamically unfavourable reactions to give a higher conversion of the target product. By coupling an energetically unfavourable reaction with a more favourable one, the multi-enzyme cascade mimics the approach taken in nature in metabolic pathways. Nevertheless......, it can be challenging to combine several engineered enzymes in vitro for the conversion of non-natural substrates. In this mini-review we focus on enzyme coupling reactions as a tool to alleviate thermodynamic constraints in synthetically useful biocatalytic reactions. The implications of thermodynamic...... parameters such as the equilibrium constant on the multienzyme cascades and the conventional methods of equilibrium shifting are also discussed in addition to methods used to estimate such values....

  7. Biocatalytic Resolution of para-Nitrostyrene Oxide by Resting Cells of Different Aspergillus niger Strains

    Institute of Scientific and Technical Information of China (English)

    金浩; 李祖义; 王清

    2001-01-01

    Biocatalytic resolution of racemic para-nitrostyrene oxide was accomplished by employing the epoxide hydrolases from the whole cells of several Aspergillus niger (A. niger) strains. In the cases investigated, excellent selectivity was achieved with such strains as A, niger 5450, A. niger 5320.

  8. Biocatalytic oxidation of benzyl alcohol to benzaldehyde via hydrogen transfer

    NARCIS (Netherlands)

    Orbegozo, Thomas; Lavandera, Iván; Fabian, Walter M.F.; Mautner, Barbara; Vries, Johannes G. de; Kroutil, Wolfgang

    2009-01-01

    Various types of biocatalysts like oxidases, alcohol dehydrogenases, and microbial cells were tested for the oxidation of benzyl alcohol. Oxidases in combination with molecular oxygen led to low conversion. Alcohol dehydrogenases and microbial cells were tested in a hydrogen transfer reaction employ

  9. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase.

    Science.gov (United States)

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping

    2014-09-12

    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture.

  10. Biocatalytic anode for glucose oxidation utilizing carbon nanotubes for direct electron transfer with glucose oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Vaze, Abhay; Hussain, Nighat; Tang, Chi [Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060 (United States); Leech, Donal [School of Chemistry, National University of Ireland, Galway (Ireland); Rusling, James [Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060 (United States); Department of Cell Biology, University of Connecticut Health Center, Farmington, CT 06032 (United States); School of Chemistry, National University of Ireland, Galway (Ireland)

    2009-10-15

    Covalently linked layers of glucose oxidase, single-wall carbon nanotubes and poly-L-lysine on pyrolytic graphite resulted in a stable biofuel cell anode featuring direct electron transfer from the enzyme. Catalytic response observed upon addition of glucose was due to electrochemical oxidation of FADH{sub 2} under aerobic conditions. The electrode potential depended on glucose concentration. This system has essential attributes of an anode in a mediator-free biocatalytic fuel cell. (author)

  11. From waste to value - direct utilization of limonene from orange peel in a biocatalytic cascade reaction towards chiral carvolactone

    NARCIS (Netherlands)

    Oberleitner, N.; Ressmann, A. K.; Bica, K.; Gaertner, P.; Fraaije, M. W.; Bornscheuer, U. T.; Rudroff, F.; Mihovilovic, M. D.

    2017-01-01

    In this proof of concept study we demonstrate direct utilization of limonene containing waste product orange peel as starting material for a biocatalytic cascade reaction. The product of this cascade is chiral carvolactone, a promising building block for thermoplastic polymers. Four different concep

  12. Biocatalytic conversion of epoxides

    NARCIS (Netherlands)

    de Vries, Erik; Janssen, DB

    2003-01-01

    Epoxides are attractive intermediates for producing chiral compounds. Important biocatalytic reactions involving epoxides include epoxide hydrolase mediated kinetic resolution, leading to the formation of diols and enantiopure remaining substrates, and enantioconvergent enzymatic hydrolysis, which g

  13. Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions.

    Science.gov (United States)

    Hernández, Karel; Parella, Teodor; Joglar, Jesús; Bujons, Jordi; Pohl, Martina; Clapés, Pere

    2015-02-16

    The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology.

  14. Two-Input Enzymatic Logic Gates Made Sigmoid by Modifications of the Biocatalytic Reaction Cascades

    CERN Document Server

    Zavalov, Oleksandr; Halamek, Jan; Halamkova, Lenka; Korkmaz, Sevim; Arugula, Mary A; Chinnapareddy, Soujanya; Katz, Evgeny; Privman, Vladimir

    2013-01-01

    Computing based on biochemical processes is a newest rapidly developing field of unconventional information and signal processing. In this paper we present results of our research in the field of biochemical computing and summarize the obtained numerical and experimental data for implementations of the standard two-input OR and AND gates with double-sigmoid shape of the output signal. This form of response was obtained as a function of the two inputs in each of the realized biochemical systems. The enzymatic gate processes in the first system were activated with two chemical inputs and resulted in optically detected chromogen oxidation, which happens when either one or both of the inputs are present. In this case, the biochemical system is functioning as the OR gate. We demonstrate that the addition of a "filtering" biocatalytic process leads to a considerable reduction of the noise transmission factor and the resulting gate response has sigmoid shape in both inputs. The second system was developed for functi...

  15. Alkene cleavage catalysed by heme and nonheme enzymes: reaction mechanisms and biocatalytic applications.

    Science.gov (United States)

    Mutti, Francesco G

    2012-01-01

    The oxidative cleavage of alkenes is classically performed by chemical methods, although they display several drawbacks. Ozonolysis requires harsh conditions (-78°C, for a safe process) and reducing reagents in a molar amount, whereas the use of poisonous heavy metals such as Cr, Os, or Ru as catalysts is additionally plagued by low yield and selectivity. Conversely, heme and nonheme enzymes can catalyse the oxidative alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing excellent chemo- and regioselectivities in certain cases. This paper focuses on the alkene cleavage catalysed by iron cofactor-dependent enzymes encompassing the reaction mechanisms (in case where it is known) and the application of these enzymes in biocatalysis.

  16. Enhanced biocatalytic esterification with lipase-immobilized chitosan/graphene oxide beads.

    Directory of Open Access Journals (Sweden)

    Siaw Cheng Lau

    Full Text Available In this work, lipase from Candida rugosa was immobilized onto chitosan/graphene oxide beads. This was to provide an enzyme-immobilizing carrier with excellent enzyme immobilization activity for an enzyme group requiring hydrophilicity on the immobilizing carrier. In addition, this work involved a process for the preparation of an enzymatically active product insoluble in a reaction medium consisting of lauric acid and oleyl alcohol as reactants and hexane as a solvent. This product enabled the stability of the enzyme under the working conditions and allowed the enzyme to be readily isolated from the support. In particular, this meant that an enzymatic reaction could be stopped by the simple mechanical separation of the "insoluble" enzyme from the reaction medium. Chitosan was incorporated with graphene oxide because the latter was able to enhance the physical strength of the chitosan beads by its superior mechanical integrity and low thermal conductivity. The X-ray diffraction pattern showed that the graphene oxide was successfully embedded within the structure of the chitosan. Further, the lipase incorporation on the beads was confirmed by a thermo-gravimetric analysis. The lipase immobilization on the beads involved the functionalization with coupling agents, N-hydroxysulfosuccinimide sodium (NHS and 1-ethyl-(3-dimethylaminopropyl carbodiimide (EDC, and it possessed a high enzyme activity of 64 U. The overall esterification conversion of the prepared product was 78% at 60 °C, and it attained conversions of 98% and 88% with commercially available lipozyme and novozyme, respectively, under similar experimental conditions.

  17. Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

    DEFF Research Database (Denmark)

    Prabhavathi Devi, Bethala Lakshmi Anu; Guo, Zheng; Xu, Xuebing

    2011-01-01

    /IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation...... a large chemical potential to move reaction equilibrium for maximum oil conversion and yield of target biodiesel. The reaction behavior and specificity of oil/IL biphasic system for enzymatic production of biodiesel were theoretically delineated through COSMO‐RS computation with experimental validation...

  18. Two-phase (bio)catalytic reactions in a table-top centrifugal contact separator

    NARCIS (Netherlands)

    Kraai, Gerard N.; Zwol, Floris van; Schuur, Boelo; Heeres, Hero J.; Vries, Johannes G. de

    2008-01-01

    A new spin on catalysis: A table-top centrifugal contact separator allows for fast continuous two-phase reactions to be performed by intimately mixing two immiscible phases and then separating them. Such a device has been used to produce biodiesel from sunflower oil and MeOH/NaOMe. A lipase-catalyze

  19. Radioactive phosphorylation of alcohols to monitor biocatalytic Diels-Alder reactions.

    Directory of Open Access Journals (Sweden)

    Alexander Nierth

    Full Text Available Nature has efficiently adopted phosphorylation for numerous biological key processes, spanning from cell signaling to energy storage and transmission. For the bioorganic chemist the number of possible ways to attach a single phosphate for radioactive labeling is surprisingly small. Here we describe a very simple and fast one-pot synthesis to phosphorylate an alcohol with phosphoric acid using trichloroacetonitrile as activating agent. Using this procedure, we efficiently attached the radioactive phosphorus isotope (32P to an anthracene diene, which is a substrate for the Diels-Alderase ribozyme-an RNA sequence that catalyzes the eponymous reaction. We used the (32P-substrate for the measurement of RNA-catalyzed reaction kinetics of several dye-labeled ribozyme variants for which precise optical activity determination (UV/vis, fluorescence failed due to interference of the attached dyes. The reaction kinetics were analyzed by thin-layer chromatographic separation of the (32P-labeled reaction components and densitometric analysis of the substrate and product radioactivities, thereby allowing iterative optimization of the dye positions for future single-molecule studies. The phosphorylation strategy with trichloroacetonitrile may be applicable for labeling numerous other compounds that contain alcoholic hydroxyl groups.

  20. Design of Laccase-Metal Organic Framework-Based Bioelectrodes for Biocatalytic Oxygen Reduction Reaction.

    Science.gov (United States)

    Patra, Snehangshu; Sene, Saad; Mousty, Christine; Serre, Christian; Chaussé, Annie; Legrand, Ludovic; Steunou, Nathalie

    2016-08-10

    Laccase in combination with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator is a well-known bioelectrocatalyst for the 4-electron oxygen reduction reactions (ORR). The present work deals with the first exploitation of mesoporous iron(III) trimesate-based metal organic frameworks (MOF) MIL-100(Fe) (MIL stands for materials from Institut Lavoisier) as a new and efficient immobilization matrix of laccase for the building up of biocathodes for ORR. First, the immobilization of ABTS in the pores of the MOF was studied by combining micro-Raman spectroscopy, X-ray powder diffraction (XRPD), and N2 porosimetry. The ABTS-MIL-100(Fe)-based modified electrode presents excellent properties in terms of charge transfer kinetics and ionic conductivity as well as a very stable and reproducible electrochemical response, showing that MIL-100(Fe) provides a suitable and stabilizing microenvironment for electroactive ABTS molecules. In a second step, laccase was further immobilized on the MIL-100(Fe)-ABTS matrix. The Lac-ABTS-MIL-100(Fe)-CIE bioelectrode presents a high electrocatalytic current density of oxygen reduction and a reproducible electrochemical response characterized by a high stability over a long period of time (3 weeks). These results constitute a significant advance in the field of laccase-based bioelectrocatalysts for ORR. According to our work, it appears that the high catalytic efficiency of Lac-ABTS-MIL-100(Fe) for ORR may result from a synergy of chemical and catalytic properties of MIL-100(Fe) and laccase.

  1. The Oxidation of Thiols by Flavoprotein Oxidases : a Biocatalytic Route to Reactive Thiocarbonyls

    NARCIS (Netherlands)

    Ewing, Tom A.; Dijkman, Willem P.; Vervoort, Jacques M.; Fraaije, Marco W.; van Berkel, Willem J. H.

    2014-01-01

    Flavoprotein oxidases are a diverse class of biocatalysts, most of which catalyze the oxidation of C-O, C-N, or C-C bonds. Flavoprotein oxidases that are known to catalyze the oxidation of C-S bonds are rare, being limited to enzymes that catalyze the oxidative cleavage of thioethers. Herein, we rep

  2. The Oxidation of Thiols by Flavoprotein Oxidases: a Biocatalytic Route to Reactive Thiocarbonyls.

    NARCIS (Netherlands)

    Ewing, T.A.; Dijkman, W.P.; Vervoort, J.J.M.; Fraaije, M.W.; Berkel, van W.J.H.

    2014-01-01

    Flavoprotein oxidases are a diverse class of biocatalysts, most of which catalyze the oxidation of C[BOND]O, C[BOND]N, or C[BOND]C bonds. Flavoprotein oxidases that are known to catalyze the oxidation of C[BOND]S bonds are rare, being limited to enzymes that catalyze the oxidative cleavage of thioet

  3. Biocatalytic conversion of ethylene to ethylene oxide using an engineered toluene monooxygenase

    Energy Technology Data Exchange (ETDEWEB)

    Carlin, DA; Bertolani, SJ; Siegel, JB

    2015-01-01

    Mutants of toluene o-xylene monooxygenase are demonstrated to oxidize ethylene to ethylene oxide in vivo at yields of >99%. The best mutant increases ethylene oxidation activity by >5500-fold relative to the native enzyme. This is the first report of a recombinant enzyme capable of carrying out this industrially significant chemical conversion.

  4. Engineering of Biocatalysts and Biocatalytic Processes

    DEFF Research Database (Denmark)

    Lima Ramos, Joana; Lima Afonso Neto, Watson; Woodley, John

    2014-01-01

    Discovering and developing new biocatalytic reactions and biocatalysts has been the major focus of the activities in the EC FP7 BIOTRAINS network. However, industrial implementation of these new reactions requires engineering of both the biocatalysts and the associated processes, to achieve the n...

  5. Separation of electron-transfer and coupled chemical reaction components of biocatalytic processes using Fourier transform ac voltammetry.

    Science.gov (United States)

    Fleming, Barry D; Zhang, Jie; Bond, Alan M; Bell, Stephen G; Wong, Luet-Lok

    2005-06-01

    The underlying electron-transfer and coupled chemical processes associated with biologically important catalytic reactions can be resolved using a combination of Fourier transform ac voltammetry with an analysis of the separated dc and ac components. This outcome can be achieved because the response associated with generation of the catalytic current is essentially confined to the steady-state dc component, whereas the electron-transfer step is dominant in the fundamental and higher harmonics. For the mediated oxidation of glucose with glucose oxidase, it was found that the underlying reversible redox chemistry of the mediator, ferrocenemonocarboxylic acid, as detected in the third and higher harmonics, was totally unaffected by introduction of the catalytic process. In contrast, for the catalytic reduction of molecular oxygen by cytochrome P450, slight changes in the P450 redox process were detected when the catalytic reaction was present. Simulations of a simple catalytic reaction scheme support the fidelity of this novel FT ac voltammetric approach for examining mechanistic nuances of catalytic forms of electrochemical reaction schemes.

  6. PSE opportunities in biocatalytic process design and development

    DEFF Research Database (Denmark)

    Tufvesson, Pär; Krühne, Ulrich; Gernaey, Krist

    2012-01-01

    to pharmaceuticals and other chemical products, since enzymes usually work in an aqueous solution and under mild conditions. Nevertheless the implementation of a biocatalytic reaction and the integration of a biocatalytic reaction into an otherwise chemical catalytic sequence is a complex task where PSE tools have...... a particularly important role to play. In this paper we will present a variety of PSE tools including computational fluid dynamics (CFD), operating windows, kinetic modelling, economic analysis and environmental assessment to support the development of economically viable biocatalytic processes....

  7. Oxygen transfer rates and requirements in oxidative biocatalysis

    DEFF Research Database (Denmark)

    Pedersen, Asbjørn Toftgaard; Rehn, Gustav; Woodley, John

    Biocatalytic oxidation reactions offer several important benefits such as regio- and stereoselectivity, avoiding the use of toxic metal based catalysts and replacing oxidizing reagents by allowing the use of oxygen. However, the development of biocatalytic oxidation processes is a complex task wh......-up is relatively straight forward (Gabelman and Hwang, 1999), and membrane contactors are implemented for various industrial applications (Klaassen et al., 2005)....

  8. Biocatalytic portfolio of Basidiomycota.

    Science.gov (United States)

    Schmidt-Dannert, Claudia

    2016-04-01

    Basidiomycota fungi have received little attention for applications in biocatalysis and biotechnology and remain greatly understudied despite their importance for carbon recycling, ecosystem functioning and medicinal properties. The steady influx of genome data has facilitated detailed studies aimed at understanding the evolution and function of fungal lignocellulose degradation. These studies and recent explorations into the secondary metabolomes have uncovered large portfolios of enzymes useful for biocatalysis and biosynthesis. This review will provide an overview of the biocatalytic repertoires of Basidiomycota characterized to date with the hope of motivation more research into the chemical toolkits of this diverse group of fungi.

  9. Significance of membrane bioreactor design on the biocatalytic performance of glucose oxidase and catalase: Free vs. immobilized enzyme systems

    DEFF Research Database (Denmark)

    Morthensen, Sofie Thage; Meyer, Anne S.; Jørgensen, Henning;

    2017-01-01

    Membrane separation of xylose and glucose can be accomplished via oxidation of glucose to gluconic acid by enzymatic glucose oxidase catalysis. Oxygen for this reaction can be supplied via decomposition of hydrogen peroxide by enzymatic catalase catalysis. In order to maximize the biocatalytic...... productivity of glucose oxidase and catalase (gluconic acid yield per total amount of enzyme) the following system set-ups were compared: immobilization of glucose oxidase alone; co-immobilization of glucose oxidase and catalase; glucose oxidase and catalase free in the membrane bioreactor. Fouling......-induced enzyme immobilization in the porous support of an ultrafiltration membrane was used as strategy for entrapment of glucose oxidase and catalase. The biocatalytic productivity of the membrane reactor was found to be highly related to the oxygen availability, which in turn depended on the reactor...

  10. Biocatalytic material comprising multilayer enzyme coated fiber

    Science.gov (United States)

    Kim, Jungbae [Richland, WA; Kwak, Ja Hun [Richland, WA; Grate, Jay W [West Richland, WA

    2009-11-03

    The present invention relates generally to high stability, high activity biocatalytic materials and processes for using the same. The materials comprise enzyme aggregate coatings having high biocatalytic activity and stability useful in heterogeneous environment. These new materials provide a new biocatalytic immobilized enzyme system with applications in bioconversion, bioremediation, biosensors, and biofuel cells.

  11. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents.

    Science.gov (United States)

    Mutti, Francesco G; Orthaber, Andreas; Schrittwieser, Joerg H; de Vries, Johannes G; Pietschnig, Rudolf; Kroutil, Wolfgang

    2010-11-14

    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to enantioenriched chlorohydrins via an oxidation-asymmetric reduction sequence.

  12. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  13. Coated-wall microreactor for continuous biocatalytic transformations using immobilized enzymes.

    Science.gov (United States)

    Thomsen, Malene S; Nidetzky, Bernd

    2009-01-01

    Microstructured flow reactors are emerging tools for biocatalytic process development. A compelling design is that of the coated-wall reactor where enzyme is present as a surface layer attached to microchannel walls. However, preparation of a highly active wall biocatalyst remains a problem. Here, a stainless steel microreactor was developed where covalent immobilization of the enzyme in multiple linear flow channels of the reaction plate was supported by a macroporous wash-coat layer of gamma-aluminum oxide. Using surface functionalization with aminopropyl triethoxysilane followed by activation with glutardialdehyde, the thermophilic beta-glycosidase CelB from Pyrococcus furiosus was bound with retention of half of the specific activity of the free enzyme (800 U/mg), yielding a high catalyst loading of about 500 U/mL. This microreactor was employed for the continuous hydrolysis of lactose (100 mM) at 80 degrees C, providing a space-time yield of 500 mg glucose/(mL h) at a stable conversion of > or =70%. The immobilized enzyme displayed a half-life of 15 days under the operational conditions. Due to the absence of hydrophobic solute-material interactions, which limit the scope of microstructures fabricated from poly(dimethylsiloxane) for biocatalytic applications, the new microreactor was fully compatible with the alternate enzyme substrate 2-nitro-phenyl-beta-D-galactoside and the 2-nitro-phenol product resulting from its hydrolysis catalyzed by CelB.

  14. Sustainable Biocatalytic Biodiesel Production

    DEFF Research Database (Denmark)

    Güzel, Günduz

    and chemical equilibria as part of his main sustainable biodiesel project. The transesterification reaction of vegetable oils or fats with an aliphatic alcohol – in most cases methanol or ethanol – yields biodiesel (long-chain fatty acid alkyl esters – FAAE) as the main product in the presence of alkaline....../acid catalysts or biocatalysts (free or immobilised lipase enzymes). The reaction by-product glycerol is immiscible with the ester products (FAAE and oils/fats) in addition to the partial miscibility problem of methanol or ethanol with oils/fats. The insoluble parts of alcohol feeds or by-products form emulsion...... droplets within the reaction media, where continuous stirring operations are applied to improve mass transfer and thus reaction rates. In all other cases, there is a heterogeneous alcohol phase in equilibrium with the ester phase under equilibrium conditions. The immiscibility and/or miscibility drawbacks...

  15. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

    NARCIS (Netherlands)

    Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang

    2010-01-01

    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to enantioenrich

  16. Oxidation state of BZ reaction mixtures.

    Science.gov (United States)

    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.

  17. The Biocatalytic Desulfurization Project

    Energy Technology Data Exchange (ETDEWEB)

    David Nunn; James Boltz; Philip M. DiGrazia; Larry Nace

    2006-03-03

    The material in this report summarizes the Diversa technical effort in development of a biocatalyst for the biodesulfurization of Petro Star diesel as well as an economic report of standalone and combined desulfurization options, prepared by Pelorus and Anvil, to support and inform the development of a commercially viable process. We will discuss goals of the projected as originally stated and their modification as guided by parallel efforts to evaluate commercialization economics and process parameters. We describe efforts to identify novel genes and hosts for the generation of an optimal biocatalyst, analysis of diesel fuels (untreated, chemically oxidized and hydrotreated) for organosulfur compound composition and directed evolution of enzymes central to the biodesulfurization pathway to optimize properties important for their use in a biocatalyst. Finally we will summarize the challenges and issues that are central to successful development of a viable biodesulfurization process.

  18. THE BIOCATALYTIC DESULFURIZATION PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Steven E. Bonde; David Nunn

    2003-01-01

    During the first quarter of the Biological Desulfurization project several activities were pursued. A project kickoff meeting was held at the Diversa facility in San Diego, CA. Activities that were in process before the meeting and begun afterwards by Diversa Corporation and Petro Star Inc. include: Technology transfer in the form of information generated by Enchira to Diversa, the purchase and installation of equipment by Diversa, development of synthetic methods and preparation of organo-sulfur substrates for use in determining enzyme activities, production of extract via Petro Star's CED process, detailed analysis of Petro Star Inc. diesel and CED extract, and several activities in molecular biology. Diversa Corporation, in the area of molecular biology, engaged in several activities in support of the task list of the contract. These included: construction of a genomic library; development and utilization of a sequence-based gene discovery effort; a parallel discovery approach based on functional expression of enzymes with the ability to oxidize organosulfur compounds. Biodesulfurization genes have already been identified and are being sequenced and subcloned for expression in heterologous biological hosts. Diversa has evaluated and adapted assays developed by Enchira used to assess the activities of DBT and DBTO{sub 2} monooxygenases. Finally, Diversa personnel have developed two novel selection/screen strategies for the improvement of biocatalyst strains by directed evolution.

  19. THE BIOCATALYTIC DESULFURIZATION PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Steven E. Bonde; David Nunn

    2003-04-01

    Research activities in the second quarter have largely been a continuation of efforts previously described in the first quarterly report as well as a degree of redirection of effort as a result of discussions during the first quarterly meeting held in San Diego. Chemical synthesis efforts have been refined and are currently being used to support generation of substrates for evaluation and evolution of enzymes for their oxidation. Analysis of the sulfur species in Petro Star diesel, CED extract and refinement of the speciation data is nearly complete. Molecular biology efforts continue with the cloning, expression and characterization of the DszA and DszC proteins as well as the flavin reductases to support regeneration of the essential FMN cofactors. In addition, we have initiated an evolution effort for the extension and improvement of DszA enzyme activity using Diversa's Gene Site Saturation Mutagenesis (GSSM{trademark}) technology. To support the evolution effort as well as of characterization of enzyme activities on a variety of substrates, a high-throughput mass spectroscopy-based assay has been developed. Two selection/screen strategies for the discovery and evolution of biocatalyst enzyme have been developed and are being evaluated for performance using gene libraries constructed from known biodesulfurization strains and environmental libraries.

  20. Biocatalytic oxidation of phenolic compounds by bovine methemoglobin in the presence of H{sub 2}O{sub 2}: Quantitative structure-activity relationships

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Prior, M. Teresa, E-mail: MariaTeresa.Perez@uclm.es [Department of Physical Chemistry, University of Castilla-La Mancha, Campus Universitario, E-02071 Albacete (Spain); Gomez-Bombarelli, Rafael, E-mail: R.GomezBombarelli@hw.ac.uk [Department of Physics, Heriot-Watt University, David Brewster Building G.45, Edinburgh (United Kingdom); Gonzalez-Sanchez, M. Isabel, E-mail: MIsabel.Gonzalez@uclm.es [Department of Physical Chemistry, University of Castilla-La Mancha, Campus Universitario, E-02071 Albacete (Spain); Valero, Edelmira, E-mail: Edelmira.Valero@uclm.es [Department of Physical Chemistry, University of Castilla-La Mancha, Campus Universitario, E-02071 Albacete (Spain)

    2012-11-30

    Highlights: Black-Right-Pointing-Pointer The kinetics of metHb-catalyzed oxidation of a group of phenols were analyzed. Black-Right-Pointing-Pointer Unusual kinetic behaviour was observed for the phenols here tested. Black-Right-Pointing-Pointer QSAR equations for a number of physicochemical parameters were established. Black-Right-Pointing-Pointer A relationship between the peroxidase and catalase activities of metHb was found. Black-Right-Pointing-Pointer Bovine metHb might represent a good economical alternative to other peroxidases. - Abstract: In the present work, 13 p-substituted phenols with different functional groups have been systematically evaluated as metHb substrates by means of HPLC analysis. Non-hyperbolic kinetics were observed and Hill coefficients in the 0.37-1.00 range were obtained. The catalytic constants and the Hill coefficients were found to be quantitatively correlated with two independent variables: the energy level of the highest-occupied molecular orbital (E{sub HOMO}), which describes the intrinsic redox activity of the substrates and the pK{sub a}-values, which are related to substrate ionization. Oxygen evolution in the presence of each phenol derivative was also measured, and good correlation between peroxidase-like and catalase-like activities of the protein was observed. It is also shown that bovine metHb, although less active than other peroxidases, may represent a good alternative from an economical point of view for phenol removal processes. The equations here obtained may serve as a basis to further explore the potential use of metHb-mediated reactions in the treatment of phenols in wastewaters and to predict which phenol will be removed most efficiently under this treatment with satisfactory reliability.

  1. Quantification and evaluation of kinetic bio-catalytic pathway of horseradish peroxidase in an electron mediated reaction system and its applications in plant extracts.

    Science.gov (United States)

    Krishna, Honnur; Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Chamaraja, Nelligere A; Aradhana, Narayan

    2013-02-01

    The intermolecular coupling of 2,5-dimethoxyaniline (DMA) as mediated electron transfer reaction in presence of H(2)O(2) and peroxidase in acetate buffer of pH 4.2 resulting green colored product having maximum absorption at λ(max)=740 nm was investigated by spectrophotometer. Under optimum conditions, linearity range for the quantification of H(2)O(2) was 2.0-288.0 μM and for peroxidase were 0.59-9.46 and 0.443-9.46 nM by kinetic and fixed-time method, respectively. The catalytic efficiency and catalytic power were K(eff)(D)=2.354 × 10(5)M(-1)min(-1) and K(pow)(D)=4.59 × 10(-4)min(-1), respectively. From the plot of d(1/D(o)) vs d(1/V(o)) and d(1/H(o)) vs d(1/V(o)), Michaelis-Menten constants for DMA and H(2)O(2)were found that K(m)(D)=1,458 μM and [Formula: see text] =301 μM. Applicability of the method was tested for peroxidase activity in some plant extracts and compared with guaiacol/peroxidase system. Regarding superiority of the method, it is suggested that DMA/peroxidase system can be a better hydrogen donor for HRP assay than guaiacol system as evident from kinetic data.

  2. Quantification and evaluation of kinetic bio-catalytic pathway of horseradish peroxidase in an electron mediated reaction system and its applications in plant extracts

    Science.gov (United States)

    Krishna, Honnur; Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Chamaraja, Nelligere A.; Aradhana, Narayan

    2013-02-01

    The intermolecular coupling of 2,5-dimethoxyaniline (DMA) as mediated electron transfer reaction in presence of H2O2 and peroxidase in acetate buffer of pH 4.2 resulting green colored product having maximum absorption at λmax = 740 nm was investigated by spectrophotometer. Under optimum conditions, linearity range for the quantification of H2O2 was 2.0-288.0 μM and for peroxidase were 0.59-9.46 and 0.443-9.46 nM by kinetic and fixed-time method, respectively. The catalytic efficiency and catalytic power were KeffD = 2.354 × 105 M-1 min-1 and KpowD = 4.59 × 10-4 min-1, respectively. From the plot of d(1/Do) vs d(1/Vo) and d(1/Ho) vs d(1/Vo), Michaelis-Menten constants for DMA and H2O2were found that KmD = 1458 μM and KmHO = 301 μM. Applicability of the method was tested for peroxidase activity in some plant extracts and compared with guaiacol/peroxidase system. Regarding superiority of the method, it is suggested that DMA/peroxidase system can be a better hydrogen donor for HRP assay than guaiacol system as evident from kinetic data.

  3. The effect of outside conditions on anaerobic ammonia oxidation reaction

    Institute of Scientific and Technical Information of China (English)

    YANG Min; WANG Shu-bo

    2016-01-01

    Organic carbon, inorganic carbon, temperature, pH and ORP are all to have a certain influence on the anaerobic ammonia oxidation reaction. We can draw some conclusions on the optimum conditions of anaerobic ammonia oxidation reaction. The optimum temperature of the anaerobic ammonia oxidation reaction is 30-35℃. And the optimum pH of the anaerobic ammonia reaction is 7.5-8.3. The presence of organic matters can affect the anaerobic ammonia reaction, and different organic matters have different influence on it. The concentration of the inorganic carbon also exist great influence on the reaction. High inorganic carbon concentration also can inhibit anaerobic ammonia oxidation reaction.

  4. Sustainable biocatalytic biodiesel production : A thermodynamic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Guezel, G.

    2012-09-15

    In the present thesis it was aimed at achieving thermodynamic analysis of reactions involved in enzymatic biodiesel production with specific focus on chemical and phase equilibria of reactive systems. Lipase-catalyzed biodiesel production (biocatalytic ethanolysis) presents significant advantages: Easy recovery of glycerol, no complex down-processing operations for elimination of catalyst and salt, and requires less organic solvent and lower energy consumption compared with conventional chemical methods. In overall, the major aims of this thesis were evaluating and subsequently finding feasible solutions to the questions emerged during the corresponding studies that have been performed worldwide. Some of the questions that were answered as appropriate as possible can be listed as follows: 1) What is the solubility of EtOH in vegetable oils and in FAEE blends and how does it change with temperature? 2) Is it possible to prevent denaturing impact of EtOH on biocatalysts? 3) What are the feedstock content (water and FFA) impacts on glycerol and EtOH miscibility with ester species? 4) Is it necessary removing glycerol by-product simultaneously? 5) Is it feasible providing monophasic or homogeneous reaction media that procure lower external mass transfer resistance? 6) What are the moisture absorption limits of FAAE species? 7) How are the interactions of reactive species in terms of miscibility/immiscibility phenomena? 8) Is it thermodynamically feasible providing monophasic reaction media? 9) How can LLE and VLE phase behaviors help to determine optimum reaction conditions? 10) How can the results of LLE and VLE studies be used so as to determine appropriate refining operations? (LN)

  5. Application of environmental and economic metrics to guide the development of biocatalytic processes

    DEFF Research Database (Denmark)

    Lima Ramos, Joana; Tufvesson, Pär; Woodley, John

    2014-01-01

    The increasing industrial interest in biocatalytic processes is predominantly driven by the need for selective chemistry, with high reaction yield (Y-reaction) and few side reactions, as well as the need for optically pure chiral molecules (in particularly in the pharmaceutical industry). Interes......The increasing industrial interest in biocatalytic processes is predominantly driven by the need for selective chemistry, with high reaction yield (Y-reaction) and few side reactions, as well as the need for optically pure chiral molecules (in particularly in the pharmaceutical industry...... processes are not yet fully optimized. Hence, in this paper we propose the use of a range of tools which can be used to guide process development, research tasks and support decision-making. Three sets of metrics are identified, each for use at different stages of process development (route selection, early...

  6. Positive patch test reactions to oxidized limonene

    DEFF Research Database (Denmark)

    Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus

    2014-01-01

    BACKGROUND: R-Limonene is a common fragrance terpene found in domestic and industrial products. R-Limonene autoxidizes on air exposure, and the oxidation products can cause contact allergy. In a recent multicentre study, 5.2% (range 2.3-12.1%) of 2900 patients showed a positive patch test reaction...... hydroperoxides at 0.33%) in petrolatum was tested in 2900 consecutive dermatitis patients in Australia, Denmark, the United Kingdom, Singapore, Spain, and Sweden. A questionnaire assessing exposure to limonene-containing products was completed. RESULTS: Overall, exposure to products containing limonene was found...... was frequently found in the labelling on the patients' products, and assessed as relevant for the patients' dermatitis. A large number of domestic and occupational sources for contact with R-limonene were identified....

  7. Model visualization for evaluation of biocatalytic processes

    DEFF Research Database (Denmark)

    Law, HEM; Lewis, DJ; McRobbie, I

    2008-01-01

    Biocatalysis offers great potential as an additional, and in some cases as an alternative, synthetic tool for organic chemists, especially as a route to introduce chirality. However, the implementation of scalable biocatalytic processes nearly always requires the introduction of process and/or bi...

  8. Lipase-immobilized biocatalytic membranes for biodiesel production.

    Science.gov (United States)

    Kuo, Chia-Hung; Peng, Li-Ting; Kan, Shu-Chen; Liu, Yung-Chuan; Shieh, Chwen-Jen

    2013-10-01

    Microbial lipase from Candida rugosa (Amano AY-30) has good transesterification activity and can be used for biodiesel production. In this study, polyvinylidene fluoride (PVDF) membrane was grafted with 1,4-diaminobutane and activated by glutaraldehyde for C. rugosa lipase immobilization. After immobilization, the biocatalytic membrane was used for producing biodiesel from soybean oil and methanol via transesterification. Response Surface Methodology (RSM) in combination with a 5-level-5-factor central composite rotatable design (CCRD) was employed to evaluate the effects of reaction time, reaction temperature, enzyme amount, substrate molar ratio and water content on the yield of soybean oil methyl ester. By ridge max analysis, the predicted and experimental yields under the optimum synthesis conditions were 97% and 95%, respectively. The lipase-immobilized PVDF membrane showed good reuse ability for biodiesel production, enabling operation for at least 165 h during five reuses of the batch, without significant loss of activity.

  9. Oxidation and Reduction Reactions in Organic Chemistry

    Science.gov (United States)

    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…

  10. Optimizing the biocatalytic productivity of an engineered sialidase from Trypanosoma rangeli for 3′-sialyllactose production

    DEFF Research Database (Denmark)

    Zeuner, Birgitte; Luo, Jianquan; Nyffenegger, Christian

    2014-01-01

    -use methods were compared to optimize the biocatalytic productivity, i.e. 3′-sialyllactose formation per amount of Tr6 employed: (i) His-tag immobilization on magnetic Cu2+-iminodiacetic acid-functionalized nanoparticles (MNPs), (ii) membrane immobilization, (iii) calcium alginate encapsulation of cross......-linked Tr6, and (iv) Tr6 catalysis in a membrane reactor. Tr6 immobilized on MNPs gave a biocatalytic productivity of 84mg 3′-sialyllactose/mg Tr6 after seven consecutive reaction runs. Calcium-alginate and membrane immobilization were inefficient. Using free Tr6 in a 10kDa membrane reactor produced a 9...

  11. Microfluidic multi-input reactor for biocatalytic synthesis using transketolase☆

    Science.gov (United States)

    Lawrence, James; O'Sullivan, Brian; Lye, Gary J.; Wohlgemuth, Roland; Szita, Nicolas

    2013-01-01

    Biocatalytic synthesis in continuous-flow microreactors is of increasing interest for the production of specialty chemicals. However, the yield of production achievable in these reactors can be limited by the adverse effects of high substrate concentration on the biocatalyst, including inhibition and denaturation. Fed-batch reactors have been developed in order to overcome this problem, but no continuous-flow solution exists. We present the design of a novel multi-input microfluidic reactor, capable of substrate feeding at multiple points, as a first step towards overcoming these problems in a continuous-flow setting. Using the transketolase-(TK) catalysed reaction of lithium hydroxypyruvate (HPA) and glycolaldehyde (GA) to l-erythrulose (ERY), we demonstrate the transposition of a fed-batch substrate feeding strategy to our microfluidic reactor. We obtained a 4.5-fold increase in output concentration and a 5-fold increase in throughput compared with a single input reactor. PMID:24187515

  12. Heterocycles 38. Biocatalytic Synthesis of New Heterocyclic Mannich Bases and Derivatives

    Directory of Open Access Journals (Sweden)

    Denisa Leonte

    2015-07-01

    Full Text Available This paper describes the biocatalytic synthesis of new Mannich bases containing various heterocyclic rings (thiazole, furane, thiophene, pyridine by applying the lipase catalyzed trimolecular condensation of the corresponding heterocyclic aldehydes with acetone and primary aromatic amines, in mild and eco-friendly reaction conditions. The obtained Mannich bases were acylated to their corresponding N-acetyl derivatives. All compounds were characterized by 1H-NMR, 13C-NMR and MS spectrometry.

  13. Some Environmentally Relevant Reactions of Cerium Oxide

    Directory of Open Access Journals (Sweden)

    Janoš Pavel

    2014-12-01

    Full Text Available Reactive forms of cerium oxide were prepared by a thermal decomposition of various precursors, namely carbonates, oxalates and citrates, commercially available nanocrystalline cerium oxide (nanoceria was involved in the study for comparison. Scanning electron microscopy (SEM and x-ray diffraction analysis (XRD were used to examine the morphology and crystallinity of the samples, respectively, whereas the Brunauer-Emmett-Teller (BET method of nitrogen adsorption was used to determine surface areas. Interactions of cerium oxide with some phosphorus-containing compounds were investigated. Some of the examined samples, especially those prepared by annealing from carbonate precursors, exhibited an outstanding ability to destroy highly toxic organophosphates, such as pesticides (parathion methyl, or nerve agents (soman, VX. There were identified some relations between the degradation efficiency of cerium oxides and their crystallinity. It was also shown that cerium oxide is able to destroy one of widely used flame retardants - triphenyl phosphate. A phosphatase-mimetic activity of various cerium oxides was examined with the aid of a standardized phosphatase test.

  14. Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers

    Institute of Scientific and Technical Information of China (English)

    WANG Gui-Xiu; ZHU Rong-Xiu; ZHANG Dong-Ju; LIU Cheng-Bu

    2006-01-01

    The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial contact charge transfer complexes (CCTCs), transition states and caged radical intermediates have been located at the B3LYP/6-31G (d) level. The bonding nature of ethers with triplet O2 in CCTCs has been analyzed, and the detailed mechanism of dark oxidation reactions of ether is presented clearly.

  15. Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Froehaug, Astrid Elisabeth

    1995-12-31

    This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

  16. The Pathophysiology of Extracellular Hemoglobin Associated with Enhanced Oxidative Reactions

    Directory of Open Access Journals (Sweden)

    Joseph M Rifkind

    2015-01-01

    Full Text Available Hemoglobin (Hb continuously undergoes autoxidation producing superoxide which dismutates into hydrogen peroxide (H2O2 and is a potential source for subsequent oxidative reactions. Autoxidation is most pronounced under hypoxic conditions in the microcirculation and for unstable dimers formed at reduced Hb concentrations. In the red blood cell (RBC, oxidative reactions are inhibited by an extensive antioxidant system. For extracellular Hb, whether from hemolysis of RBCs and/or the infusion of Hb-based blood substitutes, the oxidative reactions are not completely neutralized by the available antioxidant system. Un-neutralized H2O2 oxidizes ferrous and ferric Hbs to Fe(IV-ferrylHb and oxyferrylHb, respectively. FerrylHb further reacts with H2O2 producing heme degradation products and free iron. OxyferrylHb, in addition to Fe(IV contains a free radical that can undergo additional oxidative reactions. Fe(IIIHb produced during Hb autoxidation also readily releases heme, an additional source for oxidative stress. These oxidation products are a potential source for oxidative reactions in the plasma, but to a greater extent when the lower molecular weight Hb dimers enter cells and tissues. Heme and oxyferryl have been shown to have a proinflammatory effect further increasing their potential for oxidative stress. These oxidative reactions contribute to a number of pathological situations including atherosclerosis, kidney malfunction, sickle cell disease and malaria. The toxic effects of extracellular Hb are of particular concern for increased hemolysis due to hemolytic anemia. Hemolysis is further exacerbated in various diseases and their treatments. Blood transfusions are required whenever there is an appreciable decrease in RBCs due to hemolysis or blood loss. It is, therefore, essential that transfused blood, whether stored RBCs or blood obtained by an Autologous Blood Recovery System from the patient, does not further increase extracellular Hb.

  17. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

    DEFF Research Database (Denmark)

    Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

    2001-01-01

    the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase...

  18. Biocatalytic synthesis of silicone polyesters.

    Science.gov (United States)

    Frampton, Mark B; Subczynska, Izabela; Zelisko, Paul M

    2010-07-12

    The immobilized lipase B from Candida antarctica (CALB) was used to synthesize silicone polyesters. CALB routinely generated between 74-95% polytransesterification depending on the monomers that were used. Low molecular weight diols resulted in the highest rates of esterification. Rate constants were determined for the CALB catalyzed polytransesterifications at various reaction temperatures. The temperature dependence of the CALB-mediated polytransesterifications was examined. A lipase from C. rugosa was only successful in performing esterifications using carboxy-modified silicones that possessed alkyl chains greater than three methylene units between the carbonyl and the dimethylsiloxy groups. The proteases alpha-chymotrypsin and papain were not suitable enzymes for catalyzing any polytransesterification reactions.

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

    Science.gov (United States)

    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 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.

  20. Biocatalytic process development using microfluidic miniaturized systems

    DEFF Research Database (Denmark)

    Krühne, Ulrich; Heintz, Søren; Ringborg, Rolf Hoffmeyer

    2014-01-01

    The increasing interest in biocatalytic processes means there is a clear need for a new systematic development paradigm which encompasses both protein engineering and process engineering. This paper argues that through the use of a new microfluidic platform, data can be collected more rapidly...... and integrated with process modeling, can provide the basis for validating a reduced number of potential processes. The miniaturized platform should use a smaller reagent inventory and make better use of precious biocatalysts. The EC funded BIOINTENSE project will use ω-transaminase based synthesis of chiral...

  1. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    for the selective oxidation of alcohols was investigated. By using a straightforward screening approach, silver supported on silica prepared by impregnation was found to be catalytically active in a mixture with nano-sized ceria. The collaborative effect between ceria and silver was traced back to direct physical....... XAS revealed that silver was in the metallic state. Silver particle sizes estimated from XAS were significantly smaller (2- 3 nm) than from transmission electron microscopy (TEM) and X-ray diffraction (XRD; ca. 30 nm). It was proposed that silver-oxygen species might cause local disorder which would...... lead to an underestimated particle size by XAS. Based on catalytic studies, a simplified preliminary mechanism was proposed following the dehydrogenation mechanism over gold and palladium catalysts. Comparison of the performance of the silver catalyst with commercial palladium and gold catalysts...

  2. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  3. Biocatalytic reduction of carboxylic acids.

    Science.gov (United States)

    Napora-Wijata, Kamila; Strohmeier, Gernot A; Winkler, Margit

    2014-06-01

    An increasing demand for non-petroleum-based products is envisaged in the near future. Carboxylic acids such as citric acid, succinic acid, fatty acids, and many others are available in abundance from renewable resources and they could serve as economic precursors for bio-based products such as polymers, aldehyde building blocks, and alcohols. However, we are confronted with the problem that carboxylic acid reduction requires a high level of energy for activation due to the carboxylate's thermodynamic stability. Catalytic processes are scarce and often their chemoselectivity is insufficient. This review points at bio-alternatives: currently known enzyme classes and organisms that catalyze the reduction of carboxylic acids are summarized. Two totally distinct biocatalyst lines have evolved to catalyze the same reaction: aldehyde oxidoreductases from anaerobic bacteria and archea, and carboxylate reductases from aerobic sources such as bacteria, fungi, and plants. The majority of these enzymes remain to be identified and isolated from their natural background in order to evaluate their potential as industrial biocatalysts.

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

    Directory of Open Access Journals (Sweden)

    Seungdu Kim

    2016-07-01

    Full Text Available 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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  7. Elucidation of the regio- and chemoselectivity of enzymatic allylic oxidations with Pleurotus sapidus – conversion of selected spirocyclic terpenoids and computational analysis

    Directory of Open Access Journals (Sweden)

    Verena Weidmann

    2013-10-01

    Full Text Available Allylic oxidations of olefins to enones allow the efficient synthesis of value-added products from simple olefinic precursors like terpenes or terpenoids. Biocatalytic variants have a large potential for industrial applications, particularly in the pharmaceutical and food industry. Herein we report efficient biocatalytic allylic oxidations of spirocyclic terpenoids by a lyophilisate of the edible fungus Pleurotus sapidus. This ‘’mushroom catalysis’’ is operationally simple and allows the conversion of various unsaturated spirocyclic terpenoids. A number of new spirocyclic enones have thus been obtained with good regio- and chemoselectivity and chiral separation protocols for enantiomeric mixtures have been developed. The oxidations follow a radical mechanism and the regioselectivity of the reaction is mainly determined by bond-dissociation energies of the available allylic CH-bonds and steric accessibility of the oxidation site.

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

    Science.gov (United States)

    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.

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

    Institute of Scientific and Technical Information of China (English)

    Yang Zhang; Jinian Shu; Yuanxun Zhang; Bo Yang

    2013-01-01

    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 (VUVATOFMS).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.

  10. Evidence concerning oxidation as a surface reaction in Baltic amber

    DEFF Research Database (Denmark)

    Shashoua, Yvonne

    2012-01-01

    The aim of this study was to provide evidence about oxidation as a surface reaction during degradation of Baltic amber. A clear understanding of the amber-oxygen interaction modalities is essential to develop conservation techniques for museum collections of amber objects. Pellet-shaped samples......, obtained from pressed amber powder, were subjected to accelerated thermal ageing. Cross-sections of the pellets were analyzed by infrared micro-spectroscopy, in order to identify and quantify changes in chemical properties. The experimental results showed strong oxidation exclusively at the exterior part...

  11. Exploring the biocatalytic potential of a DyP-type peroxidase by profiling the substrate acceptance of Thermobifida fusca DyP peroxidase

    NARCIS (Netherlands)

    Loncar, Nikola; Colpa, Dana I.; Fraaije, Marco W.

    2016-01-01

    Dye-decolorizing peroxidases (DyPs) represent a new class of oxidative enzymes for which the natural substrates are largely unknown. To explore the biocatalytic potential of a DyP, we have studied the substrate acceptance profile of a robust DyP peroxidase, a DyP from Thermobifida fusca (TfuDyP). Wh

  12. Hydrogen production from methane through catalytic partial oxidation reactions

    Science.gov (United States)

    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.

  13. Effect of vegetable oil oxidation on the hydrogenation reaction process

    Directory of Open Access Journals (Sweden)

    Kalantari, Faranak

    2010-12-01

    Full Text Available Hydrogenation has been carried out in a batch reactor with three different oxidized bleached oils in order to discover the effect of oxidation on the hydrogenation reaction process. Specifications of hydrogenated oils such as melting point, Iodine value, solid fat content and fatty acid composition of the oxidized oils were compared with their un-oxidized reference oils. Oxidized bleached sunflower oil was hydrogenated to target melting points (34, 39 and 42°C at higher iodine values vs. its reference oil with the same reaction time. Oxidized bleached soybean and canola oils were hydrogenated to target melting points (34, 39 and 42°C at higher iodine values as well, but reaction times were longer than their reference oils. The resulting solid fat content and total trans fatty acids of all hydrogenated oils were less than their references. A peroxide value above 0.5meq O2/kg for non auto-oxidized oils and above 5meq O2/kg for auto-oxidized oils will significantly change the hydrogenation process.

    La hidrogenación fue llevada cabo en un reactor discontinuo con tres aceites decoloradas y oxidadas con objeto de estudiar el efecto de la oxidación en el proceso de hidrogenación. Las especificaciones de los aceites hidrogenados tales como el punto de fusión, índice de yodo, contenido de grasa sólida y composición de ácidos grasos de los aceites oxidados fueron comparados con sus correspondientes aceites de referencia sin oxidar. El aceite de girasol decolorado y oxidado fue hidrogenado hasta alcanzar un punto de fusión (34, 39 and 42°C con altos índices de yodo versus su aceite de referencia con el mismo tiempo de reacción. Aceites decolorado y oxidado de soja y de canola fueron hidrogenados hasta alcanzar puntos de fusión (34,39 y 42°C con altos valores de yodo, pero los tiempo de reacción fueron más largos que en sus aceites de referencia. Los resultados del contenido de grasa sólida y ácidos grasos

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

    Science.gov (United States)

    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.

  15. Direct partial oxidation of methane to methanol: Reaction zones and role of catalyst location

    Institute of Scientific and Technical Information of China (English)

    Qijian Zhang; Dehua He; Qiming Zhu

    2008-01-01

    Direct partial oxidation of methane to methanol was investigated in a specially designed reactor. Methanol yield of about 7%-8% was obtained in gas phase partial oxidation. It was proposed that the reactor could be divided into three reaction zones, namely pre-reaction zone, fierce reaction zone, and post-reaction zone, when the temperature was high enough to initiate a reaction. The oxidation of methane proceeded and was completed mostly in the fierce reaction zone. When the reactant mixture entered the post-reaction zone, only a small amount of produced methanol would bring about secondary reactions, because molecular oxygen had been exhausted in the fierce reaction zone. A catalyst, if necessary, should be placed either in the pre-reaction zone, to initiate a partial oxidation reaction at a lower temperature, or in the fierce reaction zone to control the homogeneous free radical reaction.

  16. Covalently Bonded Chitosan on Graphene Oxide via Redox Reaction

    Directory of Open Access Journals (Sweden)

    Víctor M. Castaño

    2013-03-01

    Full Text Available Carbon nanostructures have played an important role in creating a new field of materials based on carbon. Chemical modification of carbon nanostructures through grafting has been a successful step to improve dispersion and compatibility in solvents, with biomolecules and polymers to form nanocomposites. In this sense carbohydrates such as chitosan are extremely valuable because their functional groups play an important role in diversifying the applications of carbon nanomaterials. This paper reports the covalent attachment of chitosan onto graphene oxide, taking advantage of this carbohydrate at the nanometric level. Grafting is an innovative route to modify properties of graphene, a two-dimensional nanometric arrangement, which is one of the most novel and promising nanostructures. Chitosan grafting was achieved by redox reaction using different temperature conditions that impact on the morphology and features of graphene oxide sheets. Transmission Electron Microscopy, Fourier Transform Infrared, Raman and Energy Dispersive spectroscopies were used to study the surface of chitosan-grafted-graphene oxide. Results show a successful modification indicated by the functional groups found in the grafted material. Dispersions of chitosan-grafted-graphene oxide samples in water and hexane revealed different behavior due to the chemical groups attached to the graphene oxide sheet.

  17. Evaluation of antioxidants using oxidation reaction rate constants

    Institute of Scientific and Technical Information of China (English)

    SHI Yan; ZHAN Xiancheng; MA Lie; LI Linli; LI Chengrong

    2007-01-01

    An evaluation method for the capacity of antioxidants to protect drugs against oxidation is presented.As a new viewpoint,to determine the priority of the competitive oxidations between the antioxidant and the protected drug,and to compare the drug-protection capacity of antioxidants,it is important to determine their oxidation rate constants using chemical kinetics instead of standard oxidation (or reduction) potentials.Sodium sulfite,sodium bisulfite and sodium pyrosulfite were used as models for the determination of oxidation reaction rate constants in aqueous solutions.In the experiments,sufficient air was continually infused into the solution to keep the concentration of dissolved oxygen constant.The residual concentrations of the antioxidants were determined by iodimetry,and the concentration of dissolved oxygen by oxygen electrode.The data were fitted by linear regressions to obtain the reaction rate constants.It was found that the degradation of sodium sulfite,sodium bisulfite or sodium pyrosulfite obeyed pseudo zero-order kinetics in the buffer solutions.Because of the ionization equilibrium,these three antioxidants have the same ion form in solutions at a definite pH value and therefore their apparent rate constants were essentially the same.The average apparent rate constants of the three antioxidants at 25~C are (1.34±0.03)×10-3 at pH 6.8,(1.20±0.02) x 10-3 at pH 4.0 and (6.58±0.02)×10-3 mol.L-1.h-1 at pH 9.2,respectively.

  18. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon.

    Science.gov (United States)

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee

    2016-06-05

    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIBr-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process.

  19. Use of a Ceramic Membrane to Improve the Performance of Two-Separate-Phase Biocatalytic Membrane Reactor.

    Science.gov (United States)

    Ranieri, Giuseppe; Mazzei, Rosalinda; Wu, Zhentao; Li, Kang; Giorno, Lidietta

    2016-03-14

    Biocatalytic membrane reactors (BMR) combining reaction and separation within the same unit have many advantages over conventional reactor designs. Ceramic membranes are an attractive alternative to polymeric membranes in membrane biotechnology due to their high chemical, thermal and mechanical resistance. Another important use is their potential application in a biphasic membrane system, where support solvent resistance is highly needed. In this work, the preparation of asymmetric ceramic hollow fibre membranes and their use in a two-separate-phase biocatalytic membrane reactor will be described. The asymmetric ceramic hollow fibre membranes were prepared using a combined phase inversion and sintering technique. The prepared fibres were then used as support for lipase covalent immobilization in order to develop a two-separate-phase biocatalytic membrane reactor. A functionalization method was proposed in order to increase the density of the reactive hydroxyl groups on the surface of ceramic membranes, which were then amino-activated and treated with a crosslinker. The performance and the stability of the immobilized lipase were investigated as a function of the amount of the immobilized biocatalytst. Results showed that it is possible to immobilize lipase on a ceramic membrane without altering its catalytic performance (initial residual specific activity 93%), which remains constant after 6 reaction cycles.

  20. Use of a Ceramic Membrane to Improve the Performance of Two-Separate-Phase Biocatalytic Membrane Reactor

    Directory of Open Access Journals (Sweden)

    Giuseppe Ranieri

    2016-03-01

    Full Text Available Biocatalytic membrane reactors (BMR combining reaction and separation within the same unit have many advantages over conventional reactor designs. Ceramic membranes are an attractive alternative to polymeric membranes in membrane biotechnology due to their high chemical, thermal and mechanical resistance. Another important use is their potential application in a biphasic membrane system, where support solvent resistance is highly needed. In this work, the preparation of asymmetric ceramic hollow fibre membranes and their use in a two-separate-phase biocatalytic membrane reactor will be described. The asymmetric ceramic hollow fibre membranes were prepared using a combined phase inversion and sintering technique. The prepared fibres were then used as support for lipase covalent immobilization in order to develop a two-separate-phase biocatalytic membrane reactor. A functionalization method was proposed in order to increase the density of the reactive hydroxyl groups on the surface of ceramic membranes, which were then amino-activated and treated with a crosslinker. The performance and the stability of the immobilized lipase were investigated as a function of the amount of the immobilized biocatalytst. Results showed that it is possible to immobilize lipase on a ceramic membrane without altering its catalytic performance (initial residual specific activity 93%, which remains constant after 6 reaction cycles.

  1. Biocatalytic removal of organic sulfur from coal

    Energy Technology Data Exchange (ETDEWEB)

    Webster, D.A. [Illinois Inst. of Tech., Chicago, IL (United States); Kilbane, J.J. II [Institute of Gas Technology, Chicadgo, IL (United States)

    1994-09-09

    The objective is to characterize more completely the biochemical ability of the bacterium, Rhodococcus rhodochrous IGTS8, to cleave carbon-sulfur bonds with emphasis on data that will allow the development of a practical coal biodesulfurization process. Another approach for increasing the desulfurization activity of the IGTS8 cultures is to produce strains genetically that have higher activity. The goal of this part of research is to achieve strain improvement by introducing a stronger promoter using genetic engineering techniques. The promoter regulates the transcription of the genes for the desulfurization enzymes, and a stronger promoter, would up-regulate the expression of these genes, resulting in cells with higher desulfurization activity. Promoter probe vectors are used to identify and isolate promoters from a DNA library of the experimental organism. The major accomplishments have been to obtain high biodesulfurization activity in nonaqueous, media, especially using freeze-dried cells, and to have isolated strong promoters from R. rhodochrous IGTS8 which will be used to engineer the organism to produce strains with higher biocatalytic activity.

  2. Nanopropulsion by biocatalytic self-assembly.

    Science.gov (United States)

    Leckie, Joy; Hope, Alexander; Hughes, Meghan; Debnath, Sisir; Fleming, Scott; Wark, Alastair W; Ulijn, Rein V; Haw, Mark D

    2014-09-23

    A number of organisms and organelles are capable of self-propulsion at the micro- and nanoscales. Production of simple man-made mimics of biological transportation systems may prove relevant to achieving movement in artificial cells and nano/micronscale robotics that may be of biological and nanotechnological importance. We demonstrate the propulsion of particles based on catalytically controlled molecular self-assembly and fiber formation at the particle surface. Specifically, phosphatase enzymes (acting as the engine) are conjugated to a quantum dot (the vehicle), and are subsequently exposed to micellar aggregates (fuel) that upon biocatalytic dephosphorylation undergo fibrillar self-assembly, which in turn causes propulsion. The motion of individual enzyme/quantum dot conjugates is followed directly using fluorescence microscopy. While overall movement remains random, the enzyme-conjugates exhibit significantly faster transport in the presence of the fiber forming system, compared to controls without fuel, a non-self-assembling substrate, or a substrate which assembles into spherical, rather than fibrous structures upon enzymatic dephosphorylation. When increasing the concentration of the fiber-forming fuel, the speed of the conjugates increases compared to non-self-assembling substrate, although directionality remains random.

  3. Biocatalytic desulfurization (BDS) of petrodiesel fuels.

    Science.gov (United States)

    Mohebali, Ghasemali; Ball, Andrew S

    2008-08-01

    Oil refineries are facing many challenges, including heavier crude oils, increased fuel quality standards, and a need to reduce air pollution emissions. Global society is stepping on the road to zero-sulfur fuel, with only differences in the starting point of sulfur level and rate reduction of sulfur content between different countries. Hydrodesulfurization (HDS) is the most common technology used by refineries to remove sulfur from intermediate streams. However, HDS has several disadvantages, in that it is energy intensive, costly to install and to operate, and does not work well on refractory organosulfur compounds. Recent research has therefore focused on improving HDS catalysts and processes and also on the development of alternative technologies. Among the new technologies one possible approach is biocatalytic desulfurization (BDS). The advantage of BDS is that it can be operated in conditions that require less energy and hydrogen. BDS operates at ambient temperature and pressure with high selectivity, resulting in decreased energy costs, low emission, and no generation of undesirable side products. Over the last two decades several research groups have attempted to isolate bacteria capable of efficient desulfurization of oil fractions. This review examines the developments in our knowledge of the application of bacteria in BDS processes, assesses the technical viability of this technology and examines its future challenges.

  4. Biocatalytic potential of laccase-like multicopper oxidases from Aspergillus niger

    Directory of Open Access Journals (Sweden)

    Tamayo-Ramos Juan Antonio

    2012-12-01

    Full Text Available Abstract Background Laccase-like multicopper oxidases have been reported in several Aspergillus species but they remain uncharacterized. The biocatalytic potential of the Aspergillus niger fungal pigment multicopper oxidases McoA and McoB and ascomycete laccase McoG was investigated. Results The laccase-like multicopper oxidases McoA, McoB and McoG from the commonly used cell factory Aspergillus niger were homologously expressed, purified and analyzed for their biocatalytic potential. All three recombinant enzymes were monomers with apparent molecular masses ranging from 80 to 110 kDa. McoA and McoG resulted to be blue, whereas McoB was yellow. The newly obtained oxidases displayed strongly different activities towards aromatic compounds and synthetic dyes. McoB exhibited high catalytic efficiency with N,N-dimethyl-p-phenylenediamine (DMPPDA and 2,2-azino-di(3-ethylbenzthiazoline sulfonic acid (ABTS, and appeared to be a promising biocatalyst. Besides oxidizing a variety of phenolic compounds, McoB catalyzed successfully the decolorization and detoxification of the widely used textile dye malachite green. Conclusions The A. niger McoA, McoB, and McoG enzymes showed clearly different catalytic properties. Yellow McoB showed broad substrate specificity, catalyzing the oxidation of several phenolic compounds commonly present in different industrial effluents. It also harbored high decolorization and detoxification activity with the synthetic dye malachite green, showing to have an interesting potential as a new industrial biocatalyst.

  5. Fly Ash and Mercury Oxidation/Chlorination Reactions

    Energy Technology Data Exchange (ETDEWEB)

    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

  6. Application of Moessbauer Spectroscopy to the Carbon Oxides Hydrogenation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Cubeiro, M. L. [UCV, Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica (Venezuela, Bolivarian Republic of)], E-mail: mcubeiro@strix.ciens.ucv.ve; Gonzalez-Jimenez, F.; Goldwasser, M. R.; Perez-Zurita, M. J.; Pietri, E.; Garcia, L. [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, UCV (Venezuela, Bolivarian Republic of)

    2001-05-15

    Iron-based catalysts have favorable activity and selectivity properties for the CO and CO{sub 2} 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 CO{sub 2} 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 CO{sub 2} 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.

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

    Science.gov (United States)

    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.

  8. In situ infrared (FTIR) study of the borohydride oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Concha, B. Molina; Chatenet, M. [Laboratoire d' Electrochimie et de Physico-chimie, des Materiaux et des Interfaces (LEPMI), UMR 5631 CNRS/Grenoble-INP/UJF, 1130 Rue de la Piscine, BP75, 38402 Saint Martin d' Heres Cedex (France); Coutanceau, C.; Hahn, F. [Laboratoire de Catalyse en Chimie Organique (LACCO), UMR 6503 CNRS, Universite de Poitiers, 40 Av. du, Recteur Pineau, 86000 Poitiers (France)

    2009-01-15

    The direct borohydride fuel cell (DBFC) is an interesting alternative for the electrochemical power generation at lower temperatures due to its high anode theoretical specific capacity (5 A h g{sup -1}). However, the borohydride oxidation reaction (BOR) is a very complex eight-electron reaction, influenced by the nature of the electrode material (catalytic or not with respect to BH{sub 4}{sup -} hydrolysis), the [BH{sub 4}{sup -}][OH{sup -}] ratio and the temperature. In order to understand the BOR mechanism, we performed in situ infrared reflectance spectroscopy measurements (SPAIRS technique) in 1 M NaOH/1 M NaBH{sub 4} with the aim to study intermediate reactions occurring on a gold electrode (a poor BH{sub 4}{sup -} hydrolysis catalyst). We monitored several bands in B-H (1184 cm{sup -1}) and B-O bond regions (1326 and 1415 cm{sup -1}), appearing sequentially with increasing electrode polarisation. Thanks to these experimental findings, we propose possible initial elementary steps for the BOR. (author)

  9. Recent advances on halohydrin dehalogenases-from enzyme identification to novel biocatalytic applications.

    Science.gov (United States)

    Schallmey, Anett; Schallmey, Marcus

    2016-09-01

    Halohydrin dehalogenases are industrially relevant enzymes that catalyze the reversible dehalogenation of vicinal haloalcohols with formation of the corresponding epoxides. In the reverse reaction, also other negatively charged nucleophiles such as azide, cyanide, or nitrite are accepted besides halides to open the epoxide ring. Thus, novel C-N, C-C, or C-O bonds can be formed by halohydrin dehalogenases, which makes them attractive biocatalysts for the production of various β-substituted alcohols. Despite the fact that only five individual halohydrin dehalogenase enzyme sequences have been known until recently enabling their heterologous production, a large number of different biocatalytic applications have been reported using these enzymes. The recent characterization of specific sequence motifs has facilitated the identification of novel halohydrin dehalogenase sequences available in public databases and has largely increased the number of recombinantly available enzymes. These will help to extend the biocatalytic repertoire of this enzyme family and to foster novel biotechnological applications and developments in the future. This review gives a general overview on the halohydrin dehalogenase enzyme family and their biochemical properties and further focuses on recent developments in halohydrin dehalogenase biocatalysis and protein engineering.

  10. Experimental determination of thermodynamic equilibrium in biocatalytic transamination

    DEFF Research Database (Denmark)

    Tufvesson, Pär; Jensen, Jacob Skibsted; Kroutil, Wolfgang;

    2012-01-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones...

  11. Biocatalytic Refining of Soybean Oil into Cosmeceutical Ingredients

    Science.gov (United States)

    Our mission is to develop new, value-added uses for commodity crops and oils. We chose to fulfill this mission while adhering as closely as possible to the tenants of “green” chemistry. We have developed patented, all-natural oils called Feruloyl Soy Glycerols (FSG) from the biocatalytic transester...

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

    Science.gov (United States)

    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

  13. Immobilized biocatalytic process development and potential application in membrane separation: a review.

    Science.gov (United States)

    Chakraborty, Sudip; Rusli, Handajaya; Nath, Arijit; Sikder, Jaya; Bhattacharjee, Chiranjib; Curcio, Stefano; Drioli, Enrico

    2016-01-01

    Biocatalytic membrane reactors have been widely used in different industries including food, fine chemicals, biological, biomedical, pharmaceuticals, environmental treatment and so on. This article gives an overview of the different immobilized enzymatic processes and their advantages over the conventional chemical catalysts. The application of a membrane bioreactor (MBR) reduces the energy consumption, and system size, in line with process intensification. The performances of MBR are considerably influenced by substrate concentration, immobilized matrix material, types of immobilization and the type of reactor. Advantages of a membrane associated bioreactor over a free-enzyme biochemical reaction, and a packed bed reactor are, large surface area of immobilization matrix, reuse of enzymes, better product recovery along with heterogeneous reactions, and continuous operation of the reactor. The present research work highlights immobilization techniques, reactor setup, enzyme stability under immobilized conditions, the hydrodynamics of MBR, and its application, particularly, in the field of sugar, starch, drinks, milk, pharmaceutical industries and energy generation.

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

    Science.gov (United States)

    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.

  15. Kinetics and Mechanism of the Reaction of Coherently Synchronized Oxidation and Dehydrogenation of Cyclohexane by Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Aghamammadova S.

    2016-01-01

    Based on this experimental researches, the complex reaction, consisting of parallel-sequential oxidation and dehydrogenation reactions, which are coherently synchronized, proceeds during the process of cyclohexane oxidation with biomimetic catalyst. Depending on the reaction parameters it is possible to deliberately adjust the direction of oxidation reaction and reaction rate.

  16. Electrochemical oxidation of quaternary ammonium electrolytes : Unexpected side reactions in organic electrochemistry

    NARCIS (Netherlands)

    Nouri Nigjeh, Eslam; de Vries, Marcel; Bruins, Andries P.; Bischoff, Rainer; Permentier, Hjalmar P.

    2012-01-01

    Quaternary ammonium salts are among the most widely used electrolytes in organic electrochemistry, but there is little known about their unwanted side oxidation reactions. We have, therefore, studied the constant potential oxidation products of quaternary ammonium electrolytes using mass spectrometr

  17. Catalysis of Reduction and Oxidation Reactions for Application in Gas Particle Filters

    Energy Technology Data Exchange (ETDEWEB)

    Udron, L.; Turek, T.

    2002-09-19

    The present study is a first part of an investigation addressing the simultaneous occurrence of oxidation and reduction reactions in catalytic filters. It has the objectives (a) to assess the state of knowledge regarding suitable (types of) catalysts for reduction and oxidation, (b) to collect and analyze published information about reaction rates of both NOx reduction and VOC oxidation, and (c) to adjust a lab-scale screening method to the requirements of an activity test with various oxidation/reduction catalysts.

  18. Tandem Reaction of Deprotonation-Oxidation-Wittig Reaction:Stereoselective Synthesis of (E)-α, β-Unsaturated Enoates

    Institute of Scientific and Technical Information of China (English)

    HUANG,Zhi-Zhen(黄志真); SUN,Ruo-Jun(孙若君)

    2002-01-01

    Phosphonium or arsonium salt with primary alcohol can undergo the tandem reaction of deprotonation-oxidation-Witting reaction in the presence of sodium hydroxide and manganese dioxide, providing a general and efficient method for the stereoselective synthesis of (E)-α,β-unsaturated enoates.

  19. Nitrosation Reaction Without Nitrogen Oxide Waste Gas Emission and Its Engineering Practice

    Institute of Scientific and Technical Information of China (English)

    CHEN Chunguang; FENG Yaqing; NIU Weiwei; CHEN Xuexi

    2013-01-01

    The gas-liquid phase equilibrium is used in controlling the nitrosation reaction process.Decomposition of nitrous acid and oxidation side reaction are suppressed in a closed reaction system.The system pressure is used as the criterion of the end of reaction,avoiding excessive feeding and reducing the decomposition of nitrous acid.The head space of the reactor is used as the gas buffer,stabilizing the feeding fluctuations and inhibiting the side reaction,decomposition of nitrous acid.Nitrogen oxide concentration is controlled at the minimum level.Thus the zero release of nitrogen oxide waste gas can be achieved without using any absorption process.

  20. Ring opening reaction dynamics in the reaction of hydrogen atoms with ethylene oxide

    Science.gov (United States)

    Shin, S. K.; Jarek, R. L.; Böhmer, E.; Wittig, C.

    1994-10-01

    Ethylene oxide, C2H4O, is a three-membered ring with a single oxygen atom bridging the two carbons. Reactions of H and D atoms with ethylene oxide have been studied in the gas phase to provide insight into the dynamics of three-membered ring opening. H atoms were produced by photolyzing HI in the wavelength range 240-266 nm. The channel leading to OH+C2H4 was monitored via laser-induced fluorescence (LIF) of the OH A 2Σ←X 2Π system. The D atom reaction yields OD with no hydrogen scrambling. With an available energy of 23 000 cm-1, the average OH D rotational energy is ˜350 cm-1 for OH(v=0) and OD(v=0) and ˜250 cm-1 for OD(v=1). OH(v=1) was not observed, while the OD(v=1) population was about one-tenth that of OD(v=0). There was no apparent bias in populations between Λ doublets in each of the spin-orbit states for both OH and OD. Doppler broadening of OH(v=0) rotational lines was measured to evaluate the average center-of-mass (c.m.) translational energy, which was found to be ˜2300 cm-1. On average, the ring opening process deposits ˜10% of the available energy into c.m. translation, ˜2% into OH rotation, and ˜88% into ethylene internal energy. Comparison with CH2CH2OH unimolecular dissociation dynamics and theoretical transition state calculations leads to a likely mechanism in which hydrogen abstracts oxygen via sequential C-O bond fission without involving a long-lived CH2CH2OH intermediate.

  1. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Microscale technology and biocatalytic processes: Opportunities and challenges for synthesis

    DEFF Research Database (Denmark)

    Wohlgemuth, Roland; Plazl, Igor; Žnidaršič-Plazl, Polona

    2015-01-01

    Despite the expanding presence of microscale technology in chemical synthesis and energy production as well as in biomedical devices and analytical and diagnostic tools, its potential in biocatalytic processes for pharmaceutical and fine chemicals, as well as related industries, has not yet been ......, and the future outlook for the implementation of these key green engineering methods and the role of supporting tools such as mathematical models to establish sustainable production processes are discussed....

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Building Bridges: Biocatalytic C-C-Bond Formation toward Multifunctional Products.

    Science.gov (United States)

    Schmidt, Nina G; Eger, Elisabeth; Kroutil, Wolfgang

    2016-07-01

    Carbon-carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C-C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C-C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C-C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand.

  5. Building Bridges: Biocatalytic C–C-Bond Formation toward Multifunctional Products

    Science.gov (United States)

    2016-01-01

    Carbon–carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C–C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C–C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C–C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand. PMID:27398261

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

    Science.gov (United States)

    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.

  7. Comparative analysis of oxidation methods of reaction-sintered silicon carbide for optimization of oxidation-assisted polishing.

    Science.gov (United States)

    Shen, Xinmin; Dai, Yifan; Deng, Hui; Guan, Chaoliang; Yamamura, Kazuya

    2013-11-04

    Combination of the oxidation of reaction-sintered silicon carbide (RS-SiC) and the polishing of the oxide is an effective way of machining RS-SiC. In this study, anodic oxidation, thermal oxidation, and plasma oxidation were respectively conducted to obtain oxides on RS-SiC surfaces. By performing scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX) analysis and scanning white light interferometry (SWLI) measurement, the oxidation behavior of these oxidation methods was compared. Through ceria slurry polishing, the polishing properties of the oxides were evaluated. Analysis of the oxygen element on polished surfaces by SEM-EDX was conducted to evaluate the remaining oxide. By analyzing the three oxidation methods with corresponding polishing process on the basis of schematic diagrams, suitable application conditions for these methods were clarified. Anodic oxidation with simultaneous polishing is suitable for the rapid figuring of RS-SiC with a high material removal rate; polishing of a thermally oxidized surface is suitable for machining RS-SiC mirrors with complex shapes; combination of plasma oxidation and polishing is suitable for the fine finishing of RS-SiC with excellent surface roughness. These oxidation methods are expected to improve the machining of RS-SiC substrates and promote the application of RS-SiC products in the fields of optics, molds, and ceramics.

  8. Silicon-technology based microreactors for high-temperature heterogeneous partial oxidation reactions

    NARCIS (Netherlands)

    Tiggelaar, Roald Michel

    2004-01-01

    In this thesis the results of a study into the feasibility of silicon-technology based microreactors for fast oxidation reactions have been discussed. When designed properly, silicon microreactors are suitable for studying heterogeneous gas phase reactions, such as reaction kinetics of direct cataly

  9. [Investigation of the oxidation reaction of O3 with bromide ion in aqueous solution].

    Science.gov (United States)

    Yu, Xiao-Ting; Zhang, Jia-Hui; Pan, Xun-Xi; Zhang, Ren-Xi; Hou, Hui-Qi

    2012-09-01

    The reaction mechanism of O3 with bromide ion in aqueous solution was studied by ion chromatography and UV-Vis spectrometry instruments. Ion chromatography analysis showed that only 10% of Br- which was oxidized by ozone was formed into bromate ion. The results demonstrated that the final products of the oxidation reaction were identified as Br2 and Br3- except for BrO3-. The formation of Br3- which was yielded from the reaction of Br2 with Br- was the major process in the reaction of Br attacked by O3. The characteristic absorption spectrum of Br3- with an absorption peak at 260 nm was also investigated. The results may provide helpful information about the mechanism of the oxidation reaction of Br- with O3 and fate of Br- or its derivatives in the environment by the oxidation processes.

  10. Reaction Kinetics for Heterogeneous Oxidation of Mn(Ⅲ)—Toluene

    Institute of Scientific and Technical Information of China (English)

    张彰; 朱宪

    2002-01-01

    The reaction kinetics of the heterogeneous oxidation oftoluene with Mn3+ was studied by considering the effects of disproportionation of Mn3+ in reaction system,a “parallel”modulus was set up.And then the concentration of Mn3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn.the rate constant,order and pseudo-activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded.In addition,the reaction mechanism was analyzed.It shows that the results are completely consistent with modulus.

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

    Science.gov (United States)

    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.

  12. Comparative temporal analysis of multiwalled carbon nanotube oxidation reactions: Evaluating chemical modifications on true nanotube surface

    Science.gov (United States)

    Pacheco, Flávia G.; Cotta, Alexandre A. C.; Gorgulho, Honória F.; Santos, Adelina P.; Macedo, Waldemar A. A.; Furtado, Clascídia A.

    2015-12-01

    The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

  13. Process of forming catalytic surfaces for wet oxidation reactions

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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...

  15. A short synthesis-stuttgart of (S)-pyrrolam A via domino oxidation-witting reaction

    Digital Repository Service at National Institute of Oceanography (India)

    Majik, M.S.; Shet, J.; Tilve, S.G.; Parameswaran, P.S.

    A short synthesis of (S)-pyrrolam A starting from readily available N-(benzyloxycarbonyl)-L prolinol is described that makes use of a domino primary alcohol oxidation-Witting reaction as the key step...

  16. Reaction mechanism for methanol oxidation on Au(1 1 1): A density functional theory study

    Science.gov (United States)

    Liu, Shuping; Jin, Peng; Zhang, Donghui; Hao, Ce; Yang, Xueming

    2013-01-01

    The microscopic reaction mechanism for methanol oxidation on Au(1 1 1) surface has been thoroughly investigated by means of density functional theory (DFT) computations. The adsorption geometries and energies were obtained for all the adsorbates, including the reactants, the products, and various possible intermediates on the metal. According to different oxygen conditions, we propose two possible reaction pathways for methanol oxidation on Au(1 1 1): (1) HCHO esterification: the intermediate formaldehyde and methoxy couple to yield methyl formate at low oxygen coverage or without the presence of oxygen atoms; (2) HCHO oxidation: the formaldehyde is oxidized to form formate at high oxygen coverage, which further dissociates to give CO2. Our study emphasizes the critical role of oxygen coverage during the methanol oxidation reaction, and can perfectly explain the difference in product distributions observed in previous experiments.

  17. CO2 as an Oxidant for High Temperature Reactions

    Directory of Open Access Journals (Sweden)

    Sibudjing eKawi

    2015-03-01

    Full Text Available This paper presents a review on the developments in catalyst technology for the reactions utilizing CO2 for high temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene and finally CO2 reforming of hydrocarbon feedstock (i.e. methane and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However some reactions, such as CO2 reforming of ethanol and glycerol which have not reached industrial scale are also reviewed owing to their great potential in terms of sustainability which are essential as energy for the future. This review further illustrates the building-up of knowledge which shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts which can be adapted for the multiple CO2-related reactions.

  18. Topology optimization for biocatalytic microreactor configurations

    DEFF Research Database (Denmark)

    Pereira Rosinha, Ines; Gernaey, Krist; Woodley, John

    2015-01-01

    The aim of this study is to present an innovative strategy for selecting a reactor for a specific process. Instead of adapting the process to a well-known reactor shape, a topology optimization method is used to obtain the best reactor configuration, and is applied to a biocatalyic reaction system....... The results allow evaluating which regions in the microreactorhave more importance for the product formation. In fact, it was possible to simulate the improvement of the outlet product concentration per same amount of enzyme by modifying the spatial distribution of the immobilized enzyme....

  19. Synthesis of Quinoxaline Derivatives via Tandem Oxidative Azidation/Cyclization Reaction of N-Arylenamines.

    Science.gov (United States)

    Ma, Haichao; Li, Dianjun; Yu, Wei

    2016-02-19

    A new method was developed for the synthesis of quinoxalines. This method employs N-arylenamines and TMSN3 as the starting materials and implements two oxidative C-N bond-forming processes in a tandem pattern by using (diacetoxyiodo)benzene as the common oxidant. The present reaction conditions are mild and simple and thus are useful in practical synthesis.

  20. Optimization of reaction parameters for the electrochemical oxidation of lidocaine with a Design of Experiments approach

    NARCIS (Netherlands)

    Gul, Turan; Bischoff, Rainer; Permentier, Hjalmar

    2015-01-01

    Identification of potentially toxic oxidative drug metabolites is a crucial step in the development of new drugs. Electrochemical methods are useful to study oxidative drug metabolism, but are not widely used to synthesize metabolites for follow-up studies. Careful optimization of reaction parameter

  1. Oxidation as an important factor of protein damage: Implications for Maillard reaction

    Indian Academy of Sciences (India)

    L Trnková; J Dršata; I Boušová

    2015-06-01

    Protein oxidation, the process caused especially by reactive oxygen and nitrogen species, is thought to play a major role in various oxidative processes within cells and is implicated in the development of many human diseases. This review provides a brief overview of the protein oxidation with the emphasis on the types of oxidation (oxidation of protein backbone and amino acid residues side chains, site-specific metal-catalysed protein oxidation), oxidation-dependent generation of protein hydroperoxides, carbonyl derivatives and protein–protein cross-linkages. Non-enzymatic glycoxidation (also known as Maillard reaction) as an important factor of protein damage, consequences of oxidative protein impairment and related diseases as well as means of monitoring and assessment of protein modifications are discussed.

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

    Science.gov (United States)

    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.

  3. Silicone-modified graphene oxide fillers via the Piers-Rubinsztajn reaction

    DEFF Research Database (Denmark)

    Zhang, Jianfeng; Liang, Shuai; Yu, Liyun

    2016-01-01

    While graphene or graphene oxide can make significantimprovements in the properties of a wide variety of polymericmaterials, their incorporation can be challenged byincompatibility with the polymeric matrix. The modification ofgraphene oxide with silicones or silanes using the Piers......-Rubinsztajn reaction improves dispersibility in nonpolar materials,including organic solvents and silicone pre-elastomers. Ahigh loading (up to 10 wt %) of modified graphene oxide insilicone elastomers could be achieved, which resulted inenhanced mechanical performance and reduced gas permeability....

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

    Science.gov (United States)

    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.

  5. Highly efficient oxidation of alcohols using Oxone(R) as oxidant catalyzed by ruthenium complex under mild reaction conditions

    Institute of Scientific and Technical Information of China (English)

    Zi Qiang Lei; Jian Qiang Wang; Peng Hua Yan

    2008-01-01

    Aromatic and alkyl alcohols were oxidized to the corresponding aldehydes or ketones at room temperature with high conversion and selectivity using Oxone (2KHSO5·KHSO4·K2SO4) as oxidant catalyzed by ruthenium complex Quin-Ru-Quin (where Quin = 8-hydroxyquinoline). The reaction time is very short and the preparation of complex is simple. 2008 Zi Qiang Lei. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  6. Investigation of the solid-state reaction between nickel oxide and alumina by Rutherford backscattering (RBS)

    NARCIS (Netherlands)

    Roos, G. de; Geus, John W.; Fluit, J.M.; Wit, J.H. de

    1980-01-01

    The reaction of NiO and Al2O3 to form NiAl2O4 was investigated by means of Rutherford backscattering of 3 MeV He+-ions. The NiO was obtained by oxidation at 900°C of a nickel film vapour-deposited onto alumina substrates. The reaction of NiO and Al2O3 did not proceed markedly at 900°C. The reaction

  7. A methodology for development of biocatalytic processes

    DEFF Research Database (Denmark)

    Lima Ramos, Joana

    -enzymatic process, chiral amine production using Z-transaminase and finally long-chain chiral aliphatic Abstract ii alcohol production by a bi-enzymatic system. For each case study presented, a different tool is used to guide development and evaluate the process when different levels of underlying process knowledge...... are available. The first case study presents a rational approach for defining a development strategy for multi-enzymatic processes. The proposed methodology requires a profound and structured knowledge of the multi-enzyme systems, integrating chemistry, biological and process engineering. In order to suggest......). These process metrics can often be attained by improvements in the reaction chemistry, the biocatalyst, and/or by process engineering, which often requires a complex process development strategy. Interestingly this complexity, which arises from the need for integration of biological and process technologies...

  8. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  9. Amphiphilic Polyphosphazene with Poly(ethylene oxide) Side Chains Prepared through the Decker-Forster Reaction

    Institute of Scientific and Technical Information of China (English)

    LIU Chengmei; HU Fuzhen; QIU Jinjun; LEI Guofu; BAO Rui

    2006-01-01

    Poly(4-methylphenoxyphosphazene)-graft-poly(ethylene oxide) (PPZ-g-PEO), a novel amphiphilic grafting polymer was prepared via the Decker-Forster reaction. It is found that the graft efficiency increased with extension of reaction time. Low molecular weight of poly(ethylene oxide) favored the grafting reaction. The grafted polymer has two different glass transition temperatures(Tg) with those of pure poly(4-methylphenoxy-phopsphazene) and PEO. The emulsifying ability of grafted polymer was studied with benzene-water mixture. The emulsifying volumes increased with the decreasing of PEO's molecular weight. The contact angle of film forming from grafted polymer decreased after introduction of PEO grafting chain.

  10. Hysteresis in the solid oxide fuel cell cathode reaction

    DEFF Research Database (Denmark)

    Jacobsen, Torben; Zachau-Christiansen, Birgit; Bay, Lasse

    2001-01-01

    The oxygen electrode reaction at the Pt/yttria-stabilised zirconia (YSZ) interface is investigated at 1000degreesC on Pt point electrodes on YSZ and YSZ point contacts on Pt. Linear potential sweeps show a pronounced non-linear current-voltage relation and inductive hysteresis, in particular at l...

  11. Evaluation of Salivary Nitric Oxide Levels in Smokers, Tobacco Chewers and Patients with Oral Lichenoid Reactions

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2016-06-01

    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.

  13. Implications of sterically constrained n-butane oxidation reactions on the reaction mechanism and selectivity to 1-butanol

    Science.gov (United States)

    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.

  14. A biocatalytic approach to capuramycin analogues by exploiting a substrate permissive N-transacylase CapW.

    Science.gov (United States)

    Liu, Xiaodong; Jin, Yuanyuan; Cai, Wenlong; Green, Keith D; Goswami, Anwesha; Garneau-Tsodikova, Sylvie; Nonaka, Koichi; Baba, Satoshi; Funabashi, Masanori; Yang, Zhaoyong; Van Lanen, Steven G

    2016-04-28

    Using the ATP-independent transacylase CapW required for the biosynthesis of capuramycin-type antibiotics, we developed a biocatalytic approach for the synthesis of 43 analogues via a one-step aminolysis reaction from a methyl ester precursor as an acyl donor and various nonnative amines as acyl acceptors. Further examination of the donor substrate scope for CapW revealed that this enzyme can also catalyze a direct transamidation reaction using the major capuramycin congener as a semisynthetic precursor. Biological activity tests revealed that a few of the new capuramycin analogues have significantly improved antibiotic activity against Mycobacterium smegmatis MC2 155 and Mycobacterium tuberculosis H37Rv. Furthermore, most of the analogues are able to be covalently modified by the phosphotransferase CapP/Cpr17 involved in self resistance, providing critical insight for future studies regarding clinical development of the capuramycin antimycobacterial antibiotics.

  15. Reduction reaction analysis of nanoparticle copper oxide for copper direct bonding using formic acid

    Science.gov (United States)

    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.

  16. Assessing Effects of Oxidizer Characteristics on Composite Reaction Kinetics

    Science.gov (United States)

    2013-12-01

    these 2 reactants react to form the products shown. For a complete reaction it was necessary to have two oxygen molecules for each methane molecule. A...properties such as high density (13.31 g cm-3) and large neutron capture cross section such that Hf and HfH2 are widely used for nuclear reactor and...volume can be calculated. In this case, plastic work per volume is = = 2 (−) , where Y is the yield strength of the plate

  17. Synthesis of indium tin oxide powder by solid-phase reaction with microwave heating

    OpenAIRE

    Fukui, Kunihiro; Kanayama, Keiji; Katoh, Manabu; Yamamoto, Tetsuya; Yoshida, Hideto

    2009-01-01

    Indium tin oxide (ITO) powder was synthesized from indium oxide and tin oxide powders by a solid-phase method using microwave heating and conventional heating methods. Microwave heating could reduce the treatment time necessary for the completion of the solid-phase reaction by 1/30. This decrease was attributed to an increase in the diffusion rate of Sn at the local heat spot in the indium oxide formed by microwave irradiation. However, microwave heating also decreased the amount of ITO produ...

  18. Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction

    Science.gov (United States)

    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 activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite. ?? 1984.

  19. Role of vanadium in Keggin heteropoly molybdate supported on titania catalysts for oxidation reactions

    Indian Academy of Sciences (India)

    A Srivani; K T Venkateswara Rao; P S Sai Prasad; N Lingaiah

    2014-03-01

    Vanadium-incorporated molybdophosporic acid catalysts supported on titania were prepared and characterized by FT-IR, X-ray diffraction and laser Raman spectroscopy. Characterization data reveals the incorporation of vanadium into the primary structure of Keggin ion of MPA. Catalysts activities were evaluated for oxidation of 1,2-benzenedimethanol using H2O2 and O2 as oxidants. Vanadium-containing catalysts showed high activity compared to their parent heteropoly acids. Oxidation ability depended on the number of V atoms present in Keggin heteropoly molybdate. Effect of reaction parameters on the oxidation ability was also evaluated.

  20. Characterisation of a Recombinant Patchoulol Synthase Variant for Biocatalytic Production of Terpenes.

    Science.gov (United States)

    Frister, Thore; Hartwig, Steffen; Alemdar, Semra; Schnatz, Katharina; Thöns, Laura; Scheper, Thomas; Beutel, Sascha

    2015-08-01

    The patchoulol synthase (PTS) is a multi-product sesquiterpene synthases which is the central enzyme for biosynthesis of patchouli essential oil in the patchouli plant. Sesquiterpene synthases catalyse the formation of various complex carbon backbones difficult to approach by organic synthesis. Here, we report the characterisation of a recombinant patchoulol synthase complementary DNA (cDNA) variant (PTS var. 1), exhibiting significant amino acid exchanges compared to the native PTS. The product spectrum using the natural substrate E,E-farnesyl diphosphate (FDP) as well as terpenoid products resulting from conversions employing alternative substrates was analysed by GC-MS. In respect to a potential use as a biocatalyst, important enzymatic parameters such as the optimal reaction conditions, kinetic behaviour and the product selectivity were studied as well. Adjusting the reaction conditions, an increased patchoulol ratio in the recombinant essential oil was achieved. Nevertheless, the ratio remained lower than in plant-derived patchouli oil. As alternative substrates, several prenyl diposphates were accepted and converted in numerous compounds by the PTS var. 1, revealing its great biocatalytic potential.

  1. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet

    2012-11-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  2. Extensive Bone Reaction From Catastrophic Oxidized Zirconium Wear.

    Science.gov (United States)

    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.

  3. Oxidative catalysis using the stoichiometric oxidant as a reagent: an efficient strategy for single-electron-transfer-induced tandem anion-radical reactions.

    Science.gov (United States)

    Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císařová, Ivana; Klepetářová, Blanka; Jahn, Ullrich

    2014-09-01

    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.

  4. Photocatalytic activity of layered perovskite-like oxides in practically valuable chemical reactions

    Science.gov (United States)

    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.

  5. Measuring the complex behavior of the SO2 oxidation reaction

    Directory of Open Access Journals (Sweden)

    Muhammad Shahzad

    2015-09-01

    Full Text Available The two step reversible chemical reaction involving five chemical species is investigated. The quasi equilibrium manifold (QEM and spectral quasi equilibrium manifold (SQEM are used for initial approximation to simplify the mechanisms, which we want to utilize in order to investigate the behavior of the desired species. They show a meaningful picture, but for maximum clarity, the investigation method of invariant grid (MIG is employed. These methods simplify the complex chemical kinetics and deduce low dimensional manifold (LDM from the high dimensional mechanism. The coverage of the species near equilibrium point is investigated and then we shall discuss moving along the equilibrium of ODEs. The steady state behavior is observed and the Lyapunov function is utilized to study the stability of ODEs. Graphical results are used to describe the physical aspects of measurements.

  6. Surface-catalyzed air oxidation reactions of hydrazines: Tubular reactor studies

    Science.gov (United States)

    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.

  7. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    Science.gov (United States)

    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.

  8. Reaction Mechanism of Thiophene on Vanadium Oxides under FCC Operating Conditions

    Institute of Scientific and Technical Information of China (English)

    Wang Peng; Zheng Aiguo; Tian Huiping; Long Jun

    2004-01-01

    The reaction mechanism of thiophene on vanadium oxides under FCC operating conditions had been preliminary studied using in-situ FT-IR analysis of thiophene and atmospheric pressure continuous fixed-bed reaction, followed by characterization via pyridine adsorption-temperature programmed desorption method, and FT-IR and XPS spectra. The research had discovered that, under 500C thiophene could undergo the redox reaction with V2O5, while being converted into CO, CO2 as well as SO2 with its conversion rate reaching 41.2%. At the same time the oxidation number of vanadium decreased. The existence of a few Bronsted acid centers on V2O5 could lead to an increase of H2S yield among the products derived from the reaction with thiophene.

  9. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Bartling, Stephan, E-mail: stephan.bartling@uni-rostock.de; Meiwes-Broer, Karl-Heinz; Barke, Ingo [Department of Physics, University of Rostock, Universitätsplatz 3, D-18051 Rostock (Germany); Pohl, Marga-Martina [Leibniz-Institut für Katalyse e.V. an der Universität Rostock (LIKAT), Albert-Einstein-Str. 29a, D-18059 Rostock (Germany)

    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.

  10. Reaction Mechanism for m-Xylene Oxidation in the Claus Process by Sulfur Dioxide.

    Science.gov (United States)

    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.

  11. Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

    Science.gov (United States)

    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.

  12. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    Science.gov (United States)

    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

  13. Inclusion property and Diels-Alder reaction of bis (diphenyl-phosphine oxide) butadiyne

    Institute of Scientific and Technical Information of China (English)

    LI, Ming-Xia(李明霞); LI, Jin-Liang(李金亮); WANG, Yong-Mei(王永梅); MENG, Ji-Ben(孟继本)

    2000-01-01

    The host molecule, bis( diphenylphosphine oxide ) butadiyne (2), includes a variety of guests to form five complexes (2a-2e). In addition, the Diels-Alder reaction between 2 and anthracene gives 9, 9', 10, 10'-tetrahedron-9, 9', 10, 10'-bi-ethenoantracene- 11, 11'-bis ( diphenylphosphine oxide ) ( 3 )which is a potential di-π-methane reactant and can undergo photorearrangement.

  14. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    Science.gov (United States)

    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. Influence of reaction parameters on the synthesis of surfactant-assisted tin oxide nanoparticles

    OpenAIRE

    Farrukh, Muhammad Akhyar; ADNAN, Prisca TAN and Rohana

    2012-01-01

    Tin oxide nanoparticles were synthesized via hydrothermal method using a non-ionic surfactant, oleyl amine (OLM), in the presence of urea. The reactions were carried out at different calcination temperatures and varying concentrations of surfactant and urea. The effect of these reaction parameters on the particles' size, distribution, surface area, and the average pore diameter were investigated using X-ray diffraction analysis, transmission electron microscopy, scanning electro...

  16. On the activation energy of the formic acid oxidation reaction on platinum electrodes

    OpenAIRE

    Perales-Rondón, Juan V.; Herrero, Enrique; Feliu, Juan M

    2015-01-01

    A temperature dependent study on the formic acid oxidation reaction has been carried out in order to determine the activation energy of this reaction on different platinum single crystal electrodes, namely Pt(1 0 0), Pt(1 1 1), Pt(5 5 4) and Pt(5 4 4) surfaces. The chronoamperometric transients obtained with pulsed voltammetry have been analyzed to determine the current densities through the active intermediate and the CO formation rate. From the temperature dependency of those parameters, th...

  17. Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

    Science.gov (United States)

    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.

  18. Nonenzymatic Reactions above Phospholipid Surfaces of Biological Membranes: Reactivity of Phospholipids and Their Oxidation Derivatives.

    Science.gov (United States)

    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.

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

    NARCIS (Netherlands)

    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 o

  20. Sulphation reactions of oxidic dust particles in waste heat boiler environment. Literature review

    Energy Technology Data Exchange (ETDEWEB)

    Ranki, T.

    1999-09-01

    Sulphation of metal oxides has an important role in many industrial processes. In different applications sulphation reactions have different aims and characteristics. In the flash smelting process sulphation of oxidic flue dust is a spontaneous and inevitable phenomena, which takes place in the waste heat boiler (WHB) when cooling down hot dust laden off-gases from sulphide smelters. Oxidic dust particles (size 0 - 50 {mu}m) react with O{sub 2} and SO{sub 2} or SO{sub 3} in a certain temperature range (500 - 800 deg C). Sulphation reactions are highly exothermic releasing large amount of heat, which affects the gas cooling and thermal performance of the boiler. Thermodynamics and kinetics of the system have to be known to improve the process and WHB operation. The rate of sulphation is affected by the prevailing conditions (temperature, gas composition) and particle size and microstructure (porosity, surface area). Some metal oxides (CuO) can react readily with SO{sub 2} and O{sub 2} and act as self-catalysts, but others (NiO) require the presence of an external catalyst to enhance the SO{sub 3} formation and sulphation to proceed. Some oxides (NiO) sulphate directly, some (CuO) may form first intermediate phases (basic sulphates) depending on the reaction conditions. Thus, the reaction mechanisms are very complex. The aim of this report was to search information about the factors affecting the dust sulphation reactions and suggested reaction mechanisms and kinetics. Many investigators have studied sulphation thermodynamics and reaction kinetics and mechanisms of macroscopical metal oxide pieces, but only few articles have been published about sulphation of microscopical particles, like dust. All the found microscale studies dealt with sulphation reactions of calcium oxide, which is not present in the flash smelting process, but used as an SO{sub 2} absorbent in the combustion processes. However, also these investigations may give some hints about the sulphation

  1. Ionic Liquid-assisted Synthesis of Polyaniline/Gold Nanocomposite and Its Biocatalytic Application

    Directory of Open Access Journals (Sweden)

    Liu Jingquan

    2008-01-01

    Full Text Available Abstract In this report, a novel chemical synthesis of polyaniline/gold nanocomposite is explored using ionic liquid (IL 1-Butyl-3-methylimidazolium hexafluorophosphate. The direct chemical synthesis of polyaniline/gold nanocomposite was initiated via the spontaneous oxidation of aniline by AuCl4 −in IL. A nearly uniform dispersion of polyaniline/Au particles with a diameter of 450 ± 80 nm was produced by this method, which indicates that this method is more suitable for controlling particle dimensions. It was also found that the electrical conductivity of the polyaniline/gold nanocomposite was more than 100 times higher than that of the pure polyaniline nanoparticles. The polyaniline/gold nanocomposite displays superior function in the biocatalytic activation of microperoxidase-11 because of the high surface area of the assembly and the enhanced charge transport properties of the composite material. We also report the possible application of polyaniline/gold nanocomposite as a H2O2biosensor.

  2. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto

    2016-06-10

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  3. Building carbon-carbon bonds using a biocatalytic methanol condensation cycle.

    Science.gov (United States)

    Bogorad, Igor W; Chen, Chang-Ting; Theisen, Matthew K; Wu, Tung-Yun; Schlenz, Alicia R; Lam, Albert T; Liao, James C

    2014-11-11

    Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C-C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through (13)C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives.

  4. Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

    Science.gov (United States)

    Burkhardt, M; Koschack, T; Busch, G

    2015-02-01

    A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven.

  5. Catalytic Reaction Synthesis for the Partial Oxidation of Methane to Formaldehyde.

    Science.gov (United States)

    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

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

    OpenAIRE

    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 enz...

  7. Promotional effect of upper Ru oxides as methanol tolerant electrocatalyst for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Montiel, M.; Hernandez-Fernandez, P.; Ocon, P. [Departamento de Quimica-Fisica Aplicada C-II, Campus UAM, 28049 Madrid (Spain); Fierro, J.L.G.; Rojas, S. [Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie 2, 28049 Madrid (Spain)

    2009-06-15

    The role of Ru on the oxygen reduction reaction in the presence of methanol has been investigated. To this end a series of carbon supported Pt based electrocatalysts containing Ru and Co have been prepared and thoroughly characterized. The catalytic performance on the oxygen reduction reaction (ORR) both in the presence and in the absence of methanol by linear sweep voltammetry on rotating disk electrode has been studied. In spite of its documented ability towards methanol and CO oxidation, when Ru-containing catalysts are subjected to excursions to potentials more positive than 0.8 V vs. NHE they develop a certain tolerance to the presence of methanol. This feature is attributed to the formation of upper oxide Ru species that impede the methanol oxidation reaction to occur under the typical reaction conditions of the oxygen reduction process, i.e. potentials more positive than 0.7 V vs. NHE and oxygen saturated atmospheres. The evolution of Ru species with the applied potential has been investigated by XPS, identifying the presence of upper oxidized Ru phases. (author)

  8. In vitro mimicry of metabolic oxidation reactions by electrochemistry/mass spectrometry

    NARCIS (Netherlands)

    Jurva, U; Wikstrom, HV; Bruins, AP

    2000-01-01

    The aim of these studies was to investigate the scope and limitations of electrochemistry on-line with mass spectrometry as a quick and convenient way to mimic phase I:oxidative reactions in drug metabolism. A compound with previously reported in vitro and in vivo metabolism, the dopamine agonist 2-

  9. Oxidation induced ionization and reactions of metal carbide clusters (Nb, Zr, V, Ta)

    Science.gov (United States)

    Deng, H. T.; Kerns, K. P.; Bell, R. C.; Castleman, A. W.

    1997-11-01

    Following our recent report of the oxidation induced formation of Ti8C12+ (H.T. Deng, K.P. Kerns, and A.W. Castleman, Jr., J. Chem. Phys. 104 (1996) 4862), the oxidation induced ionization of niobium and zirconium carbide clusters are studied using a triple quadrupole mass spectrometer coupled with a laser induced plasma reaction source. It was found that reactions of both of these neutral carbide clusters with dioxygen leads to formation of carbide ions. The ion product distributions show that zirconium carbide clusters mainly take the form of Met--Car cations, but niobium carbide clusters favor a cubic-like crystalline pattern. Furthermore, reactions of mass-selected NbxCy+ with dioxygen result in a sequential loss of C2 units from NbxCy+, and leads to formation of Nbx+ and NbxC+ depending on y being an even or odd number. However, NbxCy+ shows comparably low reactivity towards nitrous oxide through a single oxygen abstraction mechanism. In comparison with the reaction products of VxCy+ with dioxygen, the complementary information obtained in the present study suggests that the C2 unit is a basic building block for formation of small early transition metal carbide clusters. The oxidation induced ionization mechanisms are also discussed in relation with the stability, ionization potentials, and structures of the clusters.

  10. Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Vojvodic, Aleksandra

    2015-01-01

    We study the interface between adsorbed water and stoichiometric, defect-free (110) rutile oxide surfaces of TiO2, RuO2, and IrO2 in order to understand how water influences the stabilities of the intermediates of the oxygen evolution reaction (OER). In our model the water is treated as explicitl...

  11. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    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…

  12. Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Carla F. Pereira

    2016-10-01

    Full Text Available Porphyrin-based Metal-Organic Frameworks (Por-MOFs constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

  13. Surface electronic structure and isomerization reactions of alkanes on some transition metal oxides

    Science.gov (United States)

    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.

  14. Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

    Science.gov (United States)

    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.

  15. On the biologic role of the reaction of NO with oxidized cytochrome c oxidase.

    Science.gov (United States)

    Antunes, Fernando; Boveris, Alberto; Cadenas, Enrique

    2007-10-01

    The inhibition of cytochrome c oxidase (CcOX) by nitric oxide (NO) is analyzed with a mathematical model that simulates the metabolism in vivo. The main results were the following: (a) We derived novel equations for the catalysis of CcOX that can be used to predict CcOX inhibition in any tissue for any [NO] or [O(2)]; (b) Competitive inhibition (resulting from the reversible binding of NO to reduced CcOX) emerges has the sole relevant component of CcOX inhibition under state 3 in vivo; (c) In state 4, contribution of uncompetitive inhibition (resulting from the reaction of oxidized CcOX with NO) represents a significant nonmajority fraction of inhibition, being favored by high [O(2)]; and (d) The main biologic role of the reaction between NO and oxidized CcOX is to consume NO. By reducing [NO], this reaction stimulates, rather than inhibits, respiration. Finally, we propose that the biologic role of NO as an inhibitor of CcOX is twofold: in state 4, it avoids an excessive buildup of mitochondrial membrane potential that triggers rapid production of oxidants, and in state 3, increases the efficiency of oxidative phosphorylation by increasing the ADP/O ratio, supporting the therapeutic use of NO in situations in which mitochondria are dysfunctional.

  16. Iron(III Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions

    Directory of Open Access Journals (Sweden)

    Susana L. H. Rebelo

    2016-04-01

    Full Text Available 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(TPFPPCl], and the use of [Fe(TPFPPCl] as an oxidation catalyst in green conditions. The preparations of H2TPFPP and [Fe(TPFPPCl] 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(IIIporphyrin 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.

  17. Effect of magnetic field on the zero valent iron induced oxidation reaction.

    Science.gov (United States)

    Kim, Dong-hyo; Kim, Jungwon; Choi, Wonyong

    2011-08-30

    The magnetic field (MF) effect on the zero valent iron (ZVI) induced oxidative reaction was investigated for the first time. The degradation of 4-chlorophenol (4-CP) in the ZVI system was employed as the test oxidative reaction. MF markedly enhanced the degradation of 4-CP with the concurrent production of chlorides. The consumption of dissolved O(2) by ZVI reaction was also enhanced in the presence of MF whereas the competing reaction of H(2) production from proton reduction was retarded. Since the ZVI-induced oxidation is mainly driven by the in situ generated hydroxyl radicals, the production of OH radicals was monitored by the spin trap method using electron spin resonance (ESR) spectroscopy. It was confirmed that the concentration of trapped OH radicals was enhanced in the presence of MF. Since both O(2) and Fe(0) are paramagnetic, the diffusion of O(2) onto the iron surface might be accelerated under MF. The magnetized iron can attract oxygen on itself, which makes the mass transfer process faster. As a result, the surface electrochemical reaction between Fe(0) and O(2) can be accelerated with the enhanced production of OH radicals. MF might retard the recombination of OH radicals as well.

  18. Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

    Science.gov (United States)

    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.

  19. Spectrophotometric Method for the Determination of Oxidative IonsWith Decoloring Reaction Using HCPCF

    Institute of Scientific and Technical Information of China (English)

    KOU Zongyan; NIU Jiwei; WANG Shuwen; GONG Xiaoming; KOU Mingze

    2001-01-01

    @@ HCPCF is a color reagent for the determination of vanadium, zinc and magnesium, etc. To the best of our knowledge, no work on the decoloring reaction for analytical use of HCPCF for the determination of oxidative anions has been report. In this work, we found that some oxidative anions can oxidize HCPCF in acid medium, forming a colorless product. In addition, surfactant was used in this work, because of the low solubility of HCPCF in aqueous solutions. The purpose of this work is to establish a new, rapid and simple spectrophotometric method for the determination of NO2-, BrO3-,IO3-, IO4-and Cr2O7-based on the reaction between HCPCF and analytes in the presence of emulsion OP.

  20. Spectrophotometric Method for the Determination of Oxidative IonsWith Decoloring Reaction Using HCPCF

    Institute of Scientific and Technical Information of China (English)

    KOU; Zongyan

    2001-01-01

    HCPCF is a color reagent for the determination of vanadium, zinc and magnesium, etc. To the best of our knowledge, no work on the decoloring reaction for analytical use of HCPCF for the determination of oxidative anions has been report. In this work, we found that some oxidative anions can oxidize HCPCF in acid medium, forming a colorless product. In addition, surfactant was used in this work, because of the low solubility of HCPCF in aqueous solutions. The purpose of this work is to establish a new, rapid and simple spectrophotometric method for the determination of NO2-, BrO3-,IO3-, IO4-and Cr2O7-based on the reaction between HCPCF and analytes in the presence of emulsion OP.……

  1. Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water.

    Science.gov (United States)

    Wols, B A; Hofman-Caris, C H M

    2012-06-01

    Emerging organic contaminants (pharmaceutical compounds, personal care products, pesticides, hormones, surfactants, fire retardants, fuel additives etc.) are increasingly found in water sources and therefore need to be controlled by water treatment technology. UV advanced oxidation technologies are often used as an effective barrier against organic contaminants. The combined operation of direct photolysis and reaction with hydroxyl radicals ensures good results for a wide range of contaminants. In this review, an overview is provided of the photochemical reaction parameters (quantum yield, molar absorption, OH radical reaction rate constant) of more than 100 organic micropollutants. These parameters allow for a prediction of organic contaminant removal by UV advanced oxidation systems. An example of contaminant degradation is elaborated for a simplified UV/H(2)O(2) system.

  2. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang

    2014-11-01

    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  3. Oxidation of triclosan by ferrate: Reaction kinetics, products identification and toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Yang Bin [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Ying Guangguo, E-mail: guang-guo.ying@csiro.au [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhao Jianliang; Zhang Lijuan; Fang Yixiang [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Nghiem, Long Duc [School of Civil Mining and Environmental Engineering, University of Wollongong, Wollongong, NSW 2522 (Australia)

    2011-02-15

    Research highlights: {yields} Triclosan reacted rapidly with ferrate. {yields} Oxidation resulted in a decrease in algal toxicity. {yields} No inhibition of algae growth from ferrate. - Abstract: The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0-10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC-MS and RRLC-MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k{sub app}, being 754.7 M{sup -1} s{sup -1} at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7({+-}1.9) x 10{sup 2} M{sup -1} s{sup -1}, while that measured for anionic triclosan was 7.6({+-}0.6) x 10{sup 3} M{sup -1} s{sup -1}. The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth.

  4. Effect of magnetic field on the zero valent iron induced oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong-hyo; Kim, Jungwon [School of Environmental Science and Engineering, Pohang University of Scienceand Technology (POSTECH), Pohang 790-784 (Korea, Republic of); Choi, Wonyong, E-mail: wchoi@postech.edu [School of Environmental Science and Engineering, Pohang University of Scienceand Technology (POSTECH), Pohang 790-784 (Korea, Republic of)

    2011-08-30

    Highlights: {yields} We investigate the zero valent iron induced oxidation in the presence of magnetic field. {yields} The oxidative degradation of 4-chlorophenol is enhanced by the magnetic field. {yields} ESR measurement confirms that more OH radicals are generated in the presence of magnetic field. {yields} The magnetic field affects the mass transfer of O{sub 2} and the recombination of radicals. - Abstract: The magnetic field (MF) effect on the zero valent iron (ZVI) induced oxidative reaction was investigated for the first time. The degradation of 4-chlorophenol (4-CP) in the ZVI system was employed as the test oxidative reaction. MF markedly enhanced the degradation of 4-CP with the concurrent production of chlorides. The consumption of dissolved O{sub 2} by ZVI reaction was also enhanced in the presence of MF whereas the competing reaction of H{sub 2} production from proton reduction was retarded. Since the ZVI-induced oxidation is mainly driven by the in situ generated hydroxyl radicals, the production of OH radicals was monitored by the spin trap method using electron spin resonance (ESR) spectroscopy. It was confirmed that the concentration of trapped OH radicals was enhanced in the presence of MF. Since both O{sub 2} and Fe{sup 0} are paramagnetic, the diffusion of O{sub 2} onto the iron surface might be accelerated under MF. The magnetized iron can attract oxygen on itself, which makes the mass transfer process faster. As a result, the surface electrochemical reaction between Fe{sup 0} and O{sub 2} can be accelerated with the enhanced production of OH radicals. MF might retard the recombination of OH radicals as well.

  5. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  6. Electrochemical reaction and oxidation of lecithin under pulsed electric fields (PEF) processing.

    Science.gov (United States)

    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.

  7. Lipoxidation products as biomarkers of oxidative damage to proteins during lipid peroxidation reactions.

    Science.gov (United States)

    Requena, J R; Fu, M X; Ahmed, M U; Jenkins, A J; Lyons, T J; Thorpe, S R

    1996-01-01

    Oxidative stress is implicated in the pathogenesis of numerous disease processes including diabetes mellitus, atherosclerosis, ischaemia reperfusion injury and rheumatoid arthritis. Chemical modification of amino acids in protein during lipid peroxidation results in the formation of lipoxidation products which may serve as indicators of oxidative stress in vivo. The focus of the studies described here was initially to identify chemical modifications of protein derived exclusively from lipids in order to assess the role of lipid peroxidative damage in the pathogenesis of disease. Malondialdehye (MDA) and 4-hydroxynonenal (HNE) are well characterized oxidation products of polyunsaturated fatty acids on low-density lipoprotein (LDL) and adducts of these compounds have been detected by immunological means in atherosclerotic plaque. Thus, we first developed gas chromatography-mass spectrometry assays for the Schiff base adduct of MDA to lysine, the lysine-MDA-lysine diimine cross-link and the Michael addition product of HNE to lysine. Using these assays, we showed that the concentrations of all three compounds increased significantly in LDL during metal-catalysed oxidation in vitro. The concentration of the advanced glycation end-product N epsilon-(carboxymethyl)lysine (CML) also increased during LDL oxidation, while that of its putative carbohydrate precursor the Amadori compound N epsilon-(1-deoxyfructose-1-yl)lysine did not change, demonstrating that CML is a marker of both glycoxidation and lipoxidation reactions. These results suggest that MDA and HNE adducts to lysine residues should serve as biomarkers of lipid modification resulting from lipid peroxidation reactions, while CML may serve as a biomarker of general oxidative stress resulting from both carbohydrate and lipid oxidation reactions.

  8. Mathematical modeling of an exothermic leaching reaction system: pressure oxidation of wide size arsenopyrite participates

    Science.gov (United States)

    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.

  9. Surface Reaction Kinetics of Steam- and CO2-Reforming as Well as Oxidation of Methane over Nickel-Based Catalysts

    OpenAIRE

    Karla Herrera Delgado; Lubow Maier; Steffen Tischer; Alexander Zellner; Henning Stotz; Olaf Deutschmann

    2015-01-01

    An experimental and kinetic modeling study on the Ni-catalyzed conversion of methane under oxidative and reforming conditions is presented. The numerical model is based on a surface reaction mechanism consisting of 52 elementary-step like reactions with 14 surface and six gas-phase species. Reactions for the conversion of methane with oxygen, steam, and CO2 as well as methanation, water-gas shift reaction and carbon formation via Boudouard reaction are included. The mechanism is implemented i...

  10. Supercritical water oxidation of Quinazoline: Effects of conversion parameters and reaction mechanism.

    Science.gov (United States)

    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. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  12. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    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. © 2015 American Chemical Society.

  13. Gas-Solid Reaction Route toward the Production of Intermetallics from Their Corresponding Oxide Mixtures

    Directory of Open Access Journals (Sweden)

    Hesham Ahmed

    2016-08-01

    Full Text Available Near-net shape forming of metallic components from metallic powders produced in situ from reduction of corresponding pure metal oxides has not been explored to a large extent. Such a process can be probably termed in short as the “Reduction-Sintering” process. This methodology can be especially effective in producing components containing refractory metals. Additionally, in situ production of metallic powder from complex oxides containing more than one metallic element may result in in situ alloying during reduction, possibly at lower temperatures. With this motivation, in situ reduction of complex oxides mixtures containing more than one metallic element has been investigated intensively over a period of years in the department of materials science, KTH, Sweden. This review highlights the most important features of that investigation. The investigation includes not only synthesis of intermetallics and refractory metals using the gas solid reaction route but also study the reaction kinetics and mechanism. Environmentally friendly gases like H2, CH4 and N2 were used for simultaneous reduction, carburization and nitridation, respectively. Different techniques have been utilized. A thermogravimetric analyzer was used to accurately control the process conditions and obtain reaction kinetics. The fluidized bed technique has been utilized to study the possibility of bulk production of intermetallics compared to milligrams in TGA. Carburization and nitridation of nascent formed intermetallics were successfully carried out. A novel method based on material thermal property was explored to track the reaction progress and estimate the reaction kinetics. This method implies the dynamic measure of thermal diffusivity using laser flash method. These efforts end up with a successful preparation of nanograined intermetallics like Fe-Mo and Ni-W. In addition, it ends up with simultaneous reduction and synthesis of Ni-WN and Ni-WC from their oxide mixtures

  14. Self-assembled platinum nanoflowers on polydopamine-coated reduced graphene oxide for methanol oxidation and oxygen reduction reactions.

    Science.gov (United States)

    Yu, Xueqing; Wang, Huan; Guo, Liping; Wang, Liang

    2014-11-01

    The morphology- and size-controlled synthesis of branched Pt nanostructures on graphene is highly favorable for enhancing the electrocatalytic activity and stability of Pt. Herein, a facile approach is developed for the efficient synthesis of well-dispersed Pt nanoflowers (PtNFs) on the surface of polydopamine (PDA)-modified reduced graphene oxide (PDRGO), denoted as PtNFs/PDRGO, in high yield. The synthesis was performed by a simple heating treatment of an aqueous solution that contained K2PtCl4 and PDA-modified graphene oxide (GO) without the need for any additional reducing agent, seed, surfactant, or organic solvent. The coated PDA serves not only as a reducing agent, but also as cross-linker to anchor and stabilize PtNFs on the PDRGO support. The as-prepared PtNFs/PDRGO hybrid, with spatially and locally separated PtNFs on PDRGO, exhibits superior electrocatalytic activity and stability toward both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline solutions.

  15. Adsorption and reaction of silver on an oxidized Si(0 0 1) surface

    Energy Technology Data Exchange (ETDEWEB)

    Ohno, S., E-mail: sohno@ynu.ac.jp [Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501 (Japan); Tanaka, H. [Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501 (Japan); Takahashi, K.; Kamada, M. [Synchrotron Light Application Center, Saga University, Honjo 1, Saga 840-8502 (Japan); Tanaka, M. [Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501 (Japan)

    2015-08-15

    Highlights: • Electronic states associated with silver adsorption processes on oxidized silicon surfaces were investigated. • Characterization of oxide thin films on Si surfaces was performed using photoelectron spectroscopy with synchrotron radiation. • The changes in the Si 2p oxide components upon silver adsorption are ascribed to charge transfer rather than a conformation change. - Abstract: The adsorption and reaction of silver on an oxidized Si(0 0 1) surface were investigated on the basis of Si 2p, Ag 3d and O 1s core-level photoemission measurements at room temperature (RT). We compared the present results with those obtained in the case of titanium in our previous study. We found that silver on an oxidized Si(0 0 1) surface at RT causes a reduction in the intensity of the Si{sup 1+} and Si{sup 2+} states and an increase in the intensity of the Si{sup 3+} and Si{sup 4+} states. Based on an analysis of the Ag 3d and O 1s states, we concluded that the change in the Si 2p oxidized states upon silver adsorption is due to charge transfer rather than conformation change, although the applicability of the charge transfer scheme may be dependent on the thickness of the silver layer. We also deduced that penetration of silver atoms through a thin silicon oxide film occurs.

  16. Novel Stereoselective Synthesis of (E)-α,β-Unsaturated Esters by the Tandem Reaction of Deprotonation-Oxidation-Wittig Reaction from Phosphonium and Arsonium Salt

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Phosphonium or arsonium salt 1 can undergo the tandem reaction of deprotonation -oxidation-Wittig reaction with alcohol 2 in the presence of sodium hydroxide and manganese dioxide, which affords a general simplified method for the stereoselective synthesis of (E)-α,β-unsaturated esters 3.

  17. Reaction behavior between the oxide film of LY12 aluminum alloy and the flux

    Institute of Scientific and Technical Information of China (English)

    薛松柏; 董健; 吕晓春; 顾文华

    2004-01-01

    In this paper, the brazing mechanism of LY12 aluminum alloy at middle range temperature was presented. The CsF-AlF3 non-corrosive flux was utilized to remove the complex oxide film on the surface of LY12 aluminum alloy. The results revealed that the oxide film was removed by the improved CsF-AlF3 flux accompanied with the occurrence of reaction as well as dissolution and the compounds CsF played an important role to remove the oxide film. Actually, the high activity of flux, say, the ability to remove the oxide film, was due to the presence of the compounds, such as NH4F,NH4AlF4 and composite molten salt. The production of HF was the key issue to accelerate the reaction and enhance to eliminate the oxide film by dissolution. It was found that the rare earth element La at small percentage was not enriched at the interface. Moreover, the rare earth fluoride enhanced the dissolution behavior.

  18. Enhancing the biocatalytic manufacture of the key intermediate of atorvastatin by focused directed evolution of halohydrin dehalogenase

    Science.gov (United States)

    Luo, Yu; Chen, Yangzi; Ma, Hongmin; Tian, ZhenHua; Zhang, Yeqi; Zhang, Jian

    2017-01-01

    Halohydrin dehalogenases (HHDHs) are biocatalytically interesting enzymes due to their ability to form C-C, C-N, C-O, and C-S bonds. One of most important application of HHDH was the protein engineering of HheC (halohydrin dehalogenase from Agrobacterium radiobacter AD1) for the industrial manufacturing of ethyl (R)-4-cyano-3-hydroxybutanoate (HN), a key chiral synthon of a cholesterol-lowering drug of atorvastatin. During our development of an alternative, more efficient and economic route for chemo-enzymatic preparation of the intermediate of atorvastatin, we found that the HheC2360 previously reported for HN manufacture, had insufficient activity for the cyanolysis production of tert-butyl (3 R,5 S)-6-cyano-3,5-dihydroxyhexanoate (A7). Herein, we present the focused directed evolution of HheC2360 with higher activity and enhanced biocatalytic performance using active site mutagenesis. Through docking of the product, A7, into the crystal structure of HheC2360, 6 residues was selected for combined active sites testing (CASTing). After library screening, the variant V84G/W86F was identified to have a 15- fold increase in activity. Time course analysis of the cyanolysis reaction catalyzed by this variant, showed 2- fold increase in space time productivity compared with HheC2360. These results demonstrate the applicability of the variant V84G/W86F as a biocatalyst for the efficient and practical production of atorvastatin intermediate. PMID:28165015

  19. Methanol oxidation in a flow reactor: Implications for the branching ratio of the CH3OH+OH reaction

    DEFF Research Database (Denmark)

    Rasmussen, Christian Lund; Wassard, K.H.; Dam-Johansen, Kim;

    2008-01-01

    The oxidation of methanol in a flow reactor has been studied experimentally under diluted, fuel-lean conditions at 650-1350 K, over a wide range of O-2 concentrations (1%-16%), and with and without the presence of nitric oxide. The reaction is initiated above 900 K, with the oxidation rate...

  20. Plasmon-enhanced reverse water gas shift reaction over oxide supported Au catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Upadhye, AA; Ro, I; Zeng, X; Kim, HJ; Tejedor, I; Anderson, MA; Dumesic, JA; Huber, GW

    2015-01-01

    We show that localized surface plasmon resonance (LSPR) can enhance the catalytic activities of different oxide-supported Au catalysts for the reverse water gas shift (RWGS) reaction. Oxide-supported Au catalysts showed 30 to 1300% higher activity for RWGS under visible light compared to dark conditions. Au/TiO2 catalyst prepared by the deposition-precipitation (DP) method with 3.5 nm average Au particle size showed the highest activity for the RWGS reaction. Visible light is converted into chemical energy for this reaction with up to a 5% overall efficiency. A shift in the apparent activation energy (from 47 kJ mol(-1) in dark to 35 kJ mol(-1) in light) and apparent reaction order with respect to CO2 (from 0.5 in dark to 1.0 in light) occurs due to the LSPR. Our kinetic results indicate that the LSPR increases the rate of either the hydroxyl hydrogenation or carboxyl decomposition more than any other steps in the reaction network.

  1. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    Science.gov (United States)

    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.

  2. Efficient oxidation of benzyl alcohol with heteropolytungstate as reaction-controlled phase-transfer catalyst

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.

  3. Substrate activation for O2 reactions by oxidized metal centers in biology.

    Science.gov (United States)

    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.

  4. Interfacial reaction between the oxidized SiC particles and Al-Mg alloys

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The interfacial reactions of oxidized SiC particles reinforced Al-Mg matrix composites were investigated by the field emission-scanning electron microscopy (FE- SEM), TEM and X-ray diffraction. It was found that the nanoscale MgO forms initially due to the interfacial reaction, then whether it reacts with molten Al continuously or not depends on the content of Mg in the matrix and its covering densification at the surface of particles. When there is not enough Mg in the matrix for the formation of dense MgO layer, MgO will transform into MgAl2O4 crystal owing to the continuous reaction with SiO2 and molten Al. When dense MgO layer forms at the surface of the particles due to the affluence of Mg for the initial reaction, it will protect the inner SiC from the attack of molten Al. However, the reaction products of both MgO and MgAl2O4 are thermo-stable phases at the surface of the particles under high temperature. The results clarify the interfacial reaction route and they are of great value to the control of the interfacial reactions and their interfacial design of the composites.

  5. Biocatalytic nerve agent detoxification in fire fighting foams.

    Science.gov (United States)

    LeJeune, K E; Russell, A J

    1999-03-20

    Current events across the globe necessitate rapid technological advances to combat the epidemic of nerve agent chemical weapons. Biocatalysis has emerged as a viable tool in the detoxification of organophosphorus neurotoxins, such as the chemical weapons VX and sarin. Efficient detoxification of contaminated equipment, machinery, and soils are of principal concern. This study describes the incorporation of a biocatalyst (organophosphorus hydrolase, E.C. 3.1.8.1) into conventional formulations of fire fighting foam. The capacity of fire fighting foams to decrease volatilization of contained contaminants, increase surface wettability, and control the rate of enzyme delivery to large areas makes them useful vehicles for enzyme application at surfaces. The performance of enzyme containing foams has been shown to be not only reproducible but also predictable. An empirical model provides reasonable estimations for the amounts of achievable surface decontamination as a function of the important parameters of the system. Theoretical modeling illustrates that the enzyme-containing foam is capable of extracting agent from the surface and is catalytically active at the foam-surface interface and throughout the foam itself. Biocatalytic foam has proven to be an effective, "environmentally friendly" means of surface and soil decontamination.

  6. A Study on Side Reactions of Hydroxyethylation of 3-Nitro-4-chlorobenzenesulfinic Acid with Ethylene Oxide

    Institute of Scientific and Technical Information of China (English)

    Zhen Tang DONG; Zu Wang WU; Zhi Wei WANG; Yun De WANG; Yin Zhou YU

    2006-01-01

    The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-(β-hydroxyethylsulfonyl)chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chlorobenzenesulfinic acid to form the target product, 2-nitro-4-(β-hydroxyethylsulfonyl)chlorobenzene, there presented three kinds of side reactions: 1. Condensation and elimination of HCl to form biphenyl sulfone derivatives; 2. Addition to give bisulfonyl ethane derivative via vinyl sulfone; and 3. Hydroxylethylation on O-atom to produce hydroxylethylsulfinate due to the tautomerism of sulfinic acid.

  7. Nitrile Oxide-Norbornene Cycloaddition as a Bioorthogonal Crosslinking Reaction for the Preparation of Hydrogels.

    Science.gov (United States)

    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.

  8. Theoretical study of the dark-oxidation reaction mechanisms for organic polymers

    Science.gov (United States)

    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.

  9. Effect of Ni Loading and Reaction Conditions on Partial Oxidation of Methane to Syngas

    Institute of Scientific and Technical Information of China (English)

    Haitao Wang; Zhenhua Li; Shuxun Tian

    2003-01-01

    The partial oxidation of methane to synthesis gas is studied in this paper over Ni/Al2O3 catalysts under atmospheric pressure. The effects of Ni loading on the activity and stability of catalysts with 5 mm α-Al2O3 and θ-Al2O3 pellets as supports were measured in a continuous fixed bed reactor. It is found that the optimum Ni loading is 10%. And the effect of reaction conditions on partial oxidation of methane is also studied. The methane conversion and CO selectivity increase with the increase of the reaction temperature and the space velocity on 10%Ni/α-Al2O3 catalysts. The best CH4/O2 mole ratio is 2 for CO selectivity, and the optimum space velocity is 5.4×105 h-1.

  10. Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. Dependence of reaction rate of pyrite oxidation on temperature, pH and oxidant concentration

    Institute of Scientific and Technical Information of China (English)

    LU; Long; WANG; Rucheng; XUE; Jiyue; CHEN; Fanrong; CHEN; J

    2005-01-01

    The kinetic sstudy of pyrite oxidation was performed in a series of experiments by a mixed flow reactor. The release rates of Fe(II) are in the order of 3.22×10-9-5.51×10-7 mol·m-2·s-1 at temperature (T ) 25 to 44℃, initial pH (pH )1.4 to 2.7, and initial Fe(III) concentration ([Fe(III)]I) 10-5 to 5×10-3 mol·kg-1. The release rate of Fe(II) increased with increasing T or/and pH or/and [Fe(III)]I in the above range. The rate law and activation energy of pyrite oxidation were derived by statistical analyses of Rfe(II) vs. [Fe(III)]I, Rfe(II) vs. pH and Rfe(II) vs. T, and are given as (1) Rate law: Rfe(II)=104.65e-64.54×103/8.31T[Fe(III)]i0.6./[H+]0.45 ; (2) activation energy: 64.54 ( 8.07 kJ·mol-1. The expression can be applied to more cases (e.g., quantifying the pollutant released from sulfide-rich mining waste and assessing reliable performance of underground repository sites where pyrite acts as an engineered barrier material). Using the rate law derived from this study, the magnitude of the pollutants transferred to secondary phases, soil and water from oxidized pyrite during Jiguanshan mine waste weathering was preliminarily estimated. The estimated magnitude is very high, suggesting that the pile has possibly posed significant impact on the water quality in this region.

  12. Oxidative stress and leukocyte migration inhibition response in cutaneous adverse drug reactions

    Directory of Open Access Journals (Sweden)

    Prashant Verma

    2012-01-01

    Full Text Available Background: Cutaneous adverse drug reactions (CADRs may either be immunological or non-immunological. The precise mechanisms, however, are largely obscure. Other concomitant mechanisms may amplify and/or contribute to the severity and duration of a reaction. One such mechanism could be oxidative stress, a state of imbalance between reactive oxygen species, and their subsequent detoxification by antioxidants. Aims: (a to assess the oxidative stress status in the blood of cutaneous drug reaction patients by assaying for reduced glutathione (GSH and malondialdehyde (MDA levels, (b to determine the leukocyte migration inhibition (LMI response in these patients in response to the suspected drug (s, and (c to look for the association between oxidative stress parameters and LMI. Methods: Ethical committee approval was obtained for this study. Fresh venous blood samples were obtained from the patients of CADRs (group A during the acute phase of reaction and healthy control subjects (group B. MDA levels, a measure of oxidative lipid damage, and reduced GSH levels, a measure of anti-oxidant capacity, were assayed in the blood samples of both groups using spectrophotometry. LMI response was measured by challenging the patients′ peripheral blood mononuclear cells with the suspected drug to confirm immunological perturbation. Results: Totally 66 participants, 33 cases in group A and equal number of controls in group B, were studied. The mean MDA levels were found to be raised (P < 0.001, but GSH levels were significantly reduced in group A when compared with group B (P = <0.001. LMI response against drug(s was performed in 33 cases (group A, out of which 25 cases showed a positive LMI response as follows: fixed drug eruption (10/25, SJS (5/25, urticaria (3/25, exfoliative dermatitis (2/25, morbilliform rash (2/25, erythroderma (1/25, vasculitis (1/25, and dapsone syndrome (1/25. The mean MDA levels were found to be significantly higher in the LMI positive

  13. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    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. Quantum Diffusion-Controlled Chemistry: Reactions of Atomic Hydrogen with Nitric Oxide in Solid Parahydrogen.

    Science.gov (United States)

    Ruzi, Mahmut; Anderson, David T

    2015-12-17

    Our group has been working to develop parahydrogen (pH2) matrix isolation spectroscopy as a method to study low-temperature condensed-phase reactions of atomic hydrogen with various reaction partners. Guided by the well-defined studies of cold atom chemistry in rare-gas solids, the special properties of quantum hosts such as solid pH2 afford new opportunities to study the analogous chemical reactions under quantum diffusion conditions in hopes of discovering new types of chemical reaction mechanisms. In this study, we present Fourier transform infrared spectroscopic studies of the 193 nm photoinduced chemistry of nitric oxide (NO) isolated in solid pH2 over the 1.8 to 4.3 K temperature range. Upon short-term in situ irradiation the NO readily undergoes photolysis to yield HNO, NOH, NH, NH3, H2O, and H atoms. We map the postphotolysis reactions of mobile H atoms with NO and document first-order growth in HNO and NOH reaction products for up to 5 h after photolysis. We perform three experiments at 4.3 K and one at 1.8 K to permit the temperature dependence of the reaction kinetics to be quantified. We observe Arrhenius-type behavior with a pre-exponential factor of A = 0.036(2) min(-1) and Ea = 2.39(1) cm(-1). This is in sharp contrast to previous H atom reactions we have studied in solid pH2 that display definitively non-Arrhenius behavior. The contrasting temperature dependence measured for the H + NO reaction is likely related to the details of H atom quantum diffusion in solid pH2 and deserves further study.

  15. An improved understanding of the reaction of bis(bromomethyl)quinoxaline 1-N-oxides with amines using substituent effects.

    Science.gov (United States)

    Evans, Kathryn M; Slawin, Alexandra M Z; Lebl, Tomas; Philp, Douglas; Westwood, Nicholas J

    2007-04-27

    The reaction of bis(bromomethyl)quinoxaline N-oxides with amines is interesting from a reaction mechanism perspective and due to the reported biological activity of compounds in this general class. The complex mechanism of this reaction (particularly in the case of primary amines) is complicated further when C6 or C7 substituted mono-N-oxides are considered. In this study, the synthesis and subsequent characterization of a series of 2,3-bis(bromomethyl)quinoxaline 1-N-oxides is reported. Experimental and computational evidence is used to show that the observed product ratios from the reaction with diethylamine reflect the influence of both the C6/C7 substituent and the N-oxide functional group on the initial nucleophilic substitution reaction.

  16. Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage.

    Science.gov (United States)

    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.

  17. Surface reaction mechanisms during ozone and oxygen plasma assisted atomic layer deposition of aluminum oxide.

    Science.gov (United States)

    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.

  18. The Effect of Anodic Oxide Films on the Nickel-Aluminum Reaction in Aluminum Braze Sheet

    Science.gov (United States)

    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.

  19. Substrate Oxidation by Indoleamine 2,3-Dioxygenase: EVIDENCE FOR A COMMON REACTION MECHANISM.

    Science.gov (United States)

    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.

  20. Facile synthesis of PdSx/C porous nanospheres and their applications for ethanol oxidation reaction

    Science.gov (United States)

    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.

  1. Catalytic activity of copper (II) oxide prepared via ultrasound assisted Fenton-like reaction.

    Science.gov (United States)

    Angı, Arzu; Sanlı, Deniz; Erkey, Can; Birer, Özgür

    2014-03-01

    Copper (II) oxide nanoparticles were synthesized in an ultrasound assisted Fenton-like aqueous reaction between copper (II) cations and hydrogen peroxide. The reactions were initiated with the degradation of hydrogen peroxide by ultrasound induced cavitations at 0 °C or 5 °C and subsequent generation of the OH radical. The radical was converted into hydroxide anion in Fenton-like reactions and copper hydroxides were readily converted to oxides without the need of post annealing or aging of the samples. The products were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) surface area analysis. Catalytic activity of the nanoparticles for the hydrogen peroxide assisted degradation of polycyclic aromatic hydrocarbons in the dark was tested by UV-visible spectroscopy with methylene blue as the model compound. The rate of the reaction was first order, however the rate constants changed after the initial hour. Initial rate constants as high as 0.030 min(-1) were associated with the high values of surface area, i.e. 70 m(2)/g. Annealing of the products at 150 °C under vacuum resulted in the decrease of the catalytic activity, underlying the significance of the cavitation induced surface defects in the catalytic process.

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

    Science.gov (United States)

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

    2016-09-01

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

  3. Photoinduced Oxidation Reaction of Benzotrifluoride with OH Radical by the Laser Flash Method

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Ren-Xi; YE,Zhao-Lian; SHEN,Yan; DONG,Wen-Bo; HOU,Hui-Qi

    2008-01-01

    The optical transient and kinetics characterizations of the transients formed in the reaction of OH with benzotrifluoride (BTF) were performed by a laser flash photolysis technique. The results indicated that the formation of π-type adduct of C6H5(OH)CF3 was the major reaction channel, and the σ-type adduct of C6H5CF3OH formation was an additional minor process in the oxidation reaction of BTF attacked by OH radicals yielded from the photolysis of H2O2. Addition of OH to the CF3 group led to the fluoride ion elimination to yield α,α-difluorophenylcarbinol (C6H5CF2OH). Trifluoromethylphenol (HOC6H4CF3) of meta-, para- and ortho-substituted isomers resulted from the addition of OH to the BTF aromatic ring.

  4. Self propagating high temperature synthesis of metal oxides. Reactions in external magnetic fields

    CERN Document Server

    Aguas, M D

    2001-01-01

    The preparation of metal oxides by Self-Propagating High-Temperature Synthesis is reported. The reactions are started with a point source of ignition; typically a hot wire. A synthesis wave is observed moving out from the point source and reactions terminate in seconds. Products obtained can be classified into ferrites (magnetic applications) and stannates (gas sensing applications). Ferrites were synthesised under variable external magnetic fields. The synthesis wave is hotter in the presence of an external magnetic field for hard ferrite synthesis. For spinel ferrites the opposite was observed. Materials synthesised in the field show differences in their bulk magnetic properties (coercivity and saturation magnetisation), structures and microstructures. Combustion reactions in large fields revealed changes in unit cell volume (shrinkage was observed for hard ferrites while expansion was observed for spinel ferrites). SHS synthesised hard ferrites show two distinct components; one has large grain structure co...

  5. Reaction of cyclodextrins with propylene oxide or with glycidol: analysis of product distribution.

    Science.gov (United States)

    Pitha, J; Szabo, L; Fales, H M

    1987-11-01

    Reaction of cyclomalto-hexaose, -heptaose, or -octaose with propylene oxide in strong aqueous alkali gave products in which distribution of the degrees of substitution was relatively narrow and nearly symmetrical, and increased with the average degree of substitution. When an equimolar mixture of cyclomalto-hexaose, heptaose, or -octaose was used, the average degrees of substitution of all three carbohydrates were close to each other. These findings indicate that the reactivities of the hydroxyl groups of cyclomalto-hexaose, -heptaose, or -octaose, and of all their (2-hydroxypropyl) ethers formed in the reactions, are quite similar. Reaction of cyclomaltoheptaose with glycidol also yielded a product having a narrow distribution of degree of substitution, but which was slightly skewed towards the higher degrees. Thus, as it proceeds, this etherification leads to products having higher reactivity towards the epoxide.

  6. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  7. The Photochemical Oxidation of Siderite That Drove Hydrogen Based Microbial Redox Reactions in The Archean Biosphere

    Science.gov (United States)

    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

  8. Gold-TiO{sub 2}-Nickel catalysts for low temperature-driven CO oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Hinojosa-Reyes, Mariana, E-mail: kittyhinojosa@hotmail.com [División de Materiales Avanzados, IPICYT, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa San José 2055 Col. Lomas 4a. sección C.P. 78216, San Luis Potosí, S.L.P., México (Mexico); Zanella, Rodolfo, E-mail: rodolfo.zanella@ccadet.unam.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior S/N, Ciudad Universitaria, A. P. 70-186, Delegación Coyoacán, C.P. 04510, México D. F., México (Mexico); Maturano-Rojas, Viridiana [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior S/N, Ciudad Universitaria, A. P. 70-186, Delegación Coyoacán, C.P. 04510, México D. F., México (Mexico); and others

    2016-04-15

    Graphical abstract: - Highlights: • Nickel-doped TiO{sub 2} catalysts (1 wt. %) drive the CO oxidation at low temperature. • DRIFTS reveals the participation of nickel during the CO oxidation. • Ni(CO){sub 2} bridged species are detected by DRIFTS. • Au/TiO{sub 2}-Ni 1 is the most active and stable catalyst with respect to undoped TiO{sub 2}. • Ti{sup 3+} species corroborate Ni doped TiO{sub 2} and surface oxygen vacancies. - Abstract: Nickel-doped-TiO{sub 2} 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, N{sub 2} physisorption, STEM-HAADF microscopy and TPR hydrogen consumption. The Au/TiO{sub 2}-Ni catalysts were evaluated catalytically performing CO oxidation reactions. The catalyst with nickel content of 1 wt. % (Au/TiO{sub 2}-Ni 1) showed the highest CO conversion with respect to the high-nickel-content or bare/commercial TiO{sub 2} 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/TiO{sub 2}-Ni 1 catalyst in comparison with the Au/TiO{sub 2} one. The oxygen vacancies that were created on the sol–gel-doped TiO{sub 2} improved the catalytic behavior during the performance of CO oxidation reactions, and inhibited the AuNP sintering.

  9. Oxidation of microcystins by permanganate: reaction kinetics and implications for water treatment.

    Science.gov (United States)

    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.

  10. Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction.

    Science.gov (United States)

    Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

    2013-04-21

    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˙ 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.

  11. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Energy Technology Data Exchange (ETDEWEB)

    Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland)

    1996-12-31

    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  12. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling.

    Science.gov (United States)

    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.

  13. A novel mechanism for the oxidation reaction of VO2+ on a graphite electrode in acidic solutions

    Science.gov (United States)

    Wang, Wenjun; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei; Zeng, Chaoliu

    2014-09-01

    With the consideration of optimizing the performance of the all-vanadium redox flow battery (VRB), the oxidation reaction mechanism of VO2+ on a rotating graphite disk electrode has been investigated by potentiodynamic polarization in sulfuric acid solutions with various pH and vanadium concentrations. Furthermore, the reaction orders of VO2+ and H+ for the oxidation reaction of VO2+ have been calculated from the polarization results and compared with the theoretical results according to the possible reaction mechanisms available in the literature. However, a new oxidation reaction mechanism has been proposed to describe the oxidation of VO2+ at last, and the theoretic reaction orders of VO2+ and H+ based on the new mechanism are consistent with the experimental results when the electrochemical reaction is the rate-limited process. Moreover, a corresponding kinetic equation has been established for the oxidation reaction of VO2+ on a spectroscopically pure graphite electrode, and can be well used to predict the polarization behavior in V (IV) acidic solutions.

  14. The analysis of magnesium oxide hydration in three-phase reaction system

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

    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.

  15. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl

    2015-01-01

    of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided in an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore both NO and NH3...... are required in the reduction, and, nally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst, by combining in situ X-ray absorption spectrosocpy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....

  16. Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides.

    Science.gov (United States)

    Björkbacka, Åsa; Yang, Miao; Gasparrini, Claudia; Leygraf, Christofer; Jonsson, Mats

    2015-09-28

    One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO˙). Both H2O2 and HO˙ are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO˙ are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

  17. Abnormal Reactions of Free Radicals and Oxidative Damages in the Bodies of Patients With Chronic Glomerulonephritis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Objective To study the abnormal reactions of a series of free radicals and the oxidative damages induced by free radical abnormal reactions in the bodies of patients with chronic glomerulonephritis. Methods Eighty chronic glomerulonephritis patients (CGNP) and eighty healthy adult volunteers (HAV) were enrolled in a random control study, in which concentrations of nitric oxide (NO) in plasma, lipoperoxides (LPO) in plasma and in erythrocytes, and vitamin C (VC),vitamin E (VE) and beta-carotene (β-CAR) in plasma as well as activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX) in erythrocytes were determined with spectrophotometric assays. Results Compared with the average values of the above biochemical parameters in the HAV group, the average values of NO in plasma, and LPO in plasma and erythrocytes in the CGNP group were significantly increased (P = 0.0001), while those of VC, VE and β-CAR in plasma as well as those of SOD, CAT and GPX in erythrocytes in the CGNP group were significantly decreased (P = 0.0001). Pearson product-moment correlation analysis showed that with increase of the concentration of blood creatinine as well as prolongation of the course of disease in the CGNP, the concentrations of NO in plasma, and LPO in plasma and erythrocytes in the CGNP increased gradually, while the concentrations of VC, VE and β-CAR in plasma as well as the activities of SOD, CAT and GPX in erythrocytes in the CGNP decreased gradually (P = 0.002454 - 0.000001).The relative risk ratio (RR) of the above biochemical parameters reflecting oxidative damages in the bodies of CGNP ranged from 6.061 to 72.429. The reliability coefficient (alpha) that the above biochemical parameters were used to reflect the oxidative damages of the CGNP was 0.8137,standardized item alpha = 0.9728, Hotelling's T-Squared = 1135680.191, F = 53274.6478, P =0.000001. Conclusions The findings irt this study show that in the bodies of CGNP a series of free

  18. Gold-TiO2-Nickel catalysts for low temperature-driven CO oxidation reaction

    Science.gov (United States)

    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.

  19. Biocatalytic potential of laccase-like multicopper oxidases from Aspergillus niger

    NARCIS (Netherlands)

    Tamayo Ramos, J.A.; Berkel, van W.J.H.; Graaff, de L.H.

    2012-01-01

    BACKGROUND: Laccase-like multicopper oxidases have been reported in several Aspergillus species but they remain uncharacterized. The biocatalytic potential of the Aspergillus niger fungal pigment multicopper oxidases McoA and McoB and ascomycete laccase McoG was investigated. RESULTS: The laccase-li

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

    Science.gov (United States)

    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. Characteristics of the oxygen evolution reaction on synthetic copper - cobalt - oxide electrodes for water electrolysis

    Science.gov (United States)

    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.

  2. Iron oxide and pyrocatechol: a spectroscopy study of the reaction products

    Directory of Open Access Journals (Sweden)

    Wagner José Barreto

    2006-12-01

    Full Text Available The reaction of 1,2-dihydroxy-benzene (pyrocatechol (C6H6O2 with iron oxide (Fe2O3 and sodium thiosulfate (Na2S2O3 in aqueous medium (pH 7 was investigated. Pyrocatechol suffers autoxidation and coordinates with Fe3+ in solution. The presence of S2O3(2- in solution was fundamental to generate and stabilize the pyrocatechol oxidation products as o-semiquinones. This compound was isolated and its structure characterized using FT-IR, EPR and UV-Vis Spectroscopy as [CTA][Fe(SQ2(Cat]. A thermal mass loss mechanism was proposed based on Thermogravimetric Analysis (TG to support the structural characterization.

  3. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction

    Science.gov (United States)

    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.

  4. Characterization of Titanium Oxide Nanoparticles Obtained by Hydrolysis Reaction of Ethylene Glycol Solution of Alkoxide

    Directory of Open Access Journals (Sweden)

    Naofumi Uekawa

    2012-01-01

    Full Text Available Transparent and stable sols of titanium oxide nanoparticles were obtained by heating a mixture of ethylene glycol solution of titanium tetraisopropoxide (TIP and a NH3 aqueous solution at 368 K for 24 h. The concentration of NH3 aqueous solution affected the structure of the obtained titanium oxide nanoparticles. For NH3 aqueous solution concentrations higher than 0.2 mol/L, a mixture of anatase TiO2 nanoparticles and layered titanic acid nanoparticles was obtained. The obtained sol was very stable without formation of aggregated precipitates and gels. Coordination of ethylene glycol to Ti4+ ions inhibited the rapid hydrolysis reaction and aggregation of the obtained nanoparticles. The obtained titanium oxide nanoparticles had a large specific surface area: larger than 350 m2/g. The obtained titanium oxide nanoparticles showed an enhanced adsorption towards the cationic dye molecules. The selective adsorption corresponded to presence of layered titanic acid on the obtained anatase TiO2 nanoparticles.

  5. Catalytic methanation reaction over supported nickel-rhodium oxide for purification of simulated natural gas

    Institute of Scientific and Technical Information of China (English)

    Wan Azelee Wan Abu Bakar; Rusmidah Ali; Susilawati Toemen

    2011-01-01

    In this research,new catalyst with high industrial impact is developed,which can catalyze the conversion of CO2 to methane through methanation reaction.A series of catalysts based on nickel oxide were prepared using wetness impregnation technique and ageing,followed by calcination at 400 ℃.Rh/Ni (30∶70)/Al2O3 catalyst was revealed as the most potential catalyst based on the results of catalytic activity measurementmonitored by Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography (GC).The results showed 90.1% CO2 conversion and 70.8% yield at 400 ℃.

  6. The direct oxidative diene cyclization and related reactions in natural product synthesis

    Directory of Open Access Journals (Sweden)

    Juliane Adrian

    2016-09-01

    Full Text Available The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (diastereoselective 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.

  7. Radiolytic reactions of nitro blue tetrazolium under oxidative and reductive conditions: a pulse radiolysis study

    Science.gov (United States)

    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.

  8. Innovative Catalysis in Organic Synthesis Oxidation, Hydrogenation, and C-X Bond Forming Reactions

    CERN Document Server

    Andersson, Pher G

    2012-01-01

    Authored by a European team of leaders in the field, this book compiles innovative approaches for C-X bond forming processes frequently applied in organic synthesis. It covers all key types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is focused on the improvement of efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation and cross-coupling reactions.The result is a valuable resource for both advanced researchers in academia and industry, as well a

  9. Investigation of reaction conditions on morphology and optical properties of Zinc Oxide Nanorods

    Science.gov (United States)

    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.

  10. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

  11. Temperature dependence of the heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    Science.gov (United States)

    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.

  12. Kinetic stabilization against the oxidation reaction induced by a silaalkane cage in a thiophene-bridged molecular gyroscope.

    Science.gov (United States)

    Setaka, Wataru; Ohmizu, Soichiro; Kira, Mitsuo

    2014-02-01

    Macrocage molecules with a bridged rotor have been synthesized as molecular gyroscopes. The kinetics of the oxidation reaction of the thiophene-bridged molecular gyroscope, whose thiophene ring was bridged inside a silaalkane cage, was investigated. A remarkable kinetic stabilization against the oxidation of the thiophene moiety induced by the molecular cage framework was observed.

  13. Enhanced reversibility and durability of a solid oxide Fe-air redox battery by carbothermic reaction derived energy storage materials.

    Science.gov (United States)

    Zhao, Xuan; Li, Xue; Gong, Yunhui; Huang, Kevin

    2014-01-18

    The recently developed solid oxide metal-air redox battery is a new technology capable of high-rate chemistry. Here we report that the performance, reversibility and stability of a solid oxide iron-air redox battery can be significantly improved by nanostructuring energy storage materials from a carbothermic reaction.

  14. Reaction intermediates in the catalytic Gif-type oxidation from nuclear inelastic scattering

    Science.gov (United States)

    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.

  15. Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment.

    Directory of Open Access Journals (Sweden)

    Ruijuan Qu

    Full Text Available 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.

  16. Ultrasmooth reaction-sintered silicon carbide surface resulting from combination of thermal oxidation and ceria slurry polishing.

    Science.gov (United States)

    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.

  17. pH-Controlled Oxidation of an Aromatic Ketone: Structural Elucidation of the Products of Two Green Chemical Reactions

    Science.gov (United States)

    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…

  18. Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Bruheim, I.; Haugsgjerd, B.O.;

    2014-01-01

    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 ass......, the formation of pyrroles might help to protect the krill oil against lipid oxidation. © 2014 Elsevier Ltd. All rights reserved....

  19. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    Science.gov (United States)

    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.

  20. Heteropolymolybdate as a New Reaction-controlled Phase-transfer Catalyst for Efficient Alcohol Oxidation with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    Zhi Huan WENG; Jin Yan WANG; Xi Gao JIAN

    2006-01-01

    A new catalytic process for the synthesis of aldehyde from alcohol by oxidation with H2O2 with high selectivity was studied. In this system, heteropolymolybdate [C7H7N(CH3)3]3{PO4[MoO(O2)2]4} was utilized as the reaction-controlled phase-transfer catalyst to catalyze oxidation of benzyl and aliphatic alcohols. The molar ratio of H2O2 and alcohol was 0.75, no other by-products were detected by gas chromatography, the results of oxidation reaction indicated that the catalyst has high activity and stability.

  1. The analysis of magnesium oxide hydration in three-phase reaction system

    Science.gov (United States)

    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)2 precipitation, Mg(OH)2 peeling off from MgO particle and leaving behind fresh MgO surface.

  2. Imaging the oxidation effects of the Fenton reaction on phospholipids at the interface between aqueous phase and thermotropic liquid crystals.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  4. Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions and novel technologies

    Directory of Open Access Journals (Sweden)

    Frank eSchreiber

    2012-10-01

    Full Text Available Nitrous oxide (N2O is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH or the reduction of nitrite (NO2- to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO2- to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria. In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO2-, NH2OH and nitroxyl (HNO. Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser based absorption spectroscopy. In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build-up.

  5. Oxidation and nitration of tyrosine by ozone and nitrogen dioxide: reaction mechanisms and biological and atmospheric implications.

    Science.gov (United States)

    Sandhiya, L; Kolandaivel, P; Senthilkumar, K

    2014-04-01

    The nitration of tyrosine by atmospheric oxidants, O3 and NO2, is an important cause for the spread of allergenic diseases. In the present study, the mechanism and pathways for the reaction of tyrosine with the atmospheric oxidants O3 and NO2 are studied using DFT-M06-2X, B3LYP, and B3LYP-D methods with the 6-311+G(d,p) basis set. The energy barrier for the initial oxidation reactions is also calculated at the CCSD(T)/6-31+G(d,p) level of theory. The reaction is studied in gas, aqueous, and lipid media. The initial oxidation of tyrosine by O3 proceeds by H atom abstraction and addition reactions and leads to the formation of six different intermediates. The subsequent nitration reaction is studied for all the intermediates, and the results show that the nitration affects both the side chain and the aromatic ring of tyrosine. The rate constant of the favorable oxidation and nitration reaction is calculated using variational transition state theory over the temperature range of 278-350 K. The spectral properties of the oxidation and nitration products are calculated at the TD-M06-2X/6-311+G(d,p) level of theory. The fate of the tyrosine radical intermediate is studied by its reaction with glutathione antioxidant. This study provides an enhanced understanding of the oxidation and nitration of tyrosine by O3 and NO2 in the context of improving the air quality and reducing the allergic diseases.

  6. Metallic oxides for desulphurization catalyst reaction; Oxidos metalicos mistos como catalisadores para reacoes de dessulfurizacao

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, R.L.B.A.; Melo, D.M.A.; Melo, M.A.F. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil); Souza, K.S.G.M. [Universidade Federal da Paraiba - Departamento de Engenharia Quimica, PB (Brazil); Barros, J.M.F. [Universidade Federal de Campina Grande - Campos Cuite, PB (Brazil)

    2010-07-01

    The mixed metal oxides constitute an important class of catalytic materials widely investigated in different fields of applications. Studies of rare earth nickelates have been carried by several researchers in order to investigate the structural stability afforded by oxide formed and the existence of catalytic properties at room temperature. So, this study aims synthesize the nano sized catalyst of nickelate of lanthanum doped with strontium (La(1- x)Sr{sub x}NiO4-{sigma}; x = 0,2 and 0,3), through the Pechini method and your characterization for subsequent application in the desulfurization of thiophene reaction. The precursor solutions were calcined at 300 degree C/2h for pyrolysis of polyester and later calcinations occurred at temperatures of 500 - 1000 degree C. The resulting powders were characterized by thermogravimetric analysis (TG / DTG), surface area for adsorption of N{sub 2} by BET method, Xray diffraction (XRD), scanning electron microscopy (HR{sub S}EM) and spectrometry dispersive energy (EDS). The results of XRD had show that the perovskites obtained consist of two phases (LSN and NiO) and from 700 degree C have crystalline structure. The results of SEM evidenced the obtainment of nano metric powders. The results of BET show that the powders have surface area within the range used in catalysis (5-50m{sup 2}/g). The characterization of active sites was performed by reaction of desulfurization of thiophene at room temperature and 200 degree C, the relation F/W equal to 0,7 mol h{sup -1}m{sub c}at {sup -1}. The products of the reaction were separated by gas chromatography and identified by the selective detection PFPD sulfur. All samples had presented conversion above 95%. (author)

  7. New insights into atrazine degradation by cobalt catalyzed peroxymonosulfate oxidation: kinetics, reaction products and transformation mechanisms.

    Science.gov (United States)

    Ji, Yuefei; Dong, Changxun; Kong, Deyang; Lu, Junhe

    2015-03-21

    The widespread occurrence of atrazine in waters poses potential risk to ecosystem and human health. In this study, we investigated the underlying mechanisms and transformation pathways of atrazine degradation by cobalt catalyzed peroxymonosulfate (Co(II)/PMS). Co(II)/PMS was found to be more efficient for ATZ elimination in aqueous solution than Fe(II)/PMS process. ATZ oxidation by Co(II)/PMS followed pseudo-first-order kinetics, and the reaction rate constant (k(obs)) increased appreciably with increasing Co(II) concentration. Increasing initial PMS concentration favored the decomposition of ATZ, however, no linear relationship between k(obs) and PMS concentration was observed. Higher efficiency of ATZ oxidation was observed around neutral pH, implying the possibility of applying Co(II)/PMS process under environmental realistic conditions. Natural organic matter (NOM), chloride (Cl(-)) and bicarbonate (HCO3(-)) showed detrimental effects on ATZ degradation, particularly at higher concentrations. Eleven products were identified by applying solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC/MS) techniques. Major transformation pathways of ATZ included dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation. Detailed mechanisms responsible for these transformation pathways were discussed. Our results reveal that Co(II)/PMS process might be an efficient technique for remediation of groundwater contaminated by ATZ and structurally related s-triazine herbicides.

  8. The borohydride oxidation reaction on La-Ni-based hydrogen-storage alloys.

    Science.gov (United States)

    Paschoalino, Waldemir J; Thompson, Stephen J; Russell, Andrea E; Ticianelli, Edson A

    2014-07-21

    This work provides insights into the processes involved in the borohydride oxidation reaction (BOR) in alkaline media on metal hydride alloys formed by LaNi(4.7)Sn(0.2)Cu(0.1) and LaNi(4.78)Al(0.22) with and without deposited Pt, Pd, and Au. The results confirm the occurrence of hydrolysis of the borohydride ions when the materials are exposed to BH(4)(-) and a continuous hydriding of the alloys during BH(4)(-) oxidation measurements at low current densities. The activity for the direct BOR is low in both bare metal hydride alloys, but the rate of the BH(4)(-) hydrolysis and the hydrogen-storage capacity are higher, while the rate of H diffusion is slower for bare LaNi(4.78) Al(0.22). The addition of Pt and Pd to both alloys results in an increase of the BH(4)(-) hydrolysis, but the H(2) formed is rapidly oxidized at the Pt-modified catalysts. In the case of Au modification, a small increase in the BH(4)(-) hydrolysis is observed as compared to the bare alloys. The presence of Au and Pd also leads to a reduction of the rates of alloy hydriding/de-hydriding.

  9. Experimental and theoretical studies of the reaction between cationic vanadium oxide clusters and acetylene

    Institute of Scientific and Technical Information of China (English)

    YIN Shi; MA YanPing; DU Lin; HE ShengGui; GE MaoFa

    2008-01-01

    The time of flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor was adopted to study the reactivity of cationic vanadium oxide clusters (VmO+n) toward acetylene (C2H2) molecules under gas phase (P, ~ 1.14 kPa), under near room temperature (T, ~ 350 K) conditions. Association products, VmOnC2H+2 (m,n = 2,4; 2,6; 3,7-8; 4,9-11; 5,12-13;6,13-16, and 7,17), are observed. The oxidation of C2H2 by (V2O5)+n, (n = 1-3) is experimentally identified.The reactivity of (V2O5)+n decreases as n increases. Density functional theory (DFT) calculations were carried out to interpret the reaction mechanisms. The DFT results indicate that a terminal oxygen atom from V2O+5 can transfer overall barrierlessly to C2H2 at room temperature, which is in agreement with the experimental observation. Other experimental results such as the observation of V2O6C2H+2 and nonobservation of V2O7,8C2H+2 in the experiments are also well interpreted based on the DFT calculations.The reactivity of vanadium oxide clusters toward acetylene and other hydrocarbons may be considered in identifying molecular level mechanisms for related heterogeneous catalysis.

  10. Oxidation reactions of 1,3-diphenylpropane-1,3-dione

    Indian Academy of Sciences (India)

    Medha Rele; B S Patro; S Adhikari; G P Kalena; S Chattopadhyay; T Mukherjee

    2002-12-01

    The free radical scavenging properties and possible antioxidant activity of 1,3-diphenylpropane-1,3-dione (1) are reported. Pulse radiolysis technique was employed to study the one-electron oxidation of 1 with various radicals viz. CCl3O$_{2}^{\\bullet}$, N$_{3}^{\\bullet}$ and ${}^{\\bullet}$OH in homogeneous aqueous solution. All these radicals reacted with 1 under ambient conditions at almost diffusion controlled rates producing transient species with an absorption maximum around 420 nm that decayed at first order rates. The transient absorption peak was shifted in the case of CCl3OO$^{\\bullet}$ radical reaction with 1 due to change in the polarity of the medium. Formation of a stable product with a broad absorption band starting from 400 nm and cut off at 230 nm was observed in the oxidation of 1 with ${}^{\\bullet}$OH and ${}^{\\bullet}$N3 radicals. In a biological system also, 1 showed significant inhibitory activity against Fe2+-mediated lipid peroxidation. Based on these observations, a suitable mechanism for the oxidation of 1 has been proposed.

  11. Changes to the chemical composition of soot from heterogeneous oxidation reactions.

    Science.gov (United States)

    Browne, Eleanor C; Franklin, Jonathan P; Canagaratna, Manjula R; Massoli, Paola; Kirchstetter, Thomas W; Worsnop, Douglas R; Wilson, Kevin R; Kroll, Jesse H

    2015-02-19

    The atmospheric aging of soot particles, in which various atmospheric processes alter the particles' chemical and physical properties, is poorly understood and consequently is not well-represented in models. In this work, soot aging via heterogeneous oxidation by OH and ozone is investigated using an aerosol flow reactor coupled to a new high-resolution aerosol mass spectrometric technique that utilizes infrared vaporization and single-photon vacuum ultraviolet ionization. This analytical technique simultaneously measures the elemental and organic carbon components of soot, allowing for the composition of both fractions to be monitored. At oxidant exposures relevant to the particles' atmospheric lifetimes (the equivalent of several days of oxidation), the elemental carbon portion of the soot, which makes up the majority of the particle mass, undergoes no discernible changes in mass or composition. In contrast, the organic carbon (which in the case of methane flame soot is dominated by aliphatic species) is highly reactive, undergoing first the addition of oxygen-containing functional groups and ultimately the loss of organic carbon mass from fragmentation reactions that form volatile products. These changes occur on time scales comparable to those of other nonoxidative aging processes such as condensation, suggesting that further research into the combined effects of heterogeneous and condensational aging is needed to improve our ability to accurately predict the climate and health impacts of soot particles.

  12. Effect of calcination temperature and reaction conditions on methane partial oxidation using lanthanum-based perovskite as oxygen donor

    Institute of Scientific and Technical Information of China (English)

    DAI Xiaoping; YU Changchun; LI Ranjia; WU Qiong; SHI Kaijiao; HAO Zhengping

    2008-01-01

    We investigated the effect of calcination temperature, reaction temperature, and different amounts of replenished lattice oxygen on the partial oxidation of methane (POM) to synthesis gas using perovskite-type LaFeO3 oxide as oxygen donor instead of gaseous oxygen, which was prepared by the sol-gel method, and the oxides were characterized by XRD, TG/DTA, and BET. The results indicated that the particle size increased with the calcination temperature increasing, while BET and CH4 conversion declined with the calcination temperature increasing using LaFeO3 oxide as oxygen donor in the absence of gaseous oxygen. CO selectivity remained at a high level such as above 92%, and increased slightly as the calcination temperature increased. Exposure of LaFeO3 oxides to methane atmosphere enhanced the oxygen migration of in the bulk with time online owing to the loss of lattice oxygen and reduction of the oxidative stated Fe ion simultaneously. The high reaction temperature was favorable to the migration of oxygen species from the bulk toward the surface for the synthesis gas production with high CO selectivity. The product distribution and evolution for POM by sequential redox reaction was determined by amounts of replenished lattice oxygen with gaseous oxygen. The optimal process should decline the total oxidation of methane, and increase the selectivity of partial oxidation of methane.

  13. Effect of atmospheric oxidative plasma treatments on polypropylenic fibers surface: Characterization and reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Nisticò, Roberto, E-mail: roberto.nistico@unito.it [University of Torino, Department of Chemistry and NIS Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Magnacca, Giuliana [University of Torino, Department of Chemistry and NIS Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Faga, Maria Giulia; Gautier, Giovanna [CNR-IMAMOTER, Strada delle Cacce 73, 10135 Torino (Italy); D’Angelo, Domenico; Ciancio, Emanuele [Clean-NT Lab, Environment Park S.p.A., Via Livorno 60, 10144 Torino (Italy); Lamberti, Roberta; Martorana, Selanna [Herniamesh S.r.l., Via F.lli Meliga 1/C, 10034 Chivasso (Italy)

    2013-08-15

    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/O{sub 2}, He/O{sub 2}/H{sub 2}O) under three different values of applied power (750, 1050, 1400 W) were investigated. The formed plasma species (O{sub 2}{sup +}, 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.

  14. Nanoporous and highly active silicon carbide supported CeO₂-catalysts for the methane oxidation reaction.

    Science.gov (United States)

    Hoffmann, Claudia; Biemelt, Tim; Lohe, Martin R; Rümmeli, Mark H; Kaskel, Stefan

    2014-01-29

    CeOx @SiO2 nanoparticles are used for the first time for the generation of porous SiC materials with tailored pore diameter in the mesopore range containing encapsulated and catalytically active CeO2 nanoparticles. The nanocasting approach with a preceramic polymer and subsequent pyrolysis is performed at 1300 °C, selective leaching of the siliceous part results in CeOx /SiC catalysts with remarkable characteristics like monodisperse, spherical pores and specific surface areas of up to 438 m(2) ·g(-1) . Porous SiC materials are promising supports for high temperature applications. The catalysts show excellent activities in the oxidation of methane with onset temperatures of the reaction 270 K below the onset of the homogeneous reaction. The synthesis scheme using core-shell particles is suited to functionalize silicon carbide with a high degree of stabilization of the active nanoparticles against sintering in the core of the template even at pyrolysis temperatures of 1300 °C rendering the novel synthesis principle as an attractive approach for a wide range of catalytic reactions.

  15. An analytical model of hydrogen evolution and oxidation reactions on electrodes partially covered with a catalyst.

    Science.gov (United States)

    Kemppainen, Erno; Halme, Janne; Lund, Peter D

    2016-05-11

    Our previous theoretical study on the performance limits of the platinum (Pt) nanoparticle catalyst for the hydrogen evolution reaction (HER) had shown that the mass transport losses at a partially catalyst-covered planar electrode are independent of the catalyst loading. This suggests that the two-dimensional (2D) numerical model used could be simplified to a one-dimensional (1D) model to provide an easier but equally accurate description of the operation of these HER electrodes. In this article, we derive an analytical 1D model and show that it indeed gives results that are practically identical to the 2D numerical simulations. We discuss the general principles of the model and how it can be used to extend the applicability of existing electrochemical models of planar electrodes to low catalyst loadings suitable for operating photoelectrochemical devices under unconcentrated sunlight. Since the mass transport losses of the HER are often very sensitive to the H2 concentration, we also discuss the limiting current density of the hydrogen oxidation reaction (HOR) and how it is not necessarily independent of the reaction kinetics. The results give insight into the interplay of kinetic and mass-transport limitations at HER/HOR electrodes with implications for the design of kinetic experiments and the optimization of catalyst loadings in the photoelectrochemical cells.

  16. Size-Dependent Electrocatalytic Activity of Free Gold Nanoparticles for the Glucose Oxidation Reaction.

    Science.gov (United States)

    Hebié, Seydou; Napporn, Teko W; Morais, Cláudia; Kokoh, K Boniface

    2016-05-18

    Understanding the fundamental relationship between the size and the structure of electrode materials is essential to design catalysts and enhance their activity. Therefore, spherical gold nanoparticles (GNSs) with a mean diameter from 4 to 15 nm were synthesized. UV/Vis spectroscopy, transmission electron microscopy, and under-potential deposition of lead (UPDPb ) were used to determine the morphology, size, and surface crystallographic structure of the GNSs. The UPDPb revealed that their crystallographic facets are affected by their size and the growth process. The catalytic properties of these GNSs toward glucose electrooxidation were studied by cyclic voltammetry, taking into account the scan rate and temperature effects. The results clearly show the size-dependent electrocatalytic activity for glucose oxidation reactions that are controlled by diffusion. Small GNSs with an average size of 4.2 nm exhibited high catalytic activity. This drastic increase in activity results from the high specific area and reactivity of the surface electrons induced by their small size. The reaction mechanism was investigated by in situ Fourier transform infrared reflectance spectroscopy. Gluconolactone and gluconate were identified as the intermediate and the final reaction product, respectively, of the glucose electrooxidation.

  17. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.

    2014-04-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

  18. Superior long-term activity for a Pt-Re alloy compared to Pt in methanol oxidation reactions

    Science.gov (United States)

    Duke, Audrey S.; Xie, Kangmin; Monnier, John R.; Chen, Donna A.

    2017-03-01

    Pt-Re bimetallic catalysts have shown enhanced activity compared to pure Pt for reactions involving oxidation, but the origins of this improved activity are not fully understood. Methanol oxidation on a Pt-Re alloy surface and pure Pt foil was studied in a microreactor coupled to an ultrahigh vacuum chamber. For reaction at 60 °C, the Pt-Re alloy surface exhibits superior long-term activity over a 24 h reaction period compared to pure Pt. The initial activity of Pt is 10-15% higher than on Pt-Re; however, the Pt surface gradually loses activity after 10 h online, whereas the activity of Pt-Re does not diminish. Post-reaction XPS shows that more carbon accumulates on the Pt than on Pt-Re, and the improved long-term activity is attributed to a greater ability of Pt-Re to oxidize the carbonaceous intermediates that eventually poison active sites. Both Pt and Pt-Re surfaces have almost no activity for methanol oxidation until a minimum coverage of oxygen is achieved from O2 dissociation. A comparison with methanol oxidation studies on Pt and Pt-Re in a pressure regime that is 150 times lower than in this work demonstrates that more carbon and less oxygen accumulate on the surfaces during reaction at the lower pressures.

  19. Highly active iridium/iridium-tin/tin oxide heterogeneous nanoparticles as alternative electrocatalysts for the ethanol oxidation reaction.

    Science.gov (United States)

    Du, Wenxin; Wang, Qi; Saxner, David; Deskins, N Aaron; Su, Dong; Krzanowski, James E; Frenkel, Anatoly I; Teng, Xiaowei

    2011-09-28

    Ethanol is a promising fuel for low-temperature direct fuel cell reactions due to its low toxicity, ease of storage and transportation, high-energy density, and availability from biomass. However, the implementation of ethanol fuel cell technology has been hindered by the lack of low-cost, highly active anode catalysts. In this paper, we have studied Iridium (Ir)-based binary catalysts as low-cost alternative electrocatalysts replacing platinum (Pt)-based catalysts for the direct ethanol fuel cell (DEFC) reaction. We report the synthesis of carbon supported Ir(71)Sn(29) catalysts with an average diameter of 2.7 ± 0.6 nm through a "surfactant-free" wet chemistry approach. The complementary characterization techniques, including aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, are used to identify the "real" heterogeneous structure of Ir(71)Sn(29)/C particles as Ir/Ir-Sn/SnO(2), which consists of an Ir-rich core and an Ir-Sn alloy shell with SnO(2) present on the surface. The Ir(71)Sn(29)/C heterogeneous catalyst exhibited high electrochemical activity toward the ethanol oxidation reaction compared to the commercial Pt/C (ETEK), PtRu/C (Johnson Matthey) as well as PtSn/C catalysts. Electrochemical measurements and density functional theory calculations demonstrate that the superior electro-activity is directly related to the high degree of Ir-Sn alloy formation as well as the existence of nonalloyed SnO(2) on surface. Our cross-disciplinary work, from novel "surfactant-free" synthesis of Ir-Sn catalysts, theoretical simulations, and catalytic measurements to the characterizations of "real" heterogeneous nanostructures, will not only highlight the intriguing structure-property correlations in nanosized catalysts but also have a transformative impact on the commercialization of DEFC technology by replacing Pt with low

  20. Pyrite oxidation in the presence of hematite and alumina: II. Effects on the cathodic and anodic half-cell reactions.

    Science.gov (United States)

    Tabelin, Carlito Baltazar; Veerawattananun, Suchol; Ito, Mayumi; Hiroyoshi, Naoki; Igarashi, Toshifumi

    2017-03-01

    The oxidative dissolution of pyrite is an important process in the redox recycling of iron (Fe) and is well-known for its role in the formation of acid mine drainage (AMD), which is considered as the most serious and widespread problem after the closure of mines and mineral processing operations. Because this process requires the movement of electrons, common metal oxides in nature that have either semiconducting (e.g., hematite) or insulating (e.g., alumina) properties may have strong effects on it. In this study, changes in the electrochemical behavior of pyrite in the presence of hematite and alumina were investigated. Results showed that the formation of surface-bound species directly influenced the anodic and cathodic half-cell reactions as well as the transfer of electrons between these sites. Pyrite pretreated in the air became anodically more reactive than that pretreated in oxygenated water, but the type of oxidizing media had little effect on the cathodic half-cell reaction. The presence of hematite and alumina during pretreatment also had strong effects on the electrochemical properties of pyrite. Chronoamperometry measurements suggest that hematite and alumina enhanced the anodic half-cell reaction but suppressed the cathodic half-cell reaction of pyrite oxidation. Increased anodic half-cell reaction in the presence of hematite could be attributed to electron "bridging" and catalytic effects of this mineral. In contrast, the effects of alumina on the anodic half-cell reaction were indirect and could be explained by the formation of Fe(3+)-oxyhydroxide surface species during pretreatment. Suppression of the cathodic half-cell reaction by both minerals was attributed to their "protective" effect on cathodic sites. Our results also point to the cathodic half-cell reaction as the rate determining-step of the overall oxidative dissolution process.

  1. Ultrasensitive photoelectrochemical immunoassay of antibody against tumor-associated carbohydrate antigen amplified by functionalized graphene derivates and enzymatic biocatalytic precipitation.

    Science.gov (United States)

    Zhang, Xiaoru; Liu, Mingshuai; Mao, Yaning; Xu, Yunpeng; Niu, Shuyan

    2014-09-15

    Tumor-associated carbohydrate antigens (TACAs) are often found on the surface of cancer cells. The determination of the carbohydrate components of glycoconjugates is challenging because of the chemical complexity of glycan chains. Through monitoring corresponding antibody, we can get a good solution for clinical diagnosis. Here breast tumor-associated carbohydrate antigens Tn were used as a model and a new photoelectrochemical biosensor for ultrasensitive detection of antibody against Tn was developed. To enhance the sensitivity, both graphene oxide and graphene were used during the construction of biosensor. Through the formation of immunocomplex and the insoluble biocatalytic precipitation (BCP) product, photocurrent intensity was decreased greatly and the antibody could be detected from 0.5 to 500 pg/mL with a detection limit of 1.0×10(-13) g/mL. At the same time, the developed biosensor showed acceptable selectivity and could be used in the complex matrix. Compared with the traditional glycoarray method, this PEC method is more sensitive (5 orders of magnitude), and thus provides another platform to monitor the immune response to carbohydrate epitopes at different stages during differentiation, metastasis, or treatment.

  2. Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

    Science.gov (United States)

    Sanibondi, Paolo

    2015-09-01

    Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

  3. Magnetic Ni-Co alloys induced by water gas shift reaction, Ni-Co oxides by CO oxidation and their supercapacitor applications

    Science.gov (United States)

    Lee, Seungwon; Kang, Jung-Soo; Leung, Kam Tong; Kim, Seog K.; Sohn, Youngku

    2016-11-01

    Ni-Co alloys and oxides have attracted considerable attention in diverse fields, such as magnetic materials, energy storage and environmental/energy producing catalysts. Herein, the formation of magnetic Ni-Co alloys was induced by the water-gas shift reaction (WGSR) and the oxides were prepared by post-annealing and a CO oxidation reaction. The materials were characterized using a range of techniques. The annealed and post-CO oxidation Ni and Co-rich samples showed the crystal structures of NiCo2O4(Co3O4)/NiO and NiCo2O4/Co3O4, respectively. The Ni-Co oxides showed better supercapacitor performance than the corresponding Ni-Co alloys. The Co-rich samples exhibited better supercapacitor performance and CO oxidation activity than the Ni-rich sample. In addition, the Co-rich alloy showed a magnetization of 114 emu/g, which was approximately 2× larger than that of the Ni-rich alloy. The WGS reaction and the wide application tests are useful for designing new materials applicable to a wide range of areas.

  4. Gold-platinum bimetallic nanotubes templated from tellurium nanowires as efficient electrocatalysts for methanol oxidation reaction

    Science.gov (United States)

    Lu, Chenchen; Kong, Wei; Zhang, Huying; Song, Bo; Wang, Zhenghua

    2015-11-01

    In this paper, gold-platinum (Au-Pt) bimetallic nanotubes with different Au/Pt ratio are successfully synthesized through a simple wet-chemical reduction route in which tellurium (Te) nanowires serve as both sacrificial template and reducing agent. The hollow nanostructure of Au-Pt nanotubes is formed due to Kirkendall effect. The as-prepared Au-Pt nanotubes can be applied as catalyst for methanol oxidation reaction, and the results indicate that the Au-Pt nanotubes with an Au/Pt ratio of 1:1 show the best electrochemical catalytic performances. Furthermore, the catalytic activity of the Au-Pt nanotubes is also better than Pt nanotubes and commercial Pt/C catalyst.

  5. Graphene oxide for acid catalyzed-reactions: Effect of drying process

    Science.gov (United States)

    Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.

    2017-03-01

    Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

  6. Self-supported porous Cobalt Oxide Nanowires with enhanced Electrocatalytic performance toward Oxygen evolution reaction

    Indian Academy of Sciences (India)

    HAN XIA; ZHEN PENG; CUNCAI L V; YAOXING ZHAO; JINHUI HAO; ZHIPENG HUANG

    2016-12-01

    Development of hybrid electrocatalysts with high activity and good stability is crucial for oxygen evolution reaction (OER) of water electrocatalysis. In this work, cobalt oxide (Co₃O₄) nanowires loaded on carbon fiber paper (CFP) were synthesized via hydrothermal method and annealing. The as-synthesized Co₃O₄ nanowires exhibit an enhanced catalytic activity with low onset overpotential (1.52V vs. RHE) and a small overpotential of 330mV for a current density of 10mAcm⁻² with a Tafel slope of 60mV·dec⁻¹. In addition, the Co₃O₄ nanowires maintain its electrocatalytic activity for at least 24 h in basic media. The enhanced performance of Co₃O₄ nanowires/CFP can be attributed to the high conductivity of CFP, the synergistic effect of Co₃O₄ and carbon, and high porosity of the nanowire. This study will open new possibilities for exploring water electrocatalysis.

  7. Heterogeneous nanocomposites of silver selenide and hollow platinum nanoparticles toward methanol oxidation reaction

    Science.gov (United States)

    Cui, Penglei; He, Hongyan; Liu, Hui; Zhang, Suojiang; Yang, Jun

    2016-09-01

    Making use of the electronic coupling between different domains in composite nanomaterials is an effective way to enhance the activity of electrocatalysts. Herein, we demonstrate the preparation of nanocomposites consisting of silver selenide (Ag2Se) and platinum (Pt) nanoparticles with a hollow interior by combining the inside-out diffusion of Ag in core-shell Ag-Pt nanoparticles with the synthesis of highly active hydrophobic Se species. In specific, the Ag2Se-hPt nanocomposites are found to have superior activity and stability for methanol oxidation reaction in an acidic condition due to the strong electronic coupling effect between semiconductor and metal domains. This strategy may provide a greener and less expensive way to the large-scale synthesis of Pt-based nanocomposites, and might be used to generate other heterogeneous nanomaterials with technological importance.

  8. Enhanced photocatalytic degradation of methylene blue by ZnO-reduced graphene oxide composite synthesized via microwave-assisted reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lv Tian [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Pan Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Liu Xinjuan; Lu Ting; Zhu Guang; Sun Zhuo [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China)

    2011-10-13

    Highlights: > ZnO-reduced graphene oxide composite is synthesized via microwave assisted reaction. > The method allows a facile, safe and rapid reaction in aqueous media. > A high dye degradation efficiency is achieved under UV light irradiation. - Abstract: A quick and facile microwave-assisted reaction is used to synthesize ZnO-reduced graphene oxide (RGO) hybrid composites by reducing graphite oxide dispersion with zinc nitrate using a microwave synthesis system. Their photocatalytic performance in degradation of methylene blue is investigated and the results show that the RGO plays an important role in the enhancement of photocatalytic performance and the ZnO-RGO composite with 1.1 wt. % RGO achieves a maximum degradation efficiency of 88% in a neutral solution under UV light irradiation for 260 min as compared with pure ZnO (68%) due to the increased light absorption, the reduced charge recombination with the introduction of RGO.

  9. Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

    Science.gov (United States)

    Xiao, Kechao; Lee, Dongwoo; Vlassak, Joost J.

    2014-10-01

    Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

  10. Highly Oxidized Platinum Nanoparticles Prepared through Radio-Frequency Sputtering: Thermal Stability and Reaction Probability towards CO.

    Science.gov (United States)

    Svintsitskiy, Dmitry A; Kibis, Lidiya S; Stadnichenko, Andrey I; Koscheev, Sergei V; Zaikovskii, Vladimir I; Boronin, Andrei I

    2015-10-26

    Platinum-oxide nanoparticles were prepared through the radio-frequency (RF) discharge sputtering of a Pt electrode in an oxygen atmosphere. The structure, particles size, electronic properties, and surface composition of the RF-sputtered particles were studied by using transmission electron microscopy and X-ray photoelectron spectroscopy. The application of the RF discharge method resulted in the formation of highly oxidized Pt(4+) species that were stable under ultrahigh vacuum conditions up to 100 °C, indicating the capability of Pt(4+) -O species to play an important role in the oxidation catalysis under real conditions. The thermal stability and reaction probability of Pt(4+) oxide species were analyzed and compared with those of Pt(2+) species. The reaction probability of PtO2 nanoparticles at 90 °C was found to be about ten times higher than that of PtO-like structures.

  11. Interplay of Experiment and Theory in Elucidating Mechanisms of Oxidation Reactions by a Nonheme Ru(IV)O Complex.

    Science.gov (United States)

    Dhuri, Sunder N; Cho, Kyung-Bin; Lee, Yong-Min; Shin, Sun Young; Kim, Jin Hwa; Mandal, Debasish; Shaik, Sason; Nam, Wonwoo

    2015-07-08

    A comprehensive experimental and theoretical study of the reactivity patterns and reaction mechanisms in alkane hydroxylation, olefin epoxidation, cyclohexene oxidation, and sulfoxidation reactions by a mononuclear nonheme ruthenium(IV)-oxo complex, [Ru(IV)(O)(terpy)(bpm)](2+) (1), has been conducted. In alkane hydroxylation (i.e., oxygen rebound vs oxygen non-rebound mechanisms), both the experimental and theoretical results show that the substrate radical formed via a rate-determining H atom abstraction of alkanes by 1 prefers dissociation over oxygen rebound and desaturation processes. In the oxidation of olefins by 1, the observations of a kinetic isotope effect (KIE) value of 1 and styrene oxide formation lead us to conclude that an epoxidation reaction via oxygen atom transfer (OAT) from the Ru(IV)O complex to the C═C double bond is the dominant pathway. Density functional theory (DFT) calculations show that the epoxidation reaction is a two-step, two-spin-state process. In contrast, the oxidation of cyclohexene by 1 affords products derived from allylic C-H bond oxidation, with a high KIE value of 38(3). The preference for H atom abstraction over C═C double bond epoxidation in the oxidation of cyclohexene by 1 is elucidated by DFT calculations, which show that the energy barrier for C-H activation is 4.5 kcal mol(-1) lower than the energy barrier for epoxidation. In the oxidation of sulfides, sulfoxidation by the electrophilic Ru-oxo group of 1 occurs via a direct OAT mechanism, and DFT calculations show that this is a two-spin-state reaction in which the transition state is the lowest in the S = 0 state.

  12. Subcutaneous Connective Tissue Reaction to a New Nano Zinc-Oxide Eugenol Sealer in Rat Model

    Science.gov (United States)

    Omidi, Salma; Javidi, Maryam; Zarei, Mina; Mushakhian, Siavash; Jafarian, Amirhossein

    2017-01-01

    Introduction: The aim of this animal study was to evaluate the histological response of the new nano zinc-oxide eugenol (NZOE) sealer in comparison with Pulp Canal Sealer (ZOE based) and AH-26 (epoxy resin sealer). Methods and Materials: A total of 27 Wistar rats were used. Four polyethylene tubes were implanted in the back of each rat (three tubes containing the test materials and an empty tube as a control). Then, 9 animals were sacrificed at each interval of 15, 30 and 60 days, and the implants were removed with the surrounding tissues.Samples were evaluated for the presence of inflammatory cell (mononuclear cell), vascular changes, fibrous tissue formation and present of giant cell. Comparisons between groups and time-periods were performed using the Kruskal-Wallis and Mann-Whitney U non-parametric tests. The level of significance was set at 0.05. Results: No significant difference was observed in tissue reactions and biocompatibility pattern of three sealers during 3 experimental periods (P<0.05). In all groups the tissue behavior showed tendency to decrease the irritation effect over time. Conclusion: The new nano zinc-oxide eugenol sealer has histocompatibility properties comparable to conventional commercial sealers. PMID:28179927

  13. Short Time and Low Temperature Reaction between Metal Oxides through Microwave-Assisted Hydrothermal Method

    Directory of Open Access Journals (Sweden)

    S. M. V. Novais

    2016-01-01

    Full Text Available This work demonstrates the possibility of synthesis of cadmium tungstate at low temperatures using oxide precursors. Cadmium tungstate (CdWO4 scintillator was produced via microwave-assisted hydrothermal reaction using the precursors CdO and WO3. The methodology was based on microwave radiation for heating, which is remarkably faster than the solid-state route or conventional hydrothermal procedure. CdWO4 monoclinic (wolframite structure was successfully obtained at 120°C for synthesis times as short as 20 min. This route does not require the use of templates or surfactants and yields self-assembled nanorods with size of around 24 ± 9 nm width and 260 ± 47 nm length. The growth mechanism for the formation of CdWO4 involves microwave-induced dissociation of the reagents and solvation of Cd2+ and WO42- ions, which are free to move and start the nucleation process. The luminescence properties of the produced nanoparticles were investigated, presenting a broad emission band at around 500 nm, which is comparable to that observed for samples produced using other chemical routes. This result highlights the great potential of the proposed method as a low-cost and time saving process to fabricate luminescent oxide nanoparticles.

  14. Heterogeneous Reactions of Acetic Acid with Oxide Surfaces: Effects of Mineralogy and Relative Humidity.

    Science.gov (United States)

    Tang, Mingjin; Larish, Whitney A; Fang, Yuan; Gankanda, Aruni; Grassian, Vicki H

    2016-07-21

    We have investigated the heterogeneous uptake of gaseous acetic acid on different oxides including γ-Al2O3, SiO2, and CaO under a range of relative humidity conditions. Under dry conditions, the uptake of acetic acid leads to the formation of both acetate and molecularly adsorbed acetic acid on γ-Al2O3 and CaO and only molecularly adsorbed acetic acid on SiO2. More importantly, under the conditions of this study, dimers are the major form for molecularly adsorbed acetic acid on all three particle surfaces investigated, even at low acetic acid pressures under which monomers are the dominant species in the gas phase. We have also determined saturation surface coverages for acetic acid adsorption on these three oxides under dry conditions as well as Langmuir adsorption constants in some cases. Kinetic analysis shows that the reaction rate of acetic acid increases by a factor of 3-5 for γ-Al2O3 when relative humidity increases from 0% to 15%, whereas for SiO2 particles, acetic acid and water are found to compete for surface adsorption sites.

  15. Water gas shift reaction over Cu catalyst supported by mixed oxide materials for fuel cell application

    Directory of Open Access Journals (Sweden)

    Tepamatr Pannipa

    2016-01-01

    Full Text Available The water gas shift activities of Cu on ceria and Gd doped ceria have been studied for the further enhancement of hydrogen purity [1] after the steam reforming of ethanol. The catalytic properties of commercial catalysts were also studied to compare with the as-prepared catalysts. Copper-containing cerium oxide materials are shown in this work to be suitable for the high temperature. Copper-ceria is a stable high-temperature shift catalyst, unlike iron-chrome catalysts that deactivate severely in CO2-rich gases. We found that 5%Cu/10%GDC(D has much higher activity than other copper ceria based catalysts. The finely dispersed CuO species is favorable to the higher activity, which explained the activity enhancement of this catalyst. The kinetics of the WGS reaction over Cu catalysts supported by mixed oxide materials were measured in the temperature range 200-400 °C. An independence of the CO conversion rate on CO2 and H2 was found.

  16. Ring Walking/Oxidative Addition Reactions for the Controlled Synthesis of Conjugated Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bazan, Guillermo C

    2012-04-03

    Power conversion efficiencies of plastic solar cells depend strongly on the molecular weight characteristics of the semiconducting polymers used for their fabrication. The synthesis of these materials typically relies on transition metal mediated catalytic reactions. In many instances, the ideal structures cannot be attained because of deficiencies in these reactions, particularly when it comes to being able to achieve high number average molecular weights and narrow molecular weight distributions. Another important conjugated polymer structure of interest is one in which a single functional group is attached at the end group of the chain. Such systems would be ideal for modifying surface properties at interfaces and for labeling biomolecular probes used in fluorescent biosensors. To respond to the challenges above, our efforts have centered on the design of homogenous transition metal complexes that are easy to prepare and effective in carrying out living, or quasi-living, condensative chain polymerization reactions. The key mechanistic challenge for the success of this reaction is to force the insertion of one monomer unit at a time via a process that involves migration of the transition metal-containing fragment to one terminus of the polymer chain. Chain growth characteristics are therefore favored when the metal does not dissociate from the newly formed reductive elimination product. We have proposed that dissociation is disfavored by the formation of a -complex, in which the metal can sample various locations of the electronically delocalized framework, a process that we term ring-walking , and find the functionality where oxidative addition takes place. Success has been achieved in the nickel-mediated cross coupling reaction of Grignard reagents with aromatic halides by using bromo[1,2-bis(diphenylphosphino)ethane]phenylnickel. This reagent can yield poly(thiophene)s (one of the most widely used type of polymer in plastic solar cells) with excellent

  17. Compensation effect in reactions between trans-4,4'-dinitrostilbene oxide and arylsulfonic acids

    Science.gov (United States)

    Shpan'ko, I. V.; Sadovaya, I. V.

    2016-12-01

    The effect structure and temperature have on the rate and free activation energy of reactions between trans-4,4'-dinitrostilbene oxide and Y-substituted arylsulfonic acids YC6H4SO3H in a mixture of dioxane with 1,2-dichloroethane (7: 3 vol/vol) at 265, 281, and 298 K is studied. It is found that as a result of the nonadditivity of the joint effect of substituents Y and temperature on the rate of the process of oxirane ring opening, the cross reaction series exhibits isoparametric properties in the aspect of enthalpy-entropy compensation. This allows the experimental determination of an isoparametric point with respect to the constant of substituent Y (σY IP= 0.52), in which activation entropy Δ S ≠ = 0 and free activation energy Δ G ≠ do not depend on temperature (Δ G ≠ = Δ H ≠), and to conduct the transition through this point with inversion of the order of the effect temperature has on the value of Δ G ≠ as a result of reversing the sign of Δ S ≠: in the series Y (σY) = 4-OCH3 (-0.27), 4-CH3 (-0.17), H (0), 4-Cl (0.23), and 3-NO2 (0.71), the values of Δ S ≠ (J/(mol K)) are-140,-119,-85,-42, and 44, respectively. The possibility of using isoparametric points as quantitative mechanistic criteria is demonstrated.

  18. Experimental and theoretical study of hydrogen thiocarbonate for heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    Science.gov (United States)

    Liu, Yongchun; He, Hong

    2009-04-09

    In situ diffuse reflectance infrared Fourier transform spectroscopy combined with derivative spectroscopy analysis, two-dimensional correlation spectroscopy analysis, and quantum chemical calculations were used to investigate the infrared absorbance assignment and the molecular structure of hydrogen thiocarbonate on magnesium oxide. The bands at 1283 and 1257 cm(-1), which had the typical characteristic of intermediate, were observed in experiments for the heterogeneous reaction of COS on MgO. On the basis of two-dimensional correlation spectroscopy analysis and quantum chemical calculations, the band at 1283 cm(-1) was assigned to the v(s) band of bridged thiocarbonate which formed on the two neighboring Mg atoms in the (100) face of MgO crystal, and the band at 1257 cm(-1) was the v(s) band of monodentate thiocarbonate on MgO. The v(as)(OCO) band of thiocarbonates was invisible in the experiment due to their weak absorbance and the interruption of surface carbonate. The formation mechanism of thiocarbonates is proposed, which occurred through a nucleophilic attack of preadsorbed COS by surface -OH groups followed by hydrogen atom transfer from the -OH group to the sulfur atom of preadsorbed COS. The activation energy for the intramolecular proton-transfer reaction of bridged thiocarbonate was calculated to be 18.52 kcal x mol(-1) at the B3LYP/6-31+G(d,p) level of theory.

  19. Insulin and leptin enhance human sperm motility, acrosome reaction and nitric oxide production

    Institute of Scientific and Technical Information of China (English)

    Fanuel Lampiao; Stefan S. du Plessis

    2008-01-01

    Aim: To investigate the in vitro effects of insulin and leptin on human sperm motility, viability, acrosome reaction and nitric oxide (NO) production. Methods: Washed human spermatozoa from normozoospermic donors were treated with insulin (10 μIU) and leptin (10 nmol). Insulin and leptin effects were blocked by inhibition of their intracellular effector, phosphotidylinositol 3-kinase (PI3K), by wortmannin (10 μmol) 30 min prior to insulin and leptin being given. Computer-assisted semen analysis was used to assess motility after 1, 2 and 3 h of incubation. Viability was assessed by fluorescence-activated cell sorting using propidium iodide as a fluorescent probe. Acrosome-reacted cells were observed under a fluorescent microscope using fluorescein-isothiocyanate-Pisum sativum agglutinin as a probe. NO was measured after treating the sperm with 4,5-diaminofluorescein-2/diacetate (DAF-2/DA) and analyzed by fluorescence-activated cell sorting. Results: Insulin and leptin significantly increased total motility, progressive motility and acrosome reaction, as well as NO production. Conclusion: This study showed the in vitro beneficial effects of insulin and leptin on human sperm function. These hormones could play a role in enhancing the fertilization capacity of human spermatozoa.

  20. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    Science.gov (United States)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  1. Remarkable solvent, porphyrin ligand, and substrate effects on participation of multiple active oxidants in manganese(III) porphyrin catalyzed oxidation reactions.

    Science.gov (United States)

    Hyun, Min Young; Jo, Young Dan; Lee, Jun Ho; Lee, Hong Gyu; Park, Hyun Min; Hwang, In Hong; Kim, Kyeong Beom; Lee, Suk Joong; Kim, Cheal

    2013-01-28

    The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron-withdrawing and -donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1-octene, and ethylbenzene in various solvent systems, namely, toluene, CH(2) Cl(2) , CH(3) CN, and H(2) O/CH(3) CN (1:4). With an increase in the concentration of the easy-to-oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1a) with electron-donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)Mn-OOC(O)R] species 2a is the major active species. When the substrate was changed from the easy-to-oxidize one (cyclohexene) to difficult-to-oxidize ones (1-octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F(20) TPP)Mn-OOC(O)R] species 2b generated from the reaction of [(F(20) TPP)MnCl] (1b) with electron-withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)Mn-OOR] 2a) depending on the concentration of the easy-to-oxidize substrate cyclohexene in all aprotic solvent systems except for CH(3) CN, whereas Mn(V)=O species is the major active oxidant in the protic solvent system. With difficult-to-oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1-octene in toluene, indicating that a Mn(V)=O intermediate generated from the heterolytic cleavage of 2b becomes a major reactive species. We also studied the competitive epoxidations of cis-2-octene and trans-2-octene with two manganese(III) porphyrin complexes by meta-chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis- to trans-2-octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further

  2. Preparation of Cu@Cu₂O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol.

    Science.gov (United States)

    Jang, Seongwan; Yoon, Chohye; Lee, Jae Myung; Park, Sungkyun; Park, Kang Hyun

    2016-11-02

    HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe₃O₄@HKUST-1 by layer-by layer assembly strategy and Cu@Cu₂O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu₂O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  3. Comparison of degradation reactions of Acid Yellow 61 in both oxidation processes of H202/UV and 03

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The comparison of degradation of Acid Yellow 61 as a model dye compound in both oxidation processes of H2 O2/UV and O3 has been studied. When the decolorization rate of Acid Yellow 61 in both reactions presented similar, it was found there are some differences from the results of AOX removal and production of inorganic ions and organic acids. The results reveal that the H2O2/UV has beneficial effect on mineralization than O3 only for degradation of Acid Yellow 61 solution and it is possible for enhancement of method efficiency by taking longer reaction time and addition of high concentration of oxidants.

  4. Vanadium-catalyzed oxidative Strecker reaction: α-C-H cyanation of para-methoxyphenyl (PMP)-protected primary amines.

    Science.gov (United States)

    Zhu, Chen; Xia, Ji-Bao; Chen, Chuo

    2014-01-01

    We describe an oxidative Strecker reaction that allows for direct cyanation of para-methoxyphenyl (PMP)-protected primary amines. A vanadium(V) complex was used as the catalyst and TBHP as the oxidant. The cyanation occurs at the α-C position bearing either an alkyl or an aromatic group. This method provides a direct access to α-aminonitrile from amines with one-carbon extension.

  5. Oxidation of acetate through reactions of the citric acid cycle by Geobacter sulfurreducens in pure culture and in syntrophic coculture

    OpenAIRE

    2000-01-01

    Geobacter sulfurreducens strain PCA oxidized acetate to CO2 via citric acid cycle reactions during growth with acetate plus fumarate in pure culture, and with acetate plus nitrate in coculture with Wolinella succinogenes. Acetate was activated by succinyl-CoA:acetate CoA-transferase and also via acetate kinase plus phosphotransacetylase. Citrate was formed by citrate synthase. Soluble isocitrate and malate dehydrogenases reduced NADP+ and NAD+, respectively. Oxidation of 2-oxoglutarate was me...

  6. Ethanol oxidation: kinetics of the alpha-hydroxyethyl radical + O2 reaction.

    Science.gov (United States)

    da Silva, Gabriel; Bozzelli, Joseph W; Liang, Long; Farrell, John T

    2009-08-06

    Bioethanol is currently a significant gasoline additive and the major blend component of flex-fuel formulations. Ethanol is a high-octane fuel component, and vehicles designed to take advantage of higher octane fuel blends could operate at higher compression ratios than traditional gasoline engines, leading to improved performance and tank-to-wheel efficiency. There are significant uncertainties, however, regarding the mechanism for ethanol autoignition, especially at lower temperatures such as in the negative temperature coefficient (NTC) regime. We have studied an important chemical process in the autoignition and oxidation of ethanol, reaction of the alpha-hydroxyethyl radical with O2(3P), using first principles computational chemistry, variational transition state theory, and Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation simulations. The alpha-hydroxyethyl + O2 association reaction is found to produce an activated alpha-hydroxy-ethylperoxy adduct with ca. 37 kcal mol(-1) of excess vibrational energy. This activated adduct predominantly proceeds to acetaldehyde + HO(2), with smaller quantities of the enol vinyl alcohol (ethenol), particularly at higher temperatures. The reaction to acetaldehyde + HO2 proceeds with such a low barrier that collision stabilization of C2O3H5 isomers is unimportant, even for high-pressure/low-temperature conditions. The short lifetimes of these radicals precludes the chain-branching addition of a second O2 molecule, responsible for NTC behavior in alkane autoignition. This result helps to explain why ignition delays for ethanol are longer than those for ethane, despite ethanol having a weaker C-C bond energy. Given its relative instability, it is also unlikely that the alpha-hydroxy-ethylperoxy radical acts as a major acetaldehyde sink in the atmosphere, as has been suggested.

  7. Epoxidation and oxidation reactions using 1,4-butanediol dimethacrylate crosslinked polystyrene-supported tertiary butyl hydroperoxide

    Indian Academy of Sciences (India)

    M S Sheela; K Sreekumar

    2004-11-01

    1,4-Butanediol dimethacrylate (1,4-BDDMA) crosslinked polystyrene-supported -butyl hydroperoxide was employed in the epoxidation of olefins and oxidation of alcohols to carbonyl compounds. The reagent proved to be successful as a recyclable solid phase organic reagent with as much or more efficiency when compared to its monomeric counterpart. The extent of reaction was found to be dependent on various reaction parameters like solvent, temperature, molar concentration and presence of catalyst.

  8. Oxidation of acetate through reactions of the citric acid cycle by Geobacter sulfurreducens in pure culture and in syntrophic coculture.

    Science.gov (United States)

    Galushko, A S; Schink, B

    2000-11-01

    Geobacter sulfurreducens strain PCA oxidized acetate to CO2 via citric acid cycle reactions during growth with acetate plus fumarate in pure culture, and with acetate plus nitrate in coculture with Wolinella succinogenes. Acetate was activated by succinyl-CoA:acetate CoA-transferase and also via acetate kinase plus phosphotransacetylase. Citrate was formed by citrate synthase. Soluble isocitrate and malate dehydrogenases NADP+ and NAD+, respectively. Oxidation of 2-oxoglutarate was measured as benzyl viologen reduction and strictly CoA-dependent; a low activity was also observed with NADP+. Succinate dehydrogenase and fumarate ductase both were membrane-bound. Succinate oxidation was coupled to NADP+ reduction whereas fumarate reduction was coupled to NADPH and NADH Coupling of succinate oxidation to NADP+ or cytochrome(s) reduction required an ATP-dependent reversed electron transport. Net ATP synthesis proceeded exclusively through electron transport phosphorylation. During fumarate reduction, both NADPH and NADH delivered reducing equivalents into the electron transport chain, which contained a menaquinone. Overall, acetate oxidation with fumarate proceeded through an open loop of citric acid cycle reactions, excluding succinate dehydrogenase, with fumarate reductase as the key reaction for electron delivery, whereas acetate oxidation in the syntrophic coculture required the complete citric acid cycle.

  9. Research on optimal process parameters in thermally oxidation-assisted polishing of reaction-sintered silicon carbide

    Science.gov (United States)

    Shen, Xinmin; Yamamura, Kazuya; Zhang, Xiaonan; Zhang, Xiangpo; Wang, Dong; Peng, Kang

    2016-10-01

    Reaction-sintered silicon carbide (RS-SiC) has been widely used in space telescope systems for its excellent physical and mechanical properties. Thermally oxidation-assisted polishing is a practical machining method to obtain RS-SiC parts with high precision, and the research focus is optimization of process parameters, because there are bumpy structures on the oxidized RS-SiC. By atomic force microscopy (AFM) detection, the distributions of oxides on the oxidized RS-SiC sample are quantitative analyzed when the thermal oxidation time is 5min, 30min, and 60min, and the calculated average differences of oxide heights between the initial Si grains and SiC grains are 10.7nm, 25.1nm, and 35.2nm, respectively. Meanwhile, the volume expansion coefficient in oxidation of Si/SiC to SiO2 is 2.257 and 2.194, respectively. Through theoretical derivation based on the Deal-Grove model, the numerical relationship between differences of oxide heights and thermal oxidation time is obtained. Combining with the material removal rate of oxide by ceria slurry in the abrasive polishing, the obtained surface quality can be precisely forecasted and controlled. The oxidized RS-SiC sample, when the oxidation time is 30min, is polished with different times to verify the theoretical analysis results. When the polishing times are 20min, 30min, and 40min, the obtained differences of oxide heights by the AFM detection are consistent with theoretical calculated results. Research on the optimal process parameters in thermally oxidation-assisted polishing of RS-SiC can improve the process level of RS-SiC sample and promote the application of SiC parts.

  10. Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Soshi, E-mail: sato.soshi@cies.tohoku.ac.jp; Honjo, Hiroaki; Niwa, Masaaki [Center for Innovative Integrated Electronic Systems, Tohoku University, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); JST-ACCEL, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); Ikeda, Shoji [Center for Innovative Integrated Electronic Systems, Tohoku University, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); JST-ACCEL, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); Center for Spintronics Integrated Systems, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Research Institute of Electrical Communication, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Ohno, Hideo [Center for Innovative Integrated Electronic Systems, Tohoku University, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); Center for Spintronics Integrated Systems, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Research Institute of Electrical Communication, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); WPI-Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Endoh, Tetsuo [Center for Innovative Integrated Electronic Systems, Tohoku University, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); JST-ACCEL, 468-1 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-0845 (Japan); Center for Spintronics Integrated Systems, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Graduate School of Engineering, Tohoku University, 6-6 Aza-aoba, Aramaki, Aoba-ku, Sendai 980-8579 (Japan)

    2015-04-06

    We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.

  11. Estimating reaction constants by ab initio molecular modeling: a study on the oxidation of phenol to catechol and hydroquinone in advanced oxidation processes

    Directory of Open Access Journals (Sweden)

    B. Ramos

    2012-03-01

    Full Text Available Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

  12. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1 based on solid-state redox reaction of oxide ions.

  13. Reactions of acetone oxide stabilized Criegee intermediate with SO2, NO2, H2O and O3

    Science.gov (United States)

    Kukui, Alexandre; Chen, Hui; Xiao, Shan; Mellouki, Wahid; Daële, Veronique

    2015-04-01

    Atmospheric aerosol particles represent a critical component of the atmosphere, impacting global climate, regional air pollution, and human health. The formation of new atmospheric particles and their subsequent growth to larger sizes are the key processes for understanding of the aerosol effects. Sulphuric acid, H2SO4, has been identified to play the major role in formation of new atmospheric particles and in subsequent particle growth. Until recently the reaction of OH with SO2 has been considered as the only important source of H2SO4 in the atmosphere. However, recently it has been suggested that the oxidation of SO2 by Criegee biradicals can be a significant additional atmospheric source of H2SO4 comparable with the reaction of SO2 with OH. Here we present some results about the reactions of the acetone oxide stabilized Criegee intermediate, (CH3)2=OO, produced in the reaction of 2,3-dimethyl-butene (TME) with O3. The formation of the H2SO4 in the reaction of acetone oxide with SO2 was investigated in the specially constructed atmospheric pressure laminar flow reactor. The Criegee intermediate was generated by ozonolysis of TME. The H2SO4, generated by addition of SO2, was directly monitored with Chemical Ionization Mass Spectrometer (SAMU, LPC2E). Relative rates of reactions of acetone oxide with SO2, NO2, H2O and ozone were determined from the dependencies of the H2SO4 yield at different concentrations of the reactants. Atmospheric applications of the obtained results are discussed in relation to the importance of this additional H2SO4 formation pathway compared to the reaction of OH with SO2.

  14. Controlling the Formation of Nanocavities in Kirkendall Nanoobjects through Sequential Thermal Ex Situ Oxidation and In Situ Reduction Reactions.

    Science.gov (United States)

    Mel, Abdel-Aziz El; Tessier, Pierre-Yves; Buffiere, Marie; Gautron, Eric; Ding, JunJun; Du, Ke; Choi, Chang-Hwan; Konstantinidis, Stephanos; Snyders, Rony; Bittencourt, Carla; Molina-Luna, Leopoldo

    2016-06-01

    Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure. On the other hand, by applying a sequential oxidation and reduction reactions to copper nanowires, one can synthesize hollow nanoobjects with complex shapes and morphologies that cannot be obtained using the Kirkendall effect alone, such as necklace-like cuprous oxide nanotubes, periodic solid copper nanoparticles or hollow cuprous oxide nanospheres interconnected with single crystal cuprous oxide nanorods, and aligned and periodic hollow nanospheres embedded in a cuprous oxide nanotube. The strategy demonstrated in this study opens new avenues for the engineering of hollow nanostructures with potential applications in gas sensing, catalysis, and energy storage.

  15. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn

    2012-06-01

    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  16. Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

    Directory of Open Access Journals (Sweden)

    M. Ehn

    2012-02-01

    Full Text Available High molecular weight (300–650 Da naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night during spring and summer in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16 oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC. The ions were identified as clusters of the nitrate ion (NO3 and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4 (Hyytiälä and C3F5O2 (JPAC. The most abundant products in the ion spectra were identified as C105H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10

  17. Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

    DEFF Research Database (Denmark)

    Jensen, Frank Bo

    2008-01-01

    The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

  18. Surface Reaction Kinetics of Steam- and CO2-Reforming as Well as Oxidation of Methane over Nickel-Based Catalysts

    Directory of Open Access Journals (Sweden)

    Karla Herrera Delgado

    2015-05-01

    Full Text Available An experimental and kinetic modeling study on the Ni-catalyzed conversion of methane under oxidative and reforming conditions is presented. The numerical model is based on a surface reaction mechanism consisting of 52 elementary-step like reactions with 14 surface and six gas-phase species. Reactions for the conversion of methane with oxygen, steam, and CO2 as well as methanation, water-gas shift reaction and carbon formation via Boudouard reaction are included. The mechanism is implemented in a one-dimensional flow field description of a fixed bed reactor. The model is evaluated by comparison of numerical simulations with data derived from isothermal experiments in a flow reactor over a powdered nickel-based catalyst using varying inlet gas compositions and operating temperatures. Furthermore, the influence of hydrogen and water as co-feed on methane dry reforming with CO2 is also investigated.

  19. Measuring protection of aromatic wine thiols from oxidation by competitive reactions vs wine preservatives with ortho-quinones.

    Science.gov (United States)

    Nikolantonaki, Maria; Magiatis, Prokopios; Waterhouse, Andrew L

    2014-11-15

    Quinones are central intermediates in wine oxidation that can degrade the quality of wine by reactions with varietal thiols, such as 3-sulfanylhexanol, decreasing desirable aroma. Protection by wine preservatives (sulphur dioxide, glutathione, ascorbic acid and model tannin, phloroglucinol) was assessed by competitive sacrificial reactions with 4-methyl-1,2-benzoquinone, quantifying products and ratios by HPLC-UV-MS. Regioselectivity was assessed by product isolation and identification by NMR spectroscopy. Nucleophilic addition reactions compete with two electron reduction of quinones by sulphur dioxide or ascorbic acid, and both routes serve as effective quenching pathways, but minor secondary products from coupled redox reactions between the products and reactants are also observed. The wine preservatives were all highly reactive and thus all very protective against 3-sulfanylhexanol loss to the quinone, but showed only additive antioxidant effects. Confirmation of these reaction rates and pathways in wine is needed to assess the actual protective action of each tested preservative.

  20. Influence of Ligand Architecture in Tuning Reaction Bifurcation Pathways for Chlorite Oxidation by Non-Heme Iron Complexes

    NARCIS (Netherlands)

    Barman, Prasenjit; Faponle, Abayomi S; Vardhaman, Anil Kumar; Angelone, Davide; Löhr, Anna-Maria; Browne, Wesley R; Comba, Peter; Sastri, Chivukula V; de Visser, Sam P

    2016-01-01

    Reaction bifurcation processes are often encountered in the oxidation of substrates by enzymes and generally lead to a mixture of products. One particular bifurcation process that is common in biology relates to electron transfer versus oxygen atom transfer by high-valent iron(IV)-oxo complexes, whi

  1. An unexpected copper(II)-catalyzed three-component reaction of quinazoline 3-oxide, alkylidenecyclopropane, and water.

    Science.gov (United States)

    An, Yuanyuan; Zheng, Danqing; Wu, Jie

    2014-08-21

    An unexpected copper(II)-catalyzed three-component reaction of quinazoline-3-oxide, alkylidenecyclopropane and water under mild conditions is reported. This transformation including [3+2] cycloaddition and intramolecular rearrangement leads to N-(2-(5-oxa-6-azaspiro[2.4]hept-6-en-7-yl)phenyl)formamides in good yields.

  2. Heterogeneous reactions of NO2 and HNO3 on oxides and mineral dust: A combined laboratory and modeling study

    Science.gov (United States)

    Underwood, G. M.; Song, C. H.; Phadnis, M.; Carmichael, G. R.; Grassian, V. H.

    2001-08-01

    This study combines laboratory measurements and modeling analysis to quantify the role of heterogeneous reactions of gaseous nitrogen dioxide and nitric acid on mineral oxide and mineral dust particles in tropospheric ozone formation. At least two types of heterogeneous reactions occur on the surface of these particles. Upon initial exposure of the oxide to NO2 there is a loss of NO2 from the gas phase by adsorption on the particle surface, i.e., NO2(g) → NO2(a). As the reaction proceeds, a reduction of gaseous NO2 to NO, NO2 (g) → NO (g) is found to occur. Initial uptake coefficients γ0 for NO2 on the surface of these particles have been measured at 298 K using a Knudsen cell reactor coupled to a mass spectrometer. For the oxides studied, α,γ-Al2O3, α,γ-Fe2O3, TiO2, SiO2, CaO, and MgO, γ0 ranges from dry surfaces are just below the lower limit to have an impact on the photochemical oxidant cycle, while the heterogeneous reactivity of HNO3 is sufficiently large to have an effect. Under conditions of high mineral dust mass loadings and/or smaller size distributions the importance of these reactions (both NO2 and HNO3) is expected to increase.

  3. The Chemical Interplay between Nitric Oxide and Mitochondrial Cytochrome c Oxidase: Reactions, Effectors and Pathophysiology

    Directory of Open Access Journals (Sweden)

    Paolo Sarti

    2012-01-01

    Full Text Available Nitric oxide (NO reacts with Complex I and cytochrome c oxidase (CcOX, Complex IV, inducing detrimental or cytoprotective effects. Two alternative reaction pathways (PWs have been described whereby NO reacts with CcOX, producing either a relatively labile nitrite-bound derivative (CcOX-NO2 −, PW1 or a more stable nitrosyl-derivative (CcOX-NO, PW2. The two derivatives are both inhibited, displaying different persistency and O2 competitiveness. In the mitochondrion, during turnover with O2, one pathway prevails over the other one depending on NO, cytochrome c2+ and O2 concentration. High cytochrome c2+, and low O2 proved to be crucial in favoring CcOX nitrosylation, whereas under-standard cell-culture conditions formation of the nitrite derivative prevails. All together, these findings suggest that NO can modulate physiologically the mitochondrial respiratory/OXPHOS efficiency, eventually being converted to nitrite by CcOX, without cell detrimental effects. It is worthy to point out that nitrite, far from being a simple oxidation byproduct, represents a source of NO particularly important in view of the NO cell homeostasis, the NO production depends on the NO synthases whose activity is controlled by different stimuli/effectors; relevant to its bioavailability, NO is also produced by recycling cell/body nitrite. Bioenergetic parameters, such as mitochondrial ΔΨ, lactate, and ATP production, have been assayed in several cell lines, in the presence of endogenous or exogenous NO and the evidence collected suggests a crucial interplay between CcOX and NO with important energetic implications.

  4. Toluene removal by oxidation reaction in spray wet scrubber: experimental, modeling and optimization

    Directory of Open Access Journals (Sweden)

    Roumporn Nikom

    2006-11-01

    Full Text Available Toluene, an important volatile organic compound (VOC, is used in many kinds of industries, such as painting, printing, coating, and petrochemical industries. The emission of toluene causes serious air pollution, odor problem, flammability problem and affects human health. This paper proposes the removal of toluene from waste air using a spray wet scrubber combining the absorption and oxidation reaction. Aqueous sodium hypochlorite (NaOCl solution was used as the scrubbing liquid in the system. NaOCl, the strongest oxidative agent, presents an effective toluene removal. As the scrubbed toluene is reacted, recirculation of the scrubbing liquid could be operated with a constant removal efficiency throughout the operting time. The investigated variables affecting the removal efficiency were air flow rate, inlet toluene concentration, NaOCl concentration, scrubbing liquid flow rate and size of spray nozzle. Influence of the scrubbing parameters was experimentally studied to develop a mathematical model of the toluene removal efficiency. The removal model reveals that the increase of scrubbing liquid flow rate, toluene concentration, and NaOCl concentration together with the decrease of air flow rate and size of spray nozzle can increase the toluene removal efficiency. Optimization problem with an objective function and constraints was set to provide the maximum toluene removal efficiency and solved by Matlab optimization toolbox. The optimization constraints were formed from the mathematical model and process limitation. The solution of the optimization was an air flow rate of 100 m3/h, toluene concentration of 1500 ppm, NaOCl concentration of 0.02 mol/l, NaOCl solution feed rate of 0.8 m3/h, and spray nozzle size of 0.5 mm. Solution of the optimization gave the highest toluene removal efficiency of 91.7%.

  5. Antioxidative Mechanisms of Sulfite and Protein-Derived Thiols during Early Stages of Metal Induced Oxidative Reactions in Beer.

    Science.gov (United States)

    Lund, Marianne N; Krämer, Anna C; Andersen, Mogens L

    2015-09-23

    The radical-mediated reactions occurring during the early stages of beer storage were studied by following the rate of oxygen consumption, radical formation as detected by electron spin resonance spectroscopy, and concentrations of the antioxidant compounds sulfite and thiols. Addition of either Fe(III) or Fe(II) had similar effects, indicating that a fast redox equilibrium is obtained between the two species in beer. Addition of iron in combination with hydrogen peroxide gave the most pronounced levels of oxidation due to a direct initiation of ethanol oxidation through generation of hydroxyl radicals by the Fenton reaction. The concentration of sulfite decreased more than the thiol concentration, suggesting that thiols play a secondary role as antioxidants by mainly quenching 1-hydroxyethyl radicals that are intermediates in the oxidation of ethanol. Increasing the temperature had a minor effect on the rate of oxygen consumption.

  6. Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Yi Cheng

    2015-12-01

    Full Text Available The water electrolysis for hydrogen production is constrained by the thermodynamically unfavorable oxygen evolution reaction (OER, which requires input of a large amount of energy to drive the reaction. One of the key challenges to increase the efficiency of the water electrolysis system is to develop highly effective and robust electrocatalysts for the OER. In the past 20–30 years, significant progresses have been made in the development of efficient electrocatalysts, including metal oxides, metal oxide-carbon nanotubes (CNTs hybrid and metal-free CNTs based materials for the OER. In this critical review, the overall progress of metal oxides catalysts and the role of CNTs in the development of OER catalyst are summarized, and the latest development of new metal free CNTs-based OER catalyst is discussed.

  7. Forming mechanism of nitrogen doped graphene prepared by thermal solid-state reaction of graphite oxide and urea

    Energy Technology Data Exchange (ETDEWEB)

    Mou Zhigang [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Chen Xiaoye [Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123 (China); Du Yukou; Wang Xiaomei [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Yang Ping, E-mail: pyang@suda.edu.cn [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Wang Suidong, E-mail: wangsd@suda.edu.cn [Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123 (China)

    2011-12-15

    Nitrogen doped graphene was synthesized from graphite oxide and urea by thermal solid-state reaction. The samples were characterized by transmission electron microscopy, atomic force microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectra, element analysis, and electrical conductivity measurement. The results reveal that there is a gradual thermal transformation of nitrogen bonding configurations from amide form nitrogen to pyrrolic, then to pyridinic, and finally to 'graphitic' nitrogen in graphene sheets with increasing annealing temperature from 200 to 700 Degree-Sign C. The products prepared at 600 Degree-Sign C and 700 Degree-Sign C show that the quantity of nitrogen incorporated into graphene lattice is {approx}10 at.% with simultaneous reduction of graphite oxide. Oxygen-containing functional groups in graphite oxide are responsible for the doping reaction to produce nitrogen doped graphene.

  8. Dynamics of activity free radical oxidation reactions in students with cerebral palsy results over the course of the educational process

    Directory of Open Access Journals (Sweden)

    Makarova E.V.

    2012-12-01

    Full Text Available The dynamics of changes activity of reactions is studied freely radical oxidize for students with the consequences of child's cerebral paralysis. 20 students took part in an experiment. Found that the course of study they have more active free radical oxidation reactions and decreases the activity of antiradical protection. Given the use of additional physical activity in aerobic training indicators intracellular antioxidant defense system increased, decreased content of reaction products of lipid peroxidation. However, increased rates of maximum oxygen consumption and increased tolerance of students with cerebral palsy to the consequences of physical activity. It is set that the pathological changes of metabolism for students ground the necessity of application of the differentiated physical loadings. The optimum forms of physical rehabilitation of the aerobic training is the dosed walking, medical swimming, dosed after distance, sometimes and by the corner of getting up pedestrian ascents. Loading is increased due to a volume, but not intensity of exercises.

  9. Analysis of Absorption and Reaction Kinetics in the Oxidation of Organics in Effluents Using a Porous Electrode Ozonator

    Institute of Scientific and Technical Information of China (English)

    Alexander P. Mathews; ishora K. Panda

    2012-01-01

    A novel electrode design for the in situ generation of ozone in the reaction zone of a tubular reactor is described in this work. The ozone generator uses a porous inner electrode tube in the corona discharge assembly, and the ozone generated around the outer periphery of the porous tube diffuses into the tubular reactor and reacts with the contaminants in the fluid that is being treated. A mathematical model that includes absorption and second order reaction in the film is developed to describe ozonation kinetics of a contaminant dye in the tubular reactor. The model describes the experimental data for dye decolorization, oxidation byproducts, dissolved ozone, and ozone gas concentrations well. Model analysis indicates that the fast dye decolorization reaction occurs partly in the liquid film and partly in the bulk fluid. The model can be used in the selection of appropriate gas-liquid contactors for efficient oxidation of contaminants in effluents.

  10. Efficient Synthesis of Bi-butenolides Derivatives through Oxidative Dimeric Cyclizing-Coupling Reaction of 2,3-Allenoic Acids

    Institute of Scientific and Technical Information of China (English)

    MA Sheng-Ming; YU Zhan-Qian

    2003-01-01

    @@ Allenes are three carbon functional groups possessing two perpendicular π-orbitals. Their unique reaction be havior is spread over three carbon atoms, which shows great potential in organic synthesis in terms of chirality transfer and diversity, as a result of the axial chirality as well as the substituent-loading capability. Recently, we devoted ourselves to establish a new area of oxidative cyclization-dimerization reactions between two functionalized allenes to give interesting bicyclic compounds in a single step. The formidable challenges are to match the reactivities of two allenes, and regenerate the catalyst, which would be reduced after reductive-elimination. In this paper we wish to disclose our recent studies on the synthesis of bi-butenolides from oxidative cyclization self-coupling reaction of 2,3 allenoic acids, in which a new system (PdCl2/RI/air) for regeneration of the palladium(Ⅱ) species was observed.

  11. Studies of the Catalytic Activity and Deactivation of Calcined Layered Double Hydroxides in the Reaction of Ethanol with Propylene Oxide

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The reaction of ethanol with propylene oxide over calcined layered double hydroxides(CLDH) was investigated. The results show that CLDH has a good activity and a good selectivity, but the activity and the selectivity of CLDH decrease when CLDH reforms LDH- the so called "memory effect". The influence of the "memory effect" on the CLDH returning to LDH was studied by the hydration reaction. It is shown that the "memory effect" is not complete, and the decreases of the Mg/Al molar ratio of LDH and the crystallite size due to the increase of the hydration reaction time result in the drop of the activity and the selectivity.Keyworcds Ethanol, Propylene oxide, Calcined layered double hydroxide, "Memory effect", Hydration

  12. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  13. Optimization of preparation conditions of Fe-Co nanoparticles in low-temperature CO oxidation reaction by taguchi design method

    Institute of Scientific and Technical Information of China (English)

    Abolfazl Biabani; Mehran Rezaei; Zohreh Fattah

    2012-01-01

    Mixed iron-cobalt oxide (Co/Fe molar ratio=1/5) are prepared using a simple co-precipitation procedure and studied for the catalytic oxidation of carbon monoxide.In particular,the effects of a range of preparation variables such as pH value when precipitation,aging temperature,precipitation agent type and aging time are investigated on the catalytic performance of synthesized Fe-Co oxides in CO oxidation reaction.In addition,the preparation factors were optimized by Taguchi design method.The optimized sample was characterized by XRD,N2 adsorption/desorption,TEM and TGA/DTA techniques.The results reveal that the optimized sample shows a mesoporous structure with a narrow pore size distribution centered in the range of 2-7 nm.The sample prepared under optimized conditions has high activity and stability toward removal of carbon monoxide at lower temperatures.It is shown that different preparation variables influence the catalytic performance of Fe-Co oxide in CO oxidation reaction.

  14. Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction

    Institute of Scientific and Technical Information of China (English)

    何润霞; 姜浩强; 武芳; 智科端; 王娜; 周晨亮; 刘全生

    2014-01-01

    Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO (REO indicates La2O3, CeO2, Y2O3, or Pr6O11) as raw materials. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed reduc-tion of oxidized surfaces (s-TPR), and temperature-programmed desorption (TPD). Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.

  15. Trends in substrate hydroxylation reactions by heme and nonheme iron(IV)-oxo oxidants give correlations between intrinsic properties of the oxidant with barrier height.

    Science.gov (United States)

    de Visser, Sam P

    2010-01-27

    Iron(IV)-oxo species have been characterized in several nonheme enzymes and biomimetic systems and are efficient oxidants of aliphatic hydroxylation reactions. However, there appears to be a large variation in substrate hydroxylation ability by different iron(IV)-oxo oxidants due to the effect of the ligands bound to the metal. In this work, we have studied these indirect effects of ligands perpendicular (cis or equatorial) and opposite (trans or axial) to the iron(IV)-oxo group in heme and nonheme oxidants on the oxygenation capability of the oxidant. To this end, we have done a series of density functional theory calculations on the hydrogen atom abstraction of propene by a range of different iron(IV)-oxo oxidants that include heme and nonheme iron(IV)-oxo oxidants. We show that the hydrogen atom abstraction barrier of substrate hydroxylation correlates linearly with the strength of the Fe(III)O-H bond that is formed, i.e., BDE(OH), and that this value ranges by at least 20 kcal mol(-1) dependent on the cis- and trans-ligands attached to the metal. Thus, our studies show that ligands bound to the metal are noninnocent and influence the catalytic properties of the metal-oxo group dramatically due to involvement into the high-lying occupied and virtual orbitals. A general valence bond curve crossing model is set up that explains how the rate constant of hydrogen atom abstraction is proportional to the difference in energy of the C-H bond of the substrate that is broken and the O-H bond of the Fe(III)O-H complex that is formed, i.e., proportional to BDE(CH) - BDE(OH) or the reaction enthalpy. In addition, we show a correlation between the polarizability change and barrier height for the hydrogen atom abstraction reaction.

  16. Monoascorbate free radical-dependent oxidation-reduction reactions of liver Golgi apparatus membranes.

    Science.gov (United States)

    Navas, Placido; Sun, Iris; Crane, Frederick L; Morré, Dorothy M; Morré, D James

    2010-04-01

    Golgi apparatus from rat liver contain an ascorbate free radical oxidoreductase that oxidizes NADH at neutral pH with monodehydroascorbate as acceptor to generate a membrane potential. At pH 5.0, the reverse reaction occurs from NAD(+). The electron spin resonance signal of the ascorbate-free radical and its disappearance upon the addition of NADH (pH 7) or NAD(+) (pH 5.0) confirms monodehydroascorbate involvement. Location of monodehydroascorbate both external to and within Golgi apparatus compartments is suggested from energization provided by inward or outward flux of electrons across the Golgi apparatus membranes. The isolated membranes are sealed, oriented cytoplasmic side out and impermeable to NAD(+) and ascorbate. NAD(+) derived through the action of Golgi apparatus beta-NADP phosphohydrolase is simultaneously reduced to NADH with monodehydroascorbate present. The response of the NADH- (NAD(+)-) ascorbate free radical oxidoreductase system to pH in Golgi apparatus provides a simple regulatory mechanism to control vesicle acidification.

  17. Adsorption of Zn2+ from solutions on manganese oxide obtained via ozone precipitation reaction

    Directory of Open Access Journals (Sweden)

    Contreras-Bustos Roberto

    2016-03-01

    Full Text Available Synthesis via ozone precipitation reaction was used to obtain manganese dioxide (OMD and it was probed as an adsorbent for zinc ions. Adsorption was followed along shaking time and increasing ratio [NO3−] / [Zn2+], and isotherms were obtained at different pH values and in the presence of several anions (chloride, nitrate, sulphate, and acetate. It was found that adsorption equilibrium is fast and follows the pseudo-second order model (qe = 34 ±1 mg/g and K = 0.07 ±0.01 g/mg h. Isotherms were fitted to Langmuir, Freundlich, and Langmuir-Freundlich models, and the best fitting was found with the last one. The process is dependent on pH and the efficiency increases from pH 1 to 4. The ratio [NO3−] / [Zn2+] up to 3 does not seem to change the behaviour of the process. Regarding the anions, the efficiency of Zn(II adsorption occurs according to: acetate > nitrate and sulphate > chloride. Manganese oxide obtained via ozonization is an excellent adsorbent for zinc ions.

  18. Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation.

    Science.gov (United States)

    Hinkle, Margaret A G; Dye, Katherine G; Catalano, Jeffrey G

    2017-03-01

    Layered Mn oxide minerals (phyllomanganates) often control trace metal fate in natural systems. The strong uptake of metals such as Ni and Zn by phyllomanganates results from adsorption on or incorporation into vacancy sites. Mn(II) also binds to vacancies and subsequent comproportionation with structural Mn(IV) may alter sheet structures by forming larger and distorted Mn(III)O6 octahedra. Such Mn(II)-phyllomanganate reactions may thus alter metal uptake by blocking key reactive sites. Here we investigate the effect of Mn(II) on Ni and Zn binding to phyllomanganates of varying initial vacancy content (δ-MnO2, hexagonal birnessite, and triclinic birnessite) at pH 4 and 7 under anaerobic conditions. Dissolved Mn(II) decreases macroscopic Ni and Zn uptake at pH 4 but not pH 7. Extended X-ray absorption fine structure spectroscopy demonstrates that decreased uptake at pH 4 corresponds with altered Ni and Zn adsorption mechanisms. These metals transition from binding in the interlayer to sheet edges, with Zn increasing its tetrahedrally coordinated fraction. These effects on metal uptake and binding correlate with Mn(II)-induced structural changes, which are more substantial at pH 4 than 7. Through these structural effects and the pH-dependence of Mn(II)-metal competitive adsorption, system pH largely controls metal binding to phyllomanganates in the presence of dissolved Mn(II).

  19. Moisture effects on the electrochemical reaction and resistance switching at Ag/molybdenum oxide interfaces.

    Science.gov (United States)

    Yang, Chuan-Sen; Shang, Da-Shan; Chai, Yi-Sheng; Yan, Li-Qin; Shen, Bao-Gen; Sun, Young

    2016-05-14

    An important potential application of solid state electrochemical reactions is in redox-based resistive switching memory devices. Based on the fundamental switching mechanisms, the memory has been classified into two modes, electrochemical metallization memory (ECM) and valence change memory (VCM). In this work, we have investigated a solid state electrochemical cell with a simple Ag/MoO3-x/fluorine-doped tin oxide (FTO) sandwich structure, which shows a normal ECM switching mode after an electroforming process. While in the lower voltage sweep range, the switching behavior changes to VCM-like mode with the opposite switching polarity to the ECM mode. By current-voltage measurements under different ambient atmospheres and X-ray photoemission spectroscopy analysis, electrochemical anodic passivation of the Ag electrode and valence change of molybdenum ions during resistance switching have been demonstrated. The crucial role of moisture adsorption in the switching mode transition has been clarified based on the Pourbaix diagram for the Ag-H2O system for the first time. These results provide a fundamental insight into the resistance switching mechanism model in solid state electrochemical cells.

  20. Photocurrent Generation by Photosynthetic Purple Bacterial Reaction Centers Interfaced with a Porous Antimony-Doped Tin Oxide (ATO) Electrode.

    Science.gov (United States)

    Carey, Anne-Marie; Zhang, HaoJie; Mieritz, Daniel; Volosin, Alex; Gardiner, Alastair T; Cogdell, Richard J; Yan, Hao; Seo, Dong-Kyun; Lin, Su; Woodbury, Neal W

    2016-09-28

    The ability to exchange energy and information between biological and electronic materials is critical in the development of hybrid electronic systems in biomedicine, environmental sensing, and energy applications. While sensor technology has been extensively developed to collect detailed molecular information, less work has been done on systems that can specifically modulate the chemistry of the environment with temporal and spatial control. The bacterial photosynthetic reaction center represents an ideal photonic component of such a system in that it is capable of modifying local chemistry via light-driven redox reactions with quantitative control over reaction rates and has inherent spectroscopic probes for monitoring function. Here a well-characterized model system is presented, consisting of a transparent, porous electrode (antimony-doped tin oxide) which is electrochemically coupled to the reaction center via a cytochrome c molecule. Upon illumination, the reaction center performs the 2-step, 2-electron reduction of a ubiquinone derivative which exchanges with oxidized quinone in solution. Electrons from the electrode then move through the cytochrome to reoxidize the reaction center electron donor. The result is a facile platform for performing redox chemistry that can be optically and electronically controlled in time and space.

  1. Runaway behavior and thermally safe operation of multiple liquid–liquid reactions in the semi-batch reactor: The nitric acid oxidation of 2-octanol

    NARCIS (Netherlands)

    Woezik, van B.A.A.; Westerterp, K.R.

    2002-01-01

    The thermal runaway behavior of an exothermic, heterogeneous, multiple reaction system has been studied in a cooled semi-batch reactor. The nitric acid oxidation of 2-octanol has been used to this end. During this reaction, 2-octanone is formed, which can be further oxidized to unwanted carboxylic a

  2. Reaction Engineering of Biocatalytic Enantioselective Reduction: A Case Study for Aliphatic Ketones

    DEFF Research Database (Denmark)

    Leuchs, Susanne; Lima-Ramos, Joana; Greiner, Lasse

    2013-01-01

    Previously, it could be demonstrated, that the monophasic, enzymatic reduction of aliphatic 2-ketones into the corresponding (R)-2-alcohols is an adequate and viable method as carried out in a cascade of two enzyme–membrane reactors (Leuchs, S.; Na’amnieh, S. N.; Greiner, L. Green Chemistry 2013......, 15, 167–176.). In the present work, the process metrics of the ketone reduction were calculated. A cost analysis revealed that the enzyme costs are negligible, but the cost for nicotinamide cofactor NADP+ is dominating the overall cost of the chemical raw material followed by the ionic liquid (TEGO...... IL K5) used as solubiliser and the buffer. The overall cost of chemicals was €148/kgproduct. To assess the environmental impact of the process, the E-factor (kgwaste/kgproduct) 132 and the process mass intensity 133 (PMI, kgsubstrate/kgproduct) were calculated. A process model based on initial rate...

  3. Transient kinetics of electron transfer reactions of flavodoxin: ionic strength dependence of semiquinone oxidation by cytochrome c, ferricyanide, and ferric ethylenediaminetetraacetic acid and computer modeling of reaction complexes.

    Science.gov (United States)

    Simondsen, R P; Weber, P C; Salemme, F R; Tollin, G

    1982-12-07

    Electron transfer reactions between Clostridum pasteurianum flavodoxin semiquinone and various oxidants [horse heart cytochrome c, ferricyanide, and ferric ethylenediaminetetraacetic [horse heart cytochrome c, ferricyanide, and ferric ethylenediaminetetraacetic acid (EDTA)] have been studied as a function of ionic strength by using stopped-flow spectrophotometry. The cytochrome c reaction is complicated by the existence of two cytochrome species which react at different rates and whose relative concentrations are ionic strength dependent. Only the faster of these two reactions is considered here. At low ionic strength, complex formation between cytochrome c and flavodoxin is indicated by a leveling off of the pseudo-first-order rate constant at high cytochrome c concentration. This is not observed for either ferricyanide or ferric EDTA. For cytochrome c, the rate and association constants for complex formation were found to increase with decreasing ionic strength, consistent with negative charges on flavodoxin interacting with the positively charged cytochrome electron transfer site. Both ferricyanide and ferric EDTA are negatively charged oxidants, and the rate data respond to ionic strength changes as would be predicted for reactants of the same charge sign. These results demonstrate that electrostatic interactions involving negatively charged groups are important in orienting flavodoxin with respect to oxidants during electron transfer. We have also carried out computer modeling studies of putative complexes of flavodoxin with cytochrome c and ferricyanide, which relate their structural properties to both the observed kinetic behavior and some more general features of physiological electron transfer processes. The results of this study are consistent with the ionic strength behavior described above.

  4. Electrochemical Deposition of Platinum and Palladium on Gold Nanoparticles Loaded Carbon Nanotube Support for Oxidation Reactions in Fuel Cell

    Directory of Open Access Journals (Sweden)

    Surin Saipanya

    2014-01-01

    Full Text Available Pt and Pd sequentially electrodeposited Au nanoparticles loaded carbon nanotube (Au-CNT was prepared for the electrocatalytic study of methanol, ethanol, and formic acid oxidations. All electrochemical measurements were carried out in a three-electrode cell. A platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the Au-CNT, phosphate buffer, isopropanol, and Nafion was mixed and dropped on glassy carbon as a working electrode. By sequential deposition method, PdPtPt/Au-CNT, PtPdPd/Au-CNT, and PtPdPt/Au-CNT catalysts were prepared. Cyclic voltammograms (CVs of those catalysts in 1 M H2SO4 solution showed hydrogen adsorption and hydrogen desorption reactions. CV responses for those three catalysts in methanol, ethanol, and formic acid electrooxidations studied in 2 M CH3OH, CH3CH2OH, and HCOOH in 1 M H2SO4 show characteristic oxidation peaks. The oxidation peaks at anodic scan contribute to those organic substance oxidations while the peaks at cathodic scan are related with the reoxidation of the adsorbed carbonaceous species. Comparing all those three catalysts, it can be found that the PdPtPt/Au-CNT catalyst is good at methanol oxidation; the PtPdPt/Au-CNT effectively enhances ethanol oxidation while the PtPdPd/Au-CNT exceptionally catalyzes formic acid oxidation. Therefore, a different stoichiometry affects the electrochemical active surface area of the catalysts to achieve the catalytic oxidation reactions.

  5. Microcalorimetric Adsorption of Alumina Oxide Catalysts for Combination of Ethylbenzene dehydrogenation and carbon Dioxide Shift-reaction

    Institute of Scientific and Technical Information of China (English)

    GE Xin; SHEN Jian-yi

    2004-01-01

    Styrene (STY) is now produced industrially in fairly large quantities by the dehydrogenation of ethylbenzene (EB) using promoted iron oxide catalyst with superheated steam.In this case, small amount of carbon dioxide formed as a by-product was known to inhibit the catalytic activity of commercial catalyst. Recently, there have been some reports which carbon dioxide showed positive effects to promote catalytic activities on the reaction over several catalysts.In this study, we attempted to combine the dehydrogenation of EB to STY with the carbon dioxide shift-reaction. The combine reaction (EB + CO2 → STY + H2O + CO) can be considered as one of the ways of using CO2 resources and can yield simultaneously STY and Carbon oxide.Alumina oxide catalysts such as Al2O3, Na2O/Al2O3 and K2O/Al2O3 were prepared by the usual impregnation method with an aqueous solution of NaNO3 and KNO3, and then calcined at 650℃ for 5 h in a stream of air. The reaction condition is 600℃, flow of CO2 38ml/mon and space velocity (EB) 1.28h-1.

  6. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  7. Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)

    Energy Technology Data Exchange (ETDEWEB)

    Farberow, Carrie A.; Dumesic, James A.; Mavrikakis, Manos

    2014-10-03

    Reaction pathways are explored for low temperature (e.g., 400 K) reduction of nitric oxide by hydrogen on Pt(111). First-principles electronic structure calculations based on periodic, self-consistent density functional theory(DFT-GGA, PW91) are employed to obtain thermodynamic and kinetic parameters for proposed reaction schemes on Pt(111). The surface of Pt(111) during NO reduction by H₂ at low temperatures is predicted to operate at a high NO coverage, and this environment is explicitly taken into account in the DFT calculations. Maximum rate analyses are performed to assess the most likely reaction mechanisms leading to formation of N₂O, the major product observed experimentally at low temperatures. The results of these analyses suggest that the reaction most likely proceeds via the addition of at least two H atoms to adsorbed NO, followed by cleavage of the N-O bond.

  8. Biocatalytic resolution of enantiomeric mixtures of 1-aminoethanephosphonic acid.

    Science.gov (United States)

    Brzezińska-Rodak, Małgorzata; Klimek-Ochab, Magdalena; Zymańczyk-Duda, Ewa; Kafarski, Paweł

    2011-07-14

    Several fungal strains, namely Bauveria bassiana, Cuninghamella echinulata, Aspergillus fumigatus, Penicillium crustosum and Cladosporium herbarum, were used as biocatalysts to resolve racemic mixtures of 1-aminoethanephosphonic acid using L/D amino acid oxidase activity. The course of reaction was analyzed by 31P-NMR in the presence of cyclodextrin used as chiral discriminating agent. The best result (42% e.e of R-isomer) was obtained with a strain of Cuninghamella echinulata.

  9. Biocatalytic Resolution of Enantiomeric Mixtures of 1-Aminoethanephosphonic Acid

    Directory of Open Access Journals (Sweden)

    Paweł Kafarski

    2011-07-01

    Full Text Available Several fungal strains, namely Bauveria bassiana, Cuninghamella echinulata, Aspergillus fumigatus, Penicillium crustosum and Cladosporium herbarum, were used as biocatalysts to resolve racemic mixtures of 1-aminoethanephosphonic acid using L/D amino acid oxidase activity. The course of reaction was analyzed by 31P-NMR in the presence of cyclodextrin used as chiral discriminating agent. The best result (42% e.e of R-isomer was obtained with a strain of Cuninghamella echinulata.

  10. Controllable Synthesis of Formaldehyde Modified Manganese Oxide Based on Gas-Liquid Interfacial Reaction and Its Application of Electrochemical Sensing.

    Science.gov (United States)

    Bai, Wushuang; Sheng, Qinglin; Nie, Fei; Zheng, Jianbin

    2015-12-30

    Controllable synthesis of manganese oxides was performed via a simple one-step synthetic method. Then obtained manganese oxides which exhibit flower-like, cloud-like, hexagon-like, and rod-like morphologies were modified by formaldehyde based on a simple self-made gas-liquid reaction device respectively and the modified manganese oxides with coral-like, scallop-like and rod-like morphology were synthesized accordingly. The obtained materials were characterized and the formation mechanism was also researched. Then the modified manganese oxides were used to fabricate electrochemical sensors to detect H2O2. Comparison of electrochemical properties between three kinds of modified manganese oxides was investigated and the best one has been successfully employed as H2O2 sensor which shows a low detection limit of 0.01 μM, high sensitivity of 162.69 μA mM(-1) cm(-2), and wide linear range of 0.05 μM-12.78 mM. The study provides a new method for controllable synthesis of metal oxides, and electrochemical application of formaldehyde modified manganese oxides will provides a new strategy for electrochemical sensing with high performance, low cost, and simple fabrication.

  11. Reaction of Oxidized Polysialic Acid and a Diaminooxy Linker: Characterization and Process Optimization Using Nuclear Magnetic Resonance Spectroscopy.

    Science.gov (United States)

    Ray, G Joseph; Siekmann, Jürgen; Scheinecker, Richard; Zhang, Zhenqing; Gerasimov, Mikhail V; Szabo, Christina M; Kosma, Paul

    2016-09-21

    Native polysialic acid (natPSA) is a high-molecular-weight glycan composed of repeat units of α-(2 → 8) linked N-acetylneuraminic acid (Neu5Ac). Mild periodate oxidation of PSA selectively targets the end sialic acid ring containing three adjacent alcohols generating a putative aldehyde, which can be used, after attachment of a linker molecule, for terminal attachment of PSA to protein. Previously, we showed that the oxidized PSA (oxoPSA) contained a hemiacetal at the oxidation site and can react with a linker containing an aminooxy group in a conjugation reaction to form a stable oxime linkage. Thus, reagents containing an aminooxy group may be prepared for conjugation of PSA to the carbohydrate moiety of therapeutic proteins, thereby increasing their half-life. These aminooxy-PSA reagents can selectively react with aldehyde groups generated by mild NaIO4 oxidation of glycans on the surface of the target protein. To comprehend the conjugation, unoxidized tetrasialic acid and Neu5Ac were reacted in model reactions with a diaminooxy linker to define the nuclear magnetic resonance (NMR) chemical shifts. Based on these data, we were able to show that, in the case of PSA, the reaction with the linker occurs not only at the expected oxidized end to form an aldoxime but also at the end distal to the oxidation to form a ketoxime. We determined that, in aged solutions, both oxoPSA and PSA aldoxime were hydrolyzed. PSA aldoxime was also shown to disproportionate to form a dimer (PSA-linker-PSA), which then could react further with the released linker at one of its PSA termini. Furthermore, NMR was used to monitor the effects of deliberate process changes so that conditions could be optimized for attachment of linker at the desired end of the PSA chain, which led to a well-defined product.

  12. Electrochemical behavior of biocatalytical composite based on heme-proteins, didodecyldimethylammonium bromide and room-temperature ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Xu Yanxia, E-mail: xuyanxiatv@yahoo.com.cn [Department of Chemistry and Environmental Engineering, Wuhan Bioengineering Institute, Wuhan 430415 (China); College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 100080 (China); Hu Chengguo [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 100080 (China); Hu Shengshui, E-mail: sshu@whu.edu.cn [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 100080 (China)

    2010-03-17

    A novel biocompatible composite film based on a water-insoluble surfactant, didodecyldimethylammonium bromide (DDAB), and a hydrophobic room-temperature ionic liquid (RTIL), 1-hexyl-3-methyl-imidazolium hexafluorophosphate (HIMIMPF{sub 6}), for the immobilization of biocatalytical proteins was reported. Differential scanning calorimetry (DSC) showed that the DDAB-HIMIMPF{sub 6} composite film has higher thermal stability than the DDAB film alone. SEM images indicated that different microstructures existed between the DDAB film and the composite film, indicating the interaction between DDAB and RTILs. This composite can be used as the immobilization matrix of proteins and other biomacromolecules. Heme-proteins, including hemoglobin (Hb), myoglobin (Mb) and horseradish peroxidase (HRP), were used as model proteins for studying the electrochemical behaviors of the resulting biocatalytical composite films. In the case of Hb, a pair of well-defined quasi-reversible redox peaks was obtained when the composite film containing Hb was modified on a glassy carbon electrode. The formal potential (E{sup o}'), the surface coverage ({Gamma}{sup *}) and the electron transfer rate constant (k{sub s}) were calculated as -0.308 V, 1.32 x 10{sup -11} mol cm{sup -2} and 11.642 s{sup -1}, respectively. While, these parameters for Hb on DDAB films alone were -0.309 V, 7.20 x 10{sup -12} mol cm{sup -2} and 2.748 s{sup -1}, respectively. Therefore, the composite are more suitable for the direct electron transfer between Hb than DDAB alone. The native conformation and bioactivity of Hb adsorbed on the composite film was proved to be maintained, reflected by the unchanged ultraviolet-visible (UV-vis) as well as the catalytic activity toward hydrogen peroxide (H{sub 2}O{sub 2}) and nitric oxide (NO) compared with the free Hb molecules. Furthermore, Hb on the composite film are more sensitive for the detection of hydrogen peroxide (H{sub 2}O{sub 2}) and nitric oxide (NO) than that on

  13. Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

    KAUST Repository

    Baron, Marco

    2016-06-14

    Gold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Investigation of heat induced reactions between lipid oxidation products and amino acids in lipid rich model systems and hazelnuts.

    Science.gov (United States)

    Karademir, Yeşim; Göncüoğlu, Neslihan; Gökmen, Vural

    2013-07-01

    This study aimed to investigate the contribution of lipid oxidation to non-enzymatic browning reactions in lipid rich model and actual food systems. Hazelnut oil and model reaction mixtures consisting of different amino acids were heated under certain conditions to determine possible lipid oxidation and non-enzymatic browning reaction products. In model systems, the Schiff base of 2,4-decadienal, its decarboxylated form, and reaction products formed after hydrolytic cleavage of the Schiff base or decarboxylated form were identified by high resolution mass spectrometry. No furosine was detected in hazelnuts after roasting at 160 °C while the concentration of free amino acids significantly decreased. 2,4-Decadienal reacted effectively with all amino acids studied through a Maillard type carbonyl-amine condensation pathway. (2E,4E)-Deca-2,4-dien-1-amine was identified as a typical reaction product in model systems and roasted hazelnuts. In lipid-rich foods like hazelnuts, lipid-derived carbonyls might be responsible for potential modifications of free and protein bound amino acids during heating.

  15. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide

    Directory of Open Access Journals (Sweden)

    M.S. Fal Desai

    2015-03-01

    Full Text Available The catalytic activity of PdO/MnO2 and Rh2O3/MnO2 is investigated for NO-CO redox reaction. Supported catalysts are prepared by wet impregnation method. Among the tested catalysts, PdO/MnO2 shows higher activity for this reaction. Active metal dispersion on MnO2 enhances the selectivity for N2 over N2O in this reaction. The XRD substantiate the formation of MnO2 monophasic phase. SEM images show the formation of elongated particles. TEM images indicate nano-size rod-like morphologies. An increase in the catalytic activity is observed on supported Pd and Rh oxides on MnO2. Temperature programed desorption studies with NO and CO are undertaken to investigate the catalytic surface studies. © 2015 BCREC UNDIP. All rights reservedReceived: 22nd November 2014; Revised: 31st December 2014; Accepted: 2nd January 2015How to Cite: Fal Desai, M.S., Kunkalekar, R.K., Salker, A.V. (2015. Preparation, Characterization and NO-CO Redox Reaction Studies over Palladium and Rhodium Oxides Supported on Manganese Dioxide. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 98-103. (doi:10.9767/bcrec.10.1.7802.98-103Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7802.98-103 

  16. Activity and Stability of Rare Earth-Based Hydride Alloys as Catalysts of Hydrogen Absorption-Oxidation Reactions

    Institute of Scientific and Technical Information of China (English)

    Ying Taokai(应桃开); Gao Xueping(高学平); Hu Weikang(胡伟康); Noréus Dag

    2004-01-01

    Rare earth-based AB5-type hydrogen storage alloys as catalysts of hydrogen-diffusion electrodes for hydrogen absorption and oxidation reactions in alkaline fuel cells were investigated. It is demonstrated that the meta-hydride hydrogen-diffusion electrodes could be charged by hydrogen gas and electrochemically discharged at the same time to retain a stable oxidation potential for a long period. The catalytic activities and stability are almost comparable with a Pt catalyst on the active carbon. Further improvement of performances is expected via reduction of catalyst size into nanometers.

  17. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  18. Biocatalytic Synthesis of Chiral Alcohols and Amino Acids for Development of Pharmaceuticals

    Directory of Open Access Journals (Sweden)

    Ramesh N. Patel

    2013-10-01

    Full Text Available Chirality is a key factor in the safety and efficacy of many drug products and thus the production of single enantiomers of drug intermediates and drugs has become increasingly important in the pharmaceutical industry. There has been an increasing awareness of the enormous potential of microorganisms and enzymes derived there from for the transformation of synthetic chemicals with high chemo-, regio- and enatioselectivities. In this article, biocatalytic processes are described for the synthesis of chiral alcohols and unntural aminoacids for pharmaceuticals.

  19. Towards biochemical filters with a sigmoidal response to pH changes: buffered biocatalytic signal transduction.

    Science.gov (United States)

    Pita, Marcos; Privman, Vladimir; Arugula, Mary A; Melnikov, Dmitriy; Bocharova, Vera; Katz, Evgeny

    2011-03-14

    We realize a biochemical filtering process by introducing a buffer in a biocatalytic signal-transduction logic system based on the function of an enzyme, esterase. The input, ethyl butyrate, is converted into butyric acid--the output signal, which in turn is measured by the drop in the pH value. The developed approach offers a versatile "network element" for increasing the complexity of biochemical information processing systems. Evaluation of an optimal regime for quality filtering is accomplished in the framework of a kinetic rate-equation model.

  20. Towards biochemical filters with a sigmoidal response to pH changes: buffered biocatalytic signal transduction

    Science.gov (United States)

    Pita, Marcos; Privman, Vladimir; Arugula, Mary A.; Melnikov, Dmitriy; Bocharova, Vera; Katz, Evgeny

    We realize a biochemical filtering process by introducing a buffer in a biocatalytic signal-transduction logic system based on the function of an enzyme, esterase. The input, ethyl butyrate, is converted into butyric acid-the output signal, which in turn is measured by the drop in the pH value. The developed approach offers a versatile "network element" for increasing the complexity of biochemical information processing systems. Evaluation of an optimal regime for quality filtering is accomplished in the framework of a kinetic rate-equation model.

  1. Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

    Science.gov (United States)

    Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

    2016-05-01

    Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK.

  2. Deactivation of a mixed oxide catalyst of Mo-V-Te-Nb-O composition in the reaction of oxidative ethane dehydrogenation

    Science.gov (United States)

    Mishanin, I. I.; Kalenchuk, A. N.; Maslakov, K. I.; Lunin, V. V.; Koklin, A. E.; Finashina, E. D.; Bogdan, V. I.

    2016-06-01

    The operational stability of a mixed oxide catalyst of Mo-V-Te-Nb-O composition in the oxidative dehydrogenation of ethane (ratio of C2H6: O2 = 3: 1) is studied in a flow reactor at temperatures of 340-400°C, a pressure of 1 atm, and a WHSV of the feed mixture of 800 h-1. It is found that the selectivity toward ethylene is 98% at 340°C, but the conversion of ethane at this temperature is only 6%; when the temperature is raised to 400°C, the conversion of ethane is increased to 37%, while the selectivity toward ethylene is reduced to 85%. Using physical and chemical means (XPS, SEM), it is found that the lack of oxidant in the reaction mixture leads to irreversible changes in the catalyst, i.e., reduced selectivity and activity. Raising the reaction temperature to 400°C allows the reduction of tellurium by ethane, from the +6 oxidation state to the zerovalent state, with its subsequent sublimation and the destruction of the catalytically active and selective phase; in its characteristics, the catalyst becomes similar to the Mo-V-Nb-O system containing no tellurium.

  3. Epoxidation reaction of perfluoroalkenes with tert-amine N-oxide

    Institute of Scientific and Technical Information of China (English)

    Xing Wei Cai; Min Sha; Biao Jiang; Ren Ming Pan

    2012-01-01

    Straight-chain aliphatic tert-amine N-oxides were found to be useful oxidizing agent for epoxidation of tri-and tetra-substituted perfluoroalkenes under mild conditions in high yields.The process for epoxidation by employing tri-n-butylamine N-oxide gave the best result in the reagent survey.

  4. Tyramine-based enzymatic conjugate repeats for ultrasensitive immunoassay accompanying tyramine signal amplification with enzymatic biocatalytic precipitation.

    Science.gov (United States)

    Hou, Li; Tang, Yun; Xu, Mingdi; Gao, Zhuangqiang; Tang, Dianping

    2014-08-19

    A new impedimetric immunoassay protocol based on enzyme-triggered formation of tyramine-enzyme repeats on gold nanoparticle (AuNP) was designed for highly sensitive detection of carcinoembryonic antigen (CEA, as a model) by virtue of utilizing enzymatic biocatalytic precipitation toward 4-chloro-1-naphthol (4-CN) on anti-CEA antibody (Ab1)-modified immunosensor. Initially, AuNP was functionalized with horseradish peroxidase and detection antibody (HRP-AuNP-Ab2), and then HRP-tyramine conjugate was utilized for the formation of tyramine-HRP repeats through the triggering of the immobilized HRP on the AuNP with the aid of H2O2. In the presence of target CEA, the carried HRP-tyramine repeats accompanying the sandwiched immunocomplex catalyzed the 4-CN oxidation to produce an insoluble precipitation on the immunosensor, thus causing a local alteration of the conductivity. Three signal-transduction tags including HRP-Ab2, HRP-AuNP-Ab2, and HRP-AuNP-Ab2 with HRP-tyramine repeats were employed for target CEA evaluation, and improved analytical properties were achieved by HRP-AuNP-Ab2 with HRP-tyramine repeats. Using the unique signal-transduction tag, the analytical performance of the impedimetric immunoassay was studied in detail. Under the optimal conditions, the impedimetric immunosensor displayed a wide dynamic working range of between 0.5 pg mL(-1) and 40 ng mL(-1) with a detection limit (LOD) of 0.38 pg mL(-1) relative to target CEA. The coefficients of variation (CVs) were ≤9.3% and 13.3% for the intra-assay and interassay, respectively. The levels of CEA in eight clinical serum specimens were measured by using the developed impedimetric immunosensor. The obtained results correlated well with those from the electrochemiluminescent (ECL)-based immunoassay with a correlation coefficient of 0.998.

  5. Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions.

    Science.gov (United States)

    Liu, Wenxia; Shen, Lianfeng; Zhang, Fawen; Liu, Wenbin; Zheng, Minghui; Yang, Xitian

    2013-08-01

    Polychlorinated diphenyl ether (PCDE) has attracted great attention recently as an important type of environmental pollutant. The influence of iron and copper oxides on formation of PCDEs was investigated using laboratory-scale flow reactors under air and under nitrogen at 350 °C, a temperature corresponding to the post-combustion zone of a municipal solid waste incinerator. The results show that the 2,2',3,4,4',5,5',6-otachlorodiphenyl ether (OCDE) formed from the condensation of pentachlorophenol (PCP) and 1,2,4,5-tetrachlorobenzene (Cl4Bz) is the predominant congener formed on the SiO2/Fe2O3 surface with and without oxygen. This indicated that HCl elimination between PCP and 1,2,4,5-Cl4Bz molecules formed 2,2',3,4,4',5,5',6-OCDE in the presence of Fe2O3. On the other hand, decachlorodiphenyl ether, nonachlorodiphenyl ether, and OCDE were the dominant products on the SiO2/CuO surface without oxygen, although the 2,2',3,4,4',5,5',6-OCDE was the dominant product on the SiO2/CuO surface with oxygen. Therefore, the presence of Fe2O3 and CuO influences the formation and homologue distribution of PCDEs, which shifted towards the lower chlorinated species. Fe2O3 can promote both the condensation and dechlorination reaction without oxygen. On the contrary, with oxygen, Fe2O3 suppresses the condensation of chlorobenzene and chlorophenol to form PCDEs and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). CuO can increase the formation of lower chlorinated PCDEs and PCDDs without oxygen. In conclusion, the different fly ash components have a major influence on PCDE emissions.

  6. Induced axial chirality in biocatalytic asymmetric ketone reduction.

    Science.gov (United States)

    Agudo, Rubén; Roiban, Gheorghe-Doru; Reetz, Manfred T

    2013-02-06

    Catalytic asymmetric reduction of prochiral ketones of type 4-alkylidene cyclohexanone with formation of the corresponding axially chiral R-configurated alcohols (up to 99% ee) was achieved using alcohol dehydrogenases, whereas chiral transition-metal catalysts fail. Reversal of enantioselectivity proved to be possible by directed evolution based on saturation mutagenesis (up to 98% ee (S)). Utilization of ketone with a vinyl bromide moiety allows respective R- and S-alcohols to be exploited as key compounds in Pd-catalyzed cascade reactions.

  7. Increasing importance of protein flexibility in designing biocatalytic processes

    Directory of Open Access Journals (Sweden)

    Joyeeta Mukherjee

    2015-06-01

    Full Text Available Enzymes require some flexibility for catalysis. Biotechnologists prefer stable enzymes but often this stabilization comes at the cost of reduced efficiency. Enzymes from thermophiles have low flexibility but poor catalytic rates. Enzymes from psychrophiles are less stable but show good catalytic rates at low temperature. In organic solvents enzymes perform poorly as the prior drying makes the enzyme molecules very rigid. Adding water or increasing reaction temperature improves flexibility and catalytic rates. In case of hydrolases, flexibility and enantioselectivity have interdependence. Understanding the complex role of protein flexibility in biocatalysis can help in designing biotechnological processes.

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

    Science.gov (United States)

    2014-02-22

    16:2310 1 3 reaction and coined it a pre-ignition reaction (PIR). They showed that the alumina shell surrounding the Al particle was fluorinated by...Chem C 114:9191 9195 Clark BR, Pantoya ML (2010) The aluminium and iodine pentoxide reaction for the destruction of spore forming bacteria . Phys Chem

  9. Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

    Institute of Scientific and Technical Information of China (English)

    张焕军; 朱国才

    2004-01-01

    The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor.The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined. The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determination of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process.The apparent activation energy was calculated to be 32.8kJ·mo1-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

  10. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces

    OpenAIRE

    Chapleski, Robert C.; Zhang, Yafen; Troya, Diego; Morris, John R.

    2015-01-01

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, research...

  11. Non-oxidative dehydroaromatization of methane:an effective reaction regeneration cyclic operation for catalyst life extension

    OpenAIRE

    Portilla Ovejero, Mª Teresa; LLOPIS ALONSO, FRANCISCO; LLOPIS ALONSO, FRANCISCO JAVIER; Martínez, Cristina

    2015-01-01

    Non-oxidative methane aromatization is an attractive direct route for producing higher hydrocarbons. It is highly selective to benzene despite the low conversion due to thermodynamic limitations, and Mo/H-ZSM-5, the first catalyst proposed for this reaction, is still considered as one of the most adequate. The major problem of this process is the severe catalyst deactivation due to the rapid build-up of carbonaceous deposits on the catalysts. Here we present an effective regeneration procedur...

  12. Facile synthesis of Pd-based bimetallic nanocrystals and their application as catalysts for methanol oxidation reaction

    Science.gov (United States)

    Xi, Pinxian; Cao, Yang; Yang, Fengchun; Ma, Cai; Chen, Fengjuan; Yu, Sha; Wang, Shuai; Zeng, Zhengzhi; Zhang, Xin

    2013-06-01

    We employed an efficient and facile route to synthesise monodisperse Pd-based bimetallic nanocrystals (MPd: M = Cu, Co and Ni) via a controlled co-reduction of Pd(ii) chloride and M(ii) nitrate at 200-230 °C in the presence of oleylamine (OAm). These monodisperse Pd-based nanocrystals have small dimensions, unique structures and homogeneous morphology, thus exhibit efficient catalytic activities for methanol oxidation in alkaline solution, which is much better than commercial Pd/C with same amount of palladium. The catalytic activities of these nanocrystals followed the order of NiPd/C > CoPd/C > CuPd/C > commercial Pd/C, due to the different synergistic effects. Our results show that these Pd-based bimetallic nanocrystals can be promising as practical catalysts for methanol oxidation reactions and other catalytic reactions in further investigations.We employed an efficient and facile route to synthesise monodisperse Pd-based bimetallic nanocrystals (MPd: M = Cu, Co and Ni) via a controlled co-reduction of Pd(ii) chloride and M(ii) nitrate at 200-230 °C in the presence of oleylamine (OAm). These monodisperse Pd-based nanocrystals have small dimensions, unique structures and homogeneous morphology, thus exhibit efficient catalytic activities for methanol oxidation in alkaline solution, which is much better than commercial Pd/C with same amount of palladium. The catalytic activities of these nanocrystals followed the order of NiPd/C > CoPd/C > CuPd/C > commercial Pd/C, due to the different synergistic effects. Our results show that these Pd-based bimetallic nanocrystals can be promising as practical catalysts for methanol oxidation reactions and other catalytic reactions in further investigations. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00912b

  13. Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Xi, Yue-Ting; Wei, Ping-Jie; Wang, Ru-Chun; Liu, Jin-Gang

    2015-05-01

    Inspired by the multicopper active site of laccase, which efficiently catalyzes the oxygen reduction reaction (ORR), herein we report a novel bio-inspired ORR catalyst composed of a multinuclear copper complex that was immobilized on the surface of reduced graphene oxide (rGO) via the covalently grafted triazole-dipyridine (TADPy) dinucleating ligand. This rGO-TADPyCu catalyst exhibited high ORR activity and superior long-term stability compared to Pt/C in alkaline media.

  14. An in Situ Generated Palladium on Aluminum Oxide: Applications in Gram-Scale Matsuda-Heck Reactions.

    Science.gov (United States)

    Pape, Simon; Daukšaitė, Lauryna; Lucks, Sandra; Gu, Xiaoting; Brunner, Heiko

    2016-12-16

    In situ generated palladium on aluminum oxide provides an active catalytic system for Matsuda-Heck reactions in gram-scale. The novel catalyst proceeded through a significantly higher catalytic activity compared to the classical Pd/C system. Based on the high catalytic activity the first α,β,β-triarylation of methyl acrylate in good yields could be provided in one-step.

  15. Combination of deep eutectic solvent and ionic liquid to improve biocatalytic reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cell

    Science.gov (United States)

    Xu, Pei; Du, Peng-Xuan; Zong, Min-Hua; Li, Ning; Lou, Wen-Yong

    2016-05-01

    The efficient anti-Prelog asymmetric reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cells was successfully performed in a biphasic system consisting of deep eutectic solvent (DES) and water-immiscible ionic liquid (IL). Various DESs exerted different effects on the synthesis of (R)-2-octanol. Choline chloride/ethylene glycol (ChCl/EG) exhibited good biocompatibility and could moderately increase the cell membrane permeability thus leading to the better results. Adding ChCl/EG increased the optimal substrate concentration from 40 mM to 60 mM and the product e.e. kept above 99.9%. To further improve the reaction efficiency, water-immiscible ILs were introduced to the reaction system and an enhanced substrate concentration (1.5 M) was observed with C4MIM·PF6. Additionally, the cells manifested good operational stability in the reaction system. Thus, the efficient biocatalytic process with ChCl/EG and C4MIM·PF6 was promising for efficient synthesis of (R)-2-octanol.

  16. Combination of deep eutectic solvent and ionic liquid to improve biocatalytic reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cell.

    Science.gov (United States)

    Xu, Pei; Du, Peng-Xuan; Zong, Min-Hua; Li, Ning; Lou, Wen-Yong

    2016-01-01

    The efficient anti-Prelog asymmetric reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cells was successfully performed in a biphasic system consisting of deep eutectic solvent (DES) and water-immiscible ionic liquid (IL). Various DESs exerted different effects on the synthesis of (R)-2-octanol. Choline chloride/ethylene glycol (ChCl/EG) exhibited good biocompatibility and could moderately increase the cell membrane permeability thus leading to the better results. Adding ChCl/EG increased the optimal substrate concentration from 40 mM to 60 mM and the product e.e. kept above 99.9%. To further improve the reaction efficiency, water-immiscible ILs were introduced to the reaction system and an enhanced substrate concentration (1.5 M) was observed with C4MIM·PF6. Additionally, the cells manifested good operational stability in the reaction system. Thus, the efficient biocatalytic process with ChCl/EG and C4MIM·PF6 was promising for efficient synthesis of (R)-2-octanol.

  17. Oxidation of MC-LR and -RR with chlorine and potassium permanganate: toxicity of the reaction products.

    Science.gov (United States)

    Rodríguez, Eva M; Acero, Juan L; Spoof, Lisa; Meriluoto, Jussi

    2008-03-01

    Toxin-producing cyanobacteria are abundant in surface waters used as drinking water resources. Microcystins (MC) produced by certain cyanobacteria present acute and chronic toxicity, and their removal in drinking water treatment processes is of increasing concern. Previous studies have demonstrated that chlorine and potassium permanganate are feasible oxidants for the removal of MCs present in drinking water resources, although the oxidation might lead to toxic oxidation products. In this paper, the toxicity of the oxidation products of MC-LR and -RR has been studied using protein phosphatase 1 inhibition assay (PPIA). The HPLC and ELISA analyses correlated with the PPIA results for both toxins. The samples containing the oxidation products were fractionated by HPLC and the toxicity of the fractions was tested with PPIA. The results revealed that protein phosphatase 1 inhibition emerged only from intact MC, while the oxidation products were non-toxic. Similar results were obtained in experiments performed in natural waters: no reaction products or interactions exhibiting protein phosphatase 1 inhibition were detected.

  18. Reaction Chemistry of W-Mn/SiO2 Catalyst for the Oxidative Coupling of Methane

    Institute of Scientific and Technical Information of China (English)

    Shuben Li

    2003-01-01

    Reaction chemistry of the OCM reaction on W-Mn/SiO2 catalyst has been reviewed in thisaccount. Initial activity and selectivity, stability in a long-term reaction, reaction at elevated pressures anda modelling test in a stainless-steel fluidized-bed reactor show that W-Mn/SiO2 has promising performancefor the development of an OCM process that directly produces ethylene from natural gas. A study onsurface catalytic reaction kinetics and used catalyst structure characterization revealed a possible reasonwhy C2 and COx selectivity changed during the long-term reaction. Further improvement of the catalystcomposition and preparation method should be a future direction of study on OCM reaction over W-Mn/SiO2 catalyst.

  19. Effect of diluent and reaction parameter on selective oxidation of propane over MoVTeNb catalyst using nanoflow catalytic reactor

    Institute of Scientific and Technical Information of China (English)

    Restu Kartiko Widi; Sharifah Bee Abdul Hamid; Robert Schl(o)gl

    2008-01-01

    The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity (GHSV) and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.

  20. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces.

    Science.gov (United States)

    Chapleski, Robert C; Zhang, Yafen; Troya, Diego; Morris, John R

    2016-07-01

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases.

  1. Guidelines and cost analysis for catalyst production in biocatalytic processes

    DEFF Research Database (Denmark)

    Tufvesson, Pär; Lima Ramos, Joana; Nordblad, Mathias

    2011-01-01

    be a powerful tool to guide research and development activities in order to achieve commercial potential. This study discusses the cost contribution of the biocatalyst in processes that use isolated enzymes, immobilized enzymes, or whole cells to catalyze reactions leading to the production of chemicals...... as well as the production scale are crucial for decreasing the total cost contribution of the biocatalyst. Moreover, it is clear that, based on initial process performance, the potential to reduce production costs by several orders of magnitude is possible. Guideline minimum productivities for a feasible...... process are suggested for different types of processes and products, based on typical values of biocatalyst and product costs. Such guidelines are dependent on the format of the biocatalyst (whole-cell, soluble enzyme, immobilized enzyme), as well as product market size and value. For example commodity...

  2. The gas chromatographic analysis of the reaction products of the partial isobutane oxidation as a two phase process.

    Science.gov (United States)

    Willms, Thomas; Kryk, Holger; Hampel, Uwe

    2016-08-05

    The partial oxidation of isobutane to t-butyl hydroperoxide (TBHP) has been studied analytically for the first time as a two-phase process in a capillary micro reactor. In order to obtain detailed information on products, yields, selectivities and reaction pathways, the products have been investigated by GC/MS. An Rxi-5ms column and a PTV-injector have been used to analyze the liquid products. TBHP, di-t-butyl peroxide (DTBP), t-butanol (TBA), and propanone as main products as well as further by-products e.g. methanal, isopropanol, isobutanol and isobutanal in minor quantities have been identified by MS. The liquid products have been obtained by quenching the reaction and vaporizing the isobutane afterwards by pressure reduction using a mass flow controller allowing a constant mass flow. For all liquid reaction products calibrations, a validation of the method including limits of quantification and detection as well as calculation of uncertainties has been performed. The results have been applied successfully for the investigation of the selectivities of the main products (TBHP, DTBP, TBA, propanone) of the isobutane oxidation. In the frame of the analytical investigation of this reaction a correlation coefficient of r(2)>0.999 for TBHP and DTBP, which is necessary to perform a validation, has been obtained for the first time. The gaseous phase has been analyzed using a GASPRO column, a DEANS switch, a mole sieve column and a TCD detector. Apart from the gaseous reactants, isobutene has been found.

  3. Insight into the reaction mechanisms for oxidative addition of strong σ bonds to an Al(i) center.

    Science.gov (United States)

    Zhang, Xiangfei; Cao, Zexing

    2016-06-21

    The oxidation addition of a series of σ H-X bonds (X = H, B, C, Si, N, P, and O) to a single Al(i) supported by a (NacNac)(-) bidentate ligand ((NacNac)(-) = [ArNC(Me)CHC(Me)NAr](-) and Ar = 2,6-(i)Pr2C6H3) has been explored through extensive DFT calculations. The presented results show that activation and addition of these σ bonds follow various reaction mechanisms, in which hydride transfer, proton transfer, and Al-X bond coupling steps are involved. The predicted free energy barriers for these oxidative additions range from 8 to 32 kcal mol(-1), and all the reactions are remarkably favorable thermodynamically. However, sterically hindered ligands, for most reactants, make the formation of the initial reactant complex difficult and may reduce the efficiency of the reaction. Calculations reveal a strong dependence of the reaction mechanism and low-energy channel on the bonding features of X-H and the local structural environments.

  4. Fabrication of dendritic silver-coated copper powders by galvanic displacement reaction and their thermal stability against oxidation

    Science.gov (United States)

    Park, Yu-Seon; An, Chang Yong; Kannan, Padmanathan Karthick; Seo, Nary; Zhuo, Kai; Yoo, Tae Kyong; Chung, Chan-Hwa

    2016-12-01

    Two steps of wet chemical processes have been developed for the preparation of core-shell nanostructures of copper and silver, which is a facile and low cost method for the production of large quantity of dendritic powders. First step involves a galvanic displacement reaction with hydrogen evolution which is the motive force of spontaneous electrochemical reaction. To achieve the core-shell structure, silver has been coated on the dendritic copper using the galvanic displacement reaction. The dendritic silver-coated copper powders exhibit high surface-area, excellent conductivity, and good oxidation resistance. It has been found that silver-coated copper powders maintain the electrical conductivity even after annealing at 150 °C for several to tens of minutes, thus it is a promising material and an alternative to pure silver powders in printed electronics application.

  5. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina

    2007-01-01

    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

  6. Utilization of oxidation reactions for the spectrophotometric determination of captopril using brominating agents

    Science.gov (United States)

    El-Didamony, Akram M.; Erfan, Eman A. H.

    2010-03-01

    Three simple, accurate and sensitive methods (A-C) for the spectrophotometric assay of captopril (CPL) in bulk drug, in dosage forms and in the presence of its oxidative degradates have been described. The methods are based on the bromination of captopril with a solution of excess brominating mixture in hydrochloric acid medium. After bromination, the excess brominating mixture is followed by the estimation of surplus bromine by three different reaction schemes. In the first method (A), the determination of the residual bromine is based on its ability to bleach the indigo carmine dye and measuring the absorbance at 610 nm. Method B, involves treating the unreacted bromine with a measured excess of iron(II) and the remaining iron(II) is complexed with 1,10-phenanthroline and the increase in absorbance is measured at 510 nm. In method (C), the surplus bromine is treated with excess of iron(II) and the resulting iron(III) is complexed with thiocyanate and the absorbance is measured at 478 nm. In all the methods, the amount of bromine reacted corresponds to the drug content. The different experimental parameters affecting the development and stability of the color are carefully studied and optimized. Beer's law is valid within a concentration range of 0.4-6.0, 0.4-2.8 and 1.2-4.8 μg mL -1 for methods A, B and C, respectively. The calculated apparent molar absorptivity was found to be 5.16 × 10 4, 9.95 × 10 4 and 1.74 × 10 5 L mol -1 cm -1, for methods A, B and C, respectively. Sandell's sensitivity, correlation coefficients, detection and quantification limits are also reported. No interference was observed from common additives found in pharmaceutical preparations. The proposed methods are successfully applied to the determination of CPL in the tablet formulations with mean recoveries of 99.94-100.11% and the results were statistically compared with those of a reference method by applying Student's t- and F-test.

  7. Development of Theoretical Methods for Predicting Solvent Effects on Reaction Rates in Supercritical Water Oxidation Processes

    Science.gov (United States)

    2007-11-02

    Tucker, manuscript in preparation. “Examination of Nonequilibrium Solvent Effects on an SN2 Reaction in Supercritical Water,” R. Behera, B...DATES COVERED Final: 7/1/99 - 12/31/02 4. TITLE AND SUBTITLE Development of theoretical methods for predicting solvent effects on reactions ...computational methods for predicting how reaction rate constants will vary with thermodynamic condition in supercritical water (SCW). Towards this

  8. Photochemical Oxidative Cyclisation of Stilbenes and Stilbenoids—The Mallory-Reaction

    Directory of Open Access Journals (Sweden)

    Kåre B. Jørgensen

    2010-06-01

    Full Text Available After Mallory described in 1964 the use of iodine as catalyst for the photochemical cyclisation of stilbenes, this reaction has proven its effectiveness in the synthesis of phenanthrenes, other PAHs and phenacenes with a surprisingly large selection of substituents. The “early age” of the reaction was reviewed by Mallory in 1984in a huge chapter in the Organic Reactions series, but the development has continued. Alternative conditions accommodate more sensitive substituents, and isomers can be favoured by sacrificial substituents. Herein the further developments and applications of this reaction after 1984 are discussed and summarized.

  9. First half-reaction mechanism of nitric oxide synthase: the role of proton and oxygen coupled electron transfer in the reaction by quantum mechanics/molecular mechanics.

    Science.gov (United States)

    Cho, Kyung-Bin; Carvajal, Maria Angels; Shaik, Sason

    2009-01-08

    The first half-reaction of nitric oxide synthase (NOS) is investigated by means of quantum mechanical/molecular mechanical (QM/MM) calculations. An energetically feasible arginine hydroxylation path was found only when the iron-oxy complex accepted one proton from an external source. The so formed species has not been considered in heme chemistry; it is described as Por(+*)Fe(III)-OOH and is characterized by the same molecular constituency as the more known ferric-hydroperoxide species, compound 0, but has a cation-radical porphyrin moiety. The reaction itself is found to involve proton coupled electron transfer (PCET) and oxygen coupled electron transfer (OCET) steps en route to the formation of compound I and the ultimate monooxygenation of arginine. The cofactor H(4)B turns out to be a key player in the mechanism acting alternatively as an electron donor (when neutral) and an electron sink (when in its radical-cation state) and, thereby, providing the electron transfer component in the various coupled proton and oxygen transfer steps (see Scheme 4 ). The various pieces of this mechanism account for many of the experimental observations, such as the following: (a) the origins of the second proton supplied to the heme, (b) the elusiveness of compound I, (c) the inactivity of peroxide-shunt pathways in NOS first half-reaction, (d) the inhibition of the H(4)B analogue 4-amino-H(4)B due to protonation at the N3 position, (e) the roles of Trp188 (iNOS numbering) and the crystal water at the active site (W115), and so on. Alternative mechanistic hypotheses are tested and excluded, and a new mechanism for the NOS second half-reaction is proposed.

  10. Investigation of oxidative degradation and non‐enzymatic browning reactions in krill and fish oils

    DEFF Research Database (Denmark)

    Thomsen, Birgitte Raagaard; Haugsgjerd, Bjørn Ole; Griinari, Mikko;

    2013-01-01

    The aim of this research was to investigate the oxidation progress and pathways of krill and fish oil during 21 days of incubation at 40°C. The oxidative stability of the oils was investigated through: (i) classical methods such as peroxide value (PV), anisidine value (AV), thiobarbituric reactive...... substance (TBARS), conjugated dienes and trienes, and antioxidant content, and (ii) advanced methods such as determination of volatiles content by dynamic headspace (DHS)‐GC/MS, lipid classes, and pyrrole content. In addition, the oxidative stability of the oils was evaluated under accelerated oxidation...... conditions using the Oxipres™ at 90°C. The results from analysis of PV, AV, TBARS, conjugated dienes and trienes, and the antioxidant content suggested that krill oil was more oxidatively stable than fish oil. However, the color or other constituents of the krill oil might affect the result...

  11. Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of alpha-pinene degradation and secondary organic aerosol formation.

    Science.gov (United States)

    Librando, Vito; Tringali, Giuseppe

    2005-05-01

    This paper studies the reaction products of alpha-pinene, beta-pinene, sabinene, 3-carene and limonene with OH radicals and of alpha-pinene with ozone using FT-IR spectroscopy for measuring gas phase products and HPLC-MS-MS to measure products in the aerosol phase. These techniques were used to investigate the secondary organic aerosol (SOA) formation from the terpenes. The gas phase reaction products were all quantified using reference compounds. At low terpene concentrations (0.9-2.1 ppm), the molar yields of gas phase reaction products were: HCHO 16-92%, HCOOH 10-54% (OH source: H2O2, 6-25 ppm); HCHO 127-148%, HCOOH 4-6% (OH source: CH3ONO, 5-8 ppm). At high terpene concentrations (4.1-13.2 ppm) the results were: HCHO 9-27%, HCOOH 15-23%, CH3(CO)CH3 0-14%, CH3COOH 0-5%, nopinone 24% (only from beta-pinene oxidation), limona ketone 61% (only from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source H2O2, 23-30 ppm); HCHO 76-183%, HCOOH 12-15%, CH3(CO)CH3 0-12%, nopinone 17% (from beta-pinene oxidation), limona ketone 48% (from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source CH3ONO, 14-16 ppm). Pinic acid, pinonic acid, limonic acid, limoninic acid, 3-caric acid, 3-caronic acid and sabinic acid were identified in the aerosol phase. On the basis of these results, we propose a formation mechanism for pinonic and pinic acid in the aerosol phase explaining how degradation products could influence SOA formation and growth in the troposphere.

  12. Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway

    Indian Academy of Sciences (India)

    Sourov Ghosh; C Retna Raj

    2015-05-01

    Synthesis of highly efficient functional electrocatalyst that favours the electrochemical oxidation of formic acid via CO-free dehydrogenation pathway is required for direct formic acid fuel cells. Traditional catalysts favour the dehydration pathway involving the generation of poisonous CO. Herein we demonstrate the superior electrocatalytic performance of Pt-Pd bimetallic nanoelectrocatalyst of ultralow Pt content and tuning the reaction pathway by controlling the Pt content. Bimetallic nanoparticles of Pt4Pd96, Pt7Pd93 and Pt47Pd53 compositions are synthesized by electrochemical co-deposition method in aqueous solution. The nanoparticles of ultralow Pt content, Pt4Pd96, favour the CO-free dehydrogenation pathway for formic acid oxidation with an onset potential of 0 V (SHE) whereas the Pt47Pd53 nanoparticles favour the dehydration pathway involving the formation of CO at high positive potential. The Pt content of the bimetallic nanoparticles actually controls the oxidation peak potential and catalytic activity. Significant negative shift (∼350 mV) in the oxidation peak potential and remarkable enhancement in the current density (2.6 times) are observed for Pt4Pd96 nanoparticles with respect to Pt47Pd53. The absence of three adjacent Pt and Pd atoms could be the reason for the suppression of CO pathway. The electrochemical impedance measurements indirectly support the CO-free pathway for the formic acid oxidation on Pt4Pd96 nanoparticles.

  13. Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

    DEFF Research Database (Denmark)

    Thomsen, A.B.

    1998-01-01

    of succinic acid is suggested to be a result of a coupling reaction of the acetic acid radical A reaction mechanism is suggested for the degradation of quinoline: it involves hydroxyl radicals and the possible interaction with autoclave walls is discussed. (C) 1998 Elsevier Science Ltd. All rights reserved....

  14. The application of reaction engineering to biocatalysis

    DEFF Research Database (Denmark)

    Ringborg, Rolf Hoffmeyer; Woodley, John

    2016-01-01

    Biocatalysis is a growing area of synthetic and process chemistry with the ability to deliver not only improved processes for the synthesis of existing compounds, but also new routes to new compounds. In order to assess the many options and strategies available to an engineer developing a new...... outline the benefits of reaction engineering in this development process, with particular emphasis of reaction kinetics. Future research needs to focus on rapid methods to collect such data at sufficient accuracy that it can be used forthe effective design of new biocatalytic processes....

  15. Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH4)2SO4

    Science.gov (United States)

    Shao, Hong-mei; Shen, Xiao-yi; Sun, Yi; Liu, Yan; Zhai, Yu-chun

    2016-10-01

    An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using (NH4)2SO4. The optimized reaction conditions are defined as an (NH4)2SO4/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of (NH4)2SO4/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric-differential thermal analysis was used for (NH4)2SO4 and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle-Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.

  16. Oxidative removal of acetaminophen using zero valent aluminum-acid system:Efficacy, influencing factors, and reaction mechanism

    Institute of Scientific and Technical Information of China (English)

    Honghua Zhang; Beipei Cao; Wanpeng Liu; Kunde Lin; Jun Feng

    2012-01-01

    Commercial available zero valent aluminum under air-equilibrated acidic conditions (ZVA1/H+/air system) demonstrated an excellent capacity to remove aqueous organic compounds.Acetaminophen (ACTM),the active ingredient of the over-the-counter drug Tylenol(R),is widely present in the aquatic environment and therefore the treatment of ACTM-contaminated water calls for further research.Herein we investigated the oxidative removal of ACTM by ZVAl/H+/air system and the reaction mechanism.In acidic solutions (pH < 3.5),ZVAl displayed an excellent capacity to remove ACTM.More than 99% of ACTM was eliminated within 16 hr in pH 1.5 reaction solutions initially containing 2.0 g/L aluminum and 2.0 mg/L ACTM at 25 ± 1℃.Higher temperature and lower pH facilitated ACTM removal.The addition of different iron species Fe0,Fe2+ and Fe3+ into ZVAl/H+/air system dramatically accelerated the reaction likely due to the enhancing transformation of H2O2 to HO·via Fenton's reaction.Furthermore,the primary intermediate h.ydroquinone and the anions formate,acetate and nitrate,were identified and a possible reaction scheme was proposed.This work suggested that ZVA1/H+/air system may be potentially employed to treat ACTM-contaminated water.

  17. CFD modeling of reaction and mass transfer through a single pellet:Catalytic oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    Siavash Seyednej adian; Nakisa Yaghobi; Ramin Maghrebi; Leila Vafajoo

    2011-01-01

    In this study a mathematical model of a small scale single pellet for the oxidative coupling of methane (OCM) over titanite pervoskité isdeveloped.The method is based on a computational fluid dynamics (CFD) code which known as Fluent may be adopted to model the reactions that take place inside the porous catalyst pellet.The steady state single pellet model is coupled with a kinetic model and the intra-pellet concentration profiles of species are provided.Subsequent to achieving this goal,a nonlinear reaction network consisting of nine catalytic reactions and one gas phase reaction as an external program is successfully implemented to CFD-code as a reaction term in solving the equations.This study is based on the experimental design which is conducted in a differential reactor with a Sn/BaTiO3 catalyst (7-8 mesh) at atmospheric pressure,GHSV of 12000 h-1,ratio of methane to oxygen of 2,and three different temperatures of 1023,1048 and 1073 K.The modeling results such as selectivity and conversion at the pellet exit are in good agreement with the experimental data.Therefore,it is suggested that to achieve high yield in OCM process the modeling of the single pellet should be considered as the heart of catalytic fixed bed reactor.

  18. Enhanced methanol electro-oxidation reaction on Pt-CoO{sub x}/MWCNTs hybrid electro-catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Nouralishahi, Amideddin, E-mail: Nouralishahi@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Caspian Faculty of Engineering, University of Tehran, P.O. Box 43841-119, Rezvanshahr (Iran, Islamic Republic of); Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Rashidi, Ali Morad, E-mail: Rashidiam@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: Mortazav@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Khodadadi, Abbas Ali, E-mail: Khodadad@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Choolaei, Mohammadmehdi, E-mail: Choolaeimm@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of)

    2015-04-30

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO{sub x}/MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO{sub x} addition. • Bi-functional mechanism is facilitated in presence of CoO{sub x}. - Abstract: The electro-catalytic behavior of Pt-CoO{sub x}/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 NaBH{sub 4} as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO{sub x}, 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 CO{sub ads} on Pt active sites by the participation of CoO{sub x}. Compared to Pt/MWCNTs, Pt-CoO{sub x}/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-CoO{sub x}/MWCNTs, at small overpotentials. However, at higher overpotentials, the

  19. New class of phosphine oxide donor-based supramolecular coordination complexes from an in situ phosphine oxidation reaction or phosphine oxide ligands.

    Science.gov (United States)

    Shankar, Bhaskaran; Elumalai, Palani; Shanmugam, Ramasamy; Singh, Virender; Masram, Dhanraj T; Sathiyendiran, Malaichamy

    2013-09-16

    A one-pot, multicomponent, coordination-driven self-assembly approach was used to synthesize the first examples of neutral bridging phosphine oxide donor-based supramolecular coordination complexes. The complexes were self-assembled from a fac-Re(CO)3 acceptor, an anionic bridging O donor, and a neutral soft phosphine or hard phosphine oxide donor.

  20. Biocatalytic Synthesis of Flavor Ester “Pentyl Valerate” Using Candida rugosa Lipase Immobilized in Microemulsion Based Organogels: Effect of Parameters and Reusability

    Science.gov (United States)

    Raghavendra, Tripti; Panchal, Nilam; Divecha, Jyoti; Shah, Amita; Madamwar, Datta

    2014-01-01

    Pentyl valerate was synthesized biocatalytically using Candida rugosa lipase (CRL) immobilized in microemulsion based organogels (MBGs). The optimum conditions were found to be pH 7.0, temperature of 37°C, ratio of concentration of water to surfactant (Wo) of 60, and the surfactant sodium bis-2-(ethylhexyl)sulfosuccinate (AOT) for MBG preparation. Although kinetic studies revealed that the enzyme in free form had high affinity towards substrates (Km = 23.2 mM for pentanol and 76.92 mM for valeric acid) whereas, after immobilization, the Km values increased considerably (74.07 mM for pentanol and 83.3 mM for valeric acid) resulting in a slower reaction rate, the maximum conversion was much higher in case of immobilized enzyme (~99%) as compared to free enzyme (~19%). Simultaneous effects of important parameters were studied using response surface methodology (RSM) conjugated with Box-Behnken design (BBD) with five variables (process parameters), namely, enzyme concentration, initial water content (Wo), solvent used for MBG preparation, substrate ratio and time, and response as the final product formation, that is, pentyl valerate (%). The MBGs were reused for 10 consecutive cycles for ester synthesis. Efficacy of AOT/isooctane as dehydrating agent for extracting excess water from MBGs was found to exert a positive effect on the esterification reaction. PMID:25093166

  1. Biocatalytic Synthesis of Flavor Ester “Pentyl Valerate” Using Candida rugosa Lipase Immobilized in Microemulsion Based Organogels: Effect of Parameters and Reusability

    Directory of Open Access Journals (Sweden)

    Tripti Raghavendra

    2014-01-01

    Full Text Available Pentyl valerate was synthesized biocatalytically using Candida rugosa lipase (CRL immobilized in microemulsion based organogels (MBGs. The optimum conditions were found to be pH 7.0, temperature of 37°C, ratio of concentration of water to surfactant (Wo of 60, and the surfactant sodium bis-2-(ethylhexylsulfosuccinate (AOT for MBG preparation. Although kinetic studies revealed that the enzyme in free form had high affinity towards substrates (Km = 23.2 mM for pentanol and 76.92 mM for valeric acid whereas, after immobilization, the Km values increased considerably (74.07 mM for pentanol and 83.3 mM for valeric acid resulting in a slower reaction rate, the maximum conversion was much higher in case of immobilized enzyme (~99% as compared to free enzyme (~19%. Simultaneous effects of important parameters were studied using response surface methodology (RSM conjugated with Box-Behnken design (BBD with five variables (process parameters, namely, enzyme concentration, initial water content (Wo, solvent used for MBG preparation, substrate ratio and time, and response as the final product formation, that is, pentyl valerate (%. The MBGs were reused for 10 consecutive cycles for ester synthesis. Efficacy of AOT/isooctane as dehydrating agent for extracting excess water from MBGs was found to exert a positive effect on the esterification reaction.

  2. Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

    Science.gov (United States)

    Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

    2015-11-15

    Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution

  3. Silver nanoparticles sensitized C60(Ag@C60) as efficient electrocatalysts for hydrazine oxidation: Implication for hydrogen generation reaction

    Science.gov (United States)

    Narwade, Shankar S.; Mulik, Balaji B.; Mali, Shivsharan M.; Sathe, Bhaskar R.

    2017-02-01

    Herein, we report the synthesis of silver nanoparticles (Ag NPs; 10 ± 0.5 nm) sensitized Fullerene (C60; 15 ±2 nm) nanocatalysts (Ag@C60) for the first time showing efficient electroatalytic activity for the oxidation of hydrazine demonstrating activity comparable to that of Pt in acidic, neutral and basic media. The performance is comparable with the best available electrocatalytic system and plays a vital role in the overall hydrogen generation reactions from hydrazine as a one of the fuel cell reaction. The materials are synthesized by a simple and scalable synthetic route involving acid functionalization of C60 followed by chemical reduction of Ag+ ions in ethylene glycol at high temperature. The distributation of Silver nanoparticles (Ag NPs) (morphological information) on C60, bonding, its crystal structure, along with activity towards hydrazine oxidation (electrocatalytic) is studied using TEM, XRD, UV-vis, XPS, FTIR and electrochemical (cyclic voltammetry) studies, respectively. The observed efficient electrocatalytic activity of the as-synthesized electrode is attributed to the co-operative response and associated structural defects due to their oxidative functionalization along with thier cooperative functioning at nanodimensions.

  4. Ion-molecule reactions of O,S-dimethyl methylphosphonothioate: evidence for intramolecular sulfur oxidation during VX perhydrolysis.

    Science.gov (United States)

    McAnoy, Andrew M; Williams, Jilliarne; Paine, Martin R L; Rogers, Michael L; Blanksby, Stephen J

    2009-12-18

    The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

  5. Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Jiashen Meng; Chaojiang Niu; Xiong Liu; Ziang Liu; Hongliang Chen; Xuanpeng Wang; Jiantao Li

    2016-01-01

    Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis,chemical sensing,drug delivery,and energy storage.However,the controlled synthesis of multilevel nanotubes remains a great challenge.Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment.This versatile strategy can be effectively applied to fabricate wire-in-tube and tubein-tube nanotubes of various metal oxides.These multilevel nanotubes possess a large specific surface area,fast mass transport,good strain accommodation,and high packing density,which are advantageous for lithium-ion batteries (LIBs)and the oxygen reduction reaction (ORR).Specifically,shrinkable CoMn2O4 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of ~565 mAh.g-1 at a high rate of 2 A.g-1,maintaining 89% of the latter after 500 cycles.Further,as an oxygen reduction reaction catalyst,these nanotubes also exhibit excellent stability with about 92% current retention after 30,000 s,which is higher than that of commercial Pt/C (81%).Therefore,this feasible method may push the rapid development of one-dimensional (1D) nanomaterials.These multifunctional nanotubes have great potential in many frontier fields.

  6. Preparation of porous paper composites with ruthenium hydroxide and catalytic alcohol oxidation in a multiphase gas–liquid–solid reaction

    Energy Technology Data Exchange (ETDEWEB)

    Homma, Taichi [Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, and Biotron Application Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan); Processing Development Research Laboratory, Kao Corporation, 2606 Akabane, Ichikai-machi, Haga-gun, Tochigi 321-3497 (Japan); Kitaoka, Takuya, E-mail: tkitaoka@agr.kyushu-u.ac.jp [Department of Agro-Environmental Sciences, Graduate School of Bioresource and Bioenvironmental Sciences, and Biotron Application Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581 (Japan)

    2014-05-01

    Highlights: • Flexible and porous paper-structured Ru(OH){sub x} catalysts were prepared successfully. • Ru(OH){sub x} catalysts were dispersed on the ceramic fiber networks of paper composites. • Catalytic oxidation of benzyl alcohol proceeded efficiently in three-phase reactions. • Paper catalysts exhibited much higher performance than conventional solid catalysts. - Abstract: In situ synthesis of ruthenium hydroxide catalysts on a microporous fiber-network structure of ceramic paper composites was achieved. The efficient catalytic oxidation of alcohol was investigated in a heterogeneous, multiphase gas–liquid–solid reaction. A simple papermaking technique and subsequent immersion in a ruthenium chloride solution allowed us to fabricate novel-concept microstructured catalysts. The paper-structured catalysts possess micropores ca. 30 μm in diameter with high porosity of ca. 90%. They exhibited much higher catalytic efficiency in the O{sub 2}-mediated oxidation in toluene of benzyl alcohol to benzaldehyde in a fixed bed external loop reactor, as compared with conventional pellet- and bead-type solid catalysts. This excellent catalytic effect is possibly attributed to the porous paper composite microstructure like microreactors.

  7. Sol–gel synthesis of palladium nanoparticles supported on reduced graphene oxide: an active electrocatalyst for hydrogen evolution reaction

    Indian Academy of Sciences (India)

    Fereshteh Chekin

    2015-08-01

    In this work, the synthesis and characterization of palladium nanoparticle-reduced graphene oxide hybrid (Pd–rGO) material is reported. Techniques of X-ray diffraction, transmission electron microscope (TEM), energy-dispersive X-ray, FT-IR spectroscopy, thermogravimetric analysis and cyclic voltammetry were used to characterize the structure and properties of the Pd–rGO. Results demonstrate the effect of Pd on the reduced GO. The average particle size of the Pd nanoparticles supported on rGO obtained from TEM is about 12–18 nm. Moreover, glassy carbon electrode (GCE) modified with palladium nanoparticle–graphene oxide hybrid (Pd–rGO/GCE) was prepared by casting of the Pd–rGO solution on GCE. The electrochemical and catalytic activity of the Pd–rGO/GCE was studied in 0.1 M H2SO4 solution. The Pd–rGO/GCE electrode exhibited remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). At potential more negative than −0.4 V vs. Ag|AgCl|KCl3M, the current is mainly due to hydrogen evolution reaction. Finally, the kinetic parameters of hydrogen evolution reaction are also discussed on the Pd–rGO/GCE.

  8. Absorption of nitric oxide into aqueous solutions of ferrous chelates accompanied by instantaneous reaction

    NARCIS (Netherlands)

    Demmink, J.F; vanGils, I.C.F.; Beenackers, A.A C M

    1997-01-01

    The absorption of nitric oxide (NO) into aqueous solutions of ferrous chelates of nitrilotriacetic acid (NTA), ethylene diaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTPA) was studied in a stirred cell reactor. Experimental cond

  9. Betanin attenuates oxidative stress and inflammatory reaction in kidney of paraquat-treated rat.

    Science.gov (United States)

    Tan, Dehong; Wang, Yiheng; Bai, Bing; Yang, Xuelian; Han, Junyan

    2015-04-01

    The effects of natural pigment betanin on oxidative stress and inflammation in kidney of paraquat-treated rat were investigated. Paraquat was injected intraperitoneally into rats to induce renal damage. The rats were randomly divided into four groups: a control group, a paraquat group, and two paraquat groups that were treated with betanin at 25 and 100 mg/kg/d three days before and two days after paraquat administration. Treatment with betanin alleviated the paraquat-incurred acute kidney injury, evidenced by histological improvement, reduced serum and urine markers for kidney injury. Betanin antagonized the paraquat-induced inflammation, indicated by reduced expression of inducible nitric oxide synthase and cyclooxygenase, blunted activation of nuclear factor kappa B, and diminished lysosomal protease activities. Betanin also decreased oxidative stress elicited by paraquat. In conclusion, betanin may have a protective effect against paraquat-induced acute kidney damage. The mechanisms of the protection appear to be the inhibition of oxidative stress and inflammation.

  10. Safety analysis of switching between reductive and oxidative conditions in a reaction coupling reverse flow reactor.

    NARCIS (Netherlands)

    Sint Annaland, van M.; Kuipers, J.A.M.; Swaaij, van W.P.M.

    2001-01-01

    A new reverse flow reactor is developed where endothermic reactants (propane dehydrogenation) and exothermic reactants (fuel combustion) are fed sequentially to a monolithic catalyst, while periodically alternating the inlet and outlet positions. Upon switching from reductive to oxidative conditions

  11. Syntheses and Reactions of Novel Oxidized Variants of Sterically-Crowded Chalcogenocarbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    Kazuaki Shimada

    2005-01-01

    @@ 1Introduction d-Camphor and their derivatives have been widely used as chiral auxiliaries and synthons for organic synthesis, and our attempts are focused onto the new functionalization of these skeletons through the generation of oxidized variants of thiones and selones through in situ generation of novel oxidized variants of bornane-2-thiones and selones. In this paper, a novel generation and chemical conversion of these reactive intermediates are presented.

  12. Environmental Factors Affecting Chromium-Manganese Oxidation-Reduction Reactions in Soil

    Institute of Scientific and Technical Information of China (English)

    D.O.P.TREBIEN; L.BORTOLON; M.J.TEDESCO; C.A.BISSANI; F.A.O.CAMARGO

    2011-01-01

    Disposal of chromium (Cr) hexavalent form, Cr(Ⅵ), in soils as additions in organic fertilizers, liming materials or plant nutrient sources can be dangerous since Cr(Ⅵ) can be highly toxic to plants, animals, and humans. In order to explore soil conditions that lead to Cr(Ⅵ) generation, this study were performed using a Paleudult (Dystic Nitosol) from a region that has a high concentration of tannery operations in the Rio Grande do Sul State, southern Brazil. Three laboratory incubation experiments were carried out to examine the influences of soil moisture content and concentration of cobalt and organic matter additions on soil Cr(Ⅵ) formation and release and manganese (Mn) oxide reduction with a salt of chromium chloride (CrCl3) and tannery sludge as inorganic and organic sources of Cr(Ⅲ), respectively. The amount of Cr(Ⅲ) oxidation depended on the concentration of easily reducible Mn oxides and the oxidation was more intense at the soil water contents in which Mn(Ⅲ/Ⅳ) oxides were more stable. Soluble organic compounds in soil decreased Cr(Ⅵ) formation due to Cr(Ⅲ) complexation. This mechanism also resulted in the decrease in the oxidation of Cr(Ⅲ) due to the tannery sludge additions. Chromium(Ⅲ) oxidation to Cr(Ⅵ) at the solid/solution interface involved the following mechanisms:the formation of a precursor complex on manganese (Mn) oxide surfaces, followed by electron transfer from Cr(Ⅲ) to Mn(Ⅲ or Ⅳ),the formation of a successor complex with Mn(Ⅱ) and Cr(Ⅵ), and the breakdown of the successor complex and release of Mn(Ⅱ) and Cr(Ⅵ) into the soil solution.

  13. The synthesis of a bifunctional copper metal organic framework and its application in the aerobic oxidation/Knoevenagel condensation sequential reaction.

    Science.gov (United States)

    Miao, Zongcheng; Luan, Yi; Qi, Chao; Ramella, Daniele

    2016-09-21

    A novel one-pot aerobic oxidation/Knoevenagel condensation reaction system was developed employing a Cu(ii)/amine bifunctional, basic metal-organic framework (MOF) as the catalyst. The sequential aerobic alcohol oxidation/Knoevenagel condensation reaction was efficiently promoted by the Cu3TATAT MOF catalyst in the absence of basic additives. The benzylidenemalononitrile product was produced in high yield and selectivity from an inexpensive benzyl alcohol starting material under an oxygen atmosphere. The role of the basic functionality was studied to demonstrate its role in the aerobic oxidation and Knoevenagel condensation reactions. The reaction progress was monitored in order to identify the reaction intermediate and follow the accumulation of the desired product. Lastly, results showed that the yield was not significantly compromised by the reuse of a batch of catalyst, even after more than five cycles.

  14. Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Skulason, Egill; Tripkovic, Vladimir; Björketun, Mårten;

    2010-01-01

    charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting...... reaction on Pt(111) to be Tafel−Volmer for HOR and Volmer−Tafel for HER. Calculated rates agree well with experimental data. Both the H adsorption energy and the energy barrier for the Tafel reaction are then calculated for a range of metal electrodes, including Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Ru, Re......, W, Mo, and Nb, different facets, and step of surfaces. We compare the results for different facets of the Pt electrode to experimental data. Our results suggest that the most important parameter for describing the HOR or the HER activity of an electrode is its binding free energy of H. We present...

  15. A DFT Study Toward the Reaction Mechanisms of TNT With Hydroxyl Radicals for Advanced Oxidation Processes.

    Science.gov (United States)

    He, Xi; Zeng, Qun; Zhou, Yang; Zeng, Qingxuan; Wei, Xianfeng; Zhang, Chaoyang

    2016-05-26

    The degradation pathway of environmental contaminant 2,4,6-trinitrotoluene (TNT) was investigated computationally at the SMD(Pauling)/M06-2X/6-311+G(d,p) level of theory. The dominant decomposition pathway of TNT → 4,6-dinitro-o-cresol → 4,6-dinitro-2-hydroxybenzylalcohol → 4,6-dinitro-2-hydroxybenzaldehyde was provided, and the corresponding predicted products and their distributions are in a good agreement with available experimental data on TNT degradation by Fenton reaction. It was shown that the mechanism of addition-elimination is crucial for this stage of the reaction. The reaction of H atom abstraction is a minor competing pathway. The details on transition states, intermediate radicals, and free energy surfaces for all proposed reactions are given and make up for a lack of experimental knowledge.

  16. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela

    2016-01-25

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

  17. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  18. Effects of aluminum additions to gas atomized reaction synthesis produced oxide dispersion strengthened alloys

    Science.gov (United States)

    Spicher, Alexander Lee

    The production of an aluminum containing ferritic oxide dispersion strengthened (ODS) alloy was investigated. The production method used in this study was gas atomization reaction synthesis (GARS). GARS was chosen over the previously commercial method of mechanical alloying (MA) process due to complications from this process. The alloy compositions was determined from three main components; corrosion resistance, dispersoid formation, and additional elements. A combination of Cr and Al were necessary in order to create a protective oxide in the steam atmosphere that the boiler tubing in the next generation of coal-fired power plants would be exposed to. Hf and Y were chosen as dispersoid forming elements due to their increased thermal stability and potential to avoid decreased strength caused by additions of Al to traditional ODS materials. W was used as an additive due to benefits as a strengthener as well as its benefits for creep rupture time. The final composition chosen for the alloy was Fe-16Cr-12Al-0.9W-0.25Hf-0.2Y at%. The aforementioned alloy, GA-1-198, was created through gas atomization with atomization gas of Ar-300ppm O2. The actual composition created was found to be Fe-15Cr-12.3Al-0.9W-0.24Hf-0.19Y at%. An additional alloy that was nominally the same without the inclusion of aluminum was created as a comparison for the effects on mechanical and corrosion properties. The actual composition of the comparison alloy, GA-1-204, was Fe-16Cr-0Al-0.9W-0.25Hf-0.24Y at%. An investigation on the processing parameters for these alloys was conducted on the GA-1-198 alloy. In order to predict the necessary amount of time for heat treatment, a diffusion study was used to find the diffusion rate of oxygen in cast alloys with similar composition. The diffusion rate was found to be similar to that of other GARS compositions that have been created without the inclusion of aluminum. The effect of heat treatment time was investigated with temperatures of 950°C, 1000

  19. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler

    Directory of Open Access Journals (Sweden)

    Jun-Xia Zhang

    2016-03-01

    Full Text Available Because the air-staged combustion technology is one of the key technologies with low investment running costs and high emission reduction efficiency for the pulverized boiler, it is important to reveal the chemical reaction kinetics mechanism for developing various technologies of nitrogen oxide reduction emissions. At the present work, a three-dimensional mesh model of the large-scale four corner tangentially fired boiler furnace is established with the GAMBIT pre-processing of the FLUENT software. The partial turbulent premixed and diffusion flame was simulated for the air-staged combustion processing. Parameters distributions for the air-staged and no the air-staged were obtained, including in-furnace flow field, temperature field and nitrogen oxide concentration field. The results show that the air-staged has more regular velocity field, higher velocity of flue gas, higher turbulence intensity and more uniform temperature of flue gas. In addition, a lower negative pressure zone and lower O2 concentration zone is formed in the main combustion zone, which is conducive to the NO of fuel type reduced to N2, enhanced the effect of NOx reduction. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th November 2015; Revised: 14th January 2016; Accepted: 16th January 2016  How to Cite: Zhang, J.X., Zhang, J.F. (2016. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 100-108. (doi:10.9767/bcrec.11.1.431.100-108 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.431.100-108

  20. Oxo iron(IV) as an oxidative active intermediate of p-chlorophenol in the Fenton reaction: a DFT study.

    Science.gov (United States)

    Mignon, Pierre; Pera-Titus, Marc; Chermette, Henry

    2012-03-21

    Debate continues over which active species plays the role of oxidative agent during the Fenton reaction-the HO˙ radical or oxo iron [Fe(IV)O](2+). In this context, the present study investigates the oxidation of p-chlorophenol by [Fe(IV)O(H(2)O)(5)](2+) using DFT calculations, within gas-phase and micro-solvated models, in order to explore the possible role of oxo iron as a reactant. The results show that the chlorine atom substitution of p-chlorophenol by oxo iron is a highly stabilising step (ΔH = -83 kcal mol(-1)) with a free energy barrier of 5.8 kcal mol(-1) in the micro-solvated model. This illustrates the high oxidising power of the [Fe(IV)O(H(2)O)(5)](2+) complex. On the other hand, the breaking of the Fe-O bond, leading to the formation of hydroquinone, is observed to be the rate-determining step of the reaction. The rather large free energy barrier corresponding to this bond cleavage amounts to 10.2 and 9.3 kcal mol(-1) in the gas-phase and micro-solvated models, respectively. Elsewhere, the lifetime of the HO˙ radical has previously been shown to be extremely small. These facts, combined with observations of oxo iron under certain experimental conditions, suggest that oxo iron is a highly plausible oxidative species of the reaction. In addition, a trigonal bipyramidal iron complex, coordinated either by hydroxyl groups and/or by water molecules, has been found in all described mechanisms. This structure appears to be a stable intermediate; and to our knowledge, it has not been characterised by previous studies.

  1. Coprecipitation and redox reactions of manganese oxides with copper and nickel

    Science.gov (United States)

    Hem, J.D.; Lind, Carol J.; Roberson, C.E.

    1989-01-01

    Open-system, continuous-titration experiments have been done in which a slow flux of ???0.02 molar solution of Mn2+ chloride, nitrate, or perchlorate with Cu2+ or Ni2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu2Mn3O8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, ??MnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included ??MnOOH, Ni(OH)2, and the same two forms of MnO2. The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu2+ and Ni2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems. ?? 1989.

  2. Phase transformations in thin iron oxide films: Spectromicroscopic study of velocity and shape of the reaction fronts

    Science.gov (United States)

    Genuzio, F.; Sala, A.; Schmidt, Th.; Menzel, D.; Freund, H.-J.

    2016-06-01

    Combining low energy electron microscopy (LEEM) with low energy electron diffraction (LEED) and x-ray photoemission electron microscopy (XPEEM), we studied the phase transformations between Fe3O4, γ-Fe2O3, and α-Fe2O3, grown as 10 nm thin oxide films on Pt(111) and Ag(111) single crystals. These transformations occur as moving reaction fronts in most cases, the shapes and velocities of which show strong dependences on temperature and oxygen pressure, but also on defects like step bunches of the supporting substrate and domain boundaries in the initial oxide film. While the non-uniform moving fronts make quantitative analysis difficult, we have extracted approximate values for the average front velocities. We discuss these as well as the qualitative information on the non-uniform fronts in terms of the known geometric situations and the likely motional steps.

  3. Bioinorganic Chemistry in Thyroid Gland: Effect of Antithyroid Drugs on Peroxidase-Catalyzed Oxidation and Iodination Reactions

    Directory of Open Access Journals (Sweden)

    G. Mugesh

    2006-11-01

    Full Text Available Propylthiouracil (PTU and methimazole (MMI are the most commonly used antithyroid drugs. The available data suggest that these drugs may block the thyroid hormone synthesis by inhibiting the thyroid peroxidase (TPO or diverting oxidized iodides away from thyroglobulin. It is also known that PTU inhibits the selenocysteine-containing enzyme ID-1 by reacting with the selenenyl iodide intermediate (E-SeI. In view of the current interest in antithyroid drugs, we have recently carried out biomimetic studies to understand the mechanism by which the antithyroid drugs inhibit the thyroid hormone synthesis and found that the replacement of sulfur with selenium in MMI leads to an interesting compound that may reversibly block the thyroid hormone synthesis. Our recent results on the inhibition of lactoperoxidase (LPO-catalyzed oxidation and iodination reactions by antithyroid drugs are described.

  4. Oxidative Cyclization of Sulfamate Esters Using NaOCl - A Metal-Mediated Hoffman-Löffler Freytag Reaction.

    Science.gov (United States)

    Zalatan, David N; Du Bois, J

    2009-01-01

    Intramolecular C-H amination with sulfamate esters occurs under the action of dinuclear Rh catalysts and iodine(III) oxidants, and has recently emerged as a powerful tool for synthesis. Insights gained through mechanistic studies of this process suggest that other terminal oxidants, including common halogenating agents such as NaOCl, could function to promote the cyclization reaction. Results described in this report demonstrate that the combination of NaOCl and 3 mol% Rh(2)(oct)(4) is effective in select cases for converting sulfamate substrates to the corresponding [1,2,3]-oxathiazinane-2,2-dioxide heterocycles. The mechanism for C-H functionalization, however, is distinct from that induced by hypervalent iodine reagents and likely involves the intermediacy of an N-centered radical.

  5. Oxidative Cyclization of Sulfamate Esters Using NaOCl – A Metal-Mediated Hoffman-Löffler Freytag Reaction

    Science.gov (United States)

    Zalatan, David N.; Du Bois, J.

    2009-01-01

    Intramolecular C–H amination with sulfamate esters occurs under the action of dinuclear Rh catalysts and iodine(III) oxidants, and has recently emerged as a powerful tool for synthesis. Insights gained through mechanistic studies of this process suggest that other terminal oxidants, including common halogenating agents such as NaOCl, could function to promote the cyclization reaction. Results described in this report demonstrate that the combination of NaOCl and 3 mol% Rh2(oct)4 is effective in select cases for converting sulfamate substrates to the corresponding [1,2,3]-oxathiazinane-2,2-dioxide heterocycles. The mechanism for C–H functionalization, however, is distinct from that induced by hypervalent iodine reagents and likely involves the intermediacy of an N-centered radical. PMID:19319207

  6. Insights of ibuprofen electro-oxidation on metal-oxide-coated Ti anodes: Kinetics, energy consumption and reaction mechanisms.

    Science.gov (United States)

    Wang, Chong; Yu, Yanxin; Yin, Lifeng; Niu, Junfeng; Hou, Li-An

    2016-11-01

    Electrochemical degradation of ibuprofen (IBP) was performed on three types of Ti-based metal oxide electrodes. The degradation of IBP followed pseudo-first-order kinetics and the electrochemical degradation rate constant (k) over Ti/SnO2-Sb/Ce-PbO2 (9.4 × 10(-2) min(-1)) was 2.0 and 1.7 times of the values over Ti/Ce-PbO2 (4.7 × 10(-2) min(-1)) and Ti/SnO2-Sb (5.6 × 10(-2) min(-1)), respectively. The removal of total organic carbon and the energy consumption per order for IBP degradation were 93.2% and 13.1 Wh L(-1), respectively, under the optimal conditions using Ti/SnO2-Sb/Ce-PbO2 anode. Six aromatic intermediate products of IBP were identified by ultra-high-performance liquid chromatography coupled with a quadrupole time-of-flight mass spectrometer. The electrochemical mineralization mechanism of IBP was proposed. It was supposed that OH radicals produced on the surface of anode attacked IBP to form hydroxylated IBP derivatives that were then followed by a series of hydroxylation, loss of isopropanol and isopropyl, decarboxylation and benzene ring cleavage processes to form simple linear carboxylic acids. By successive hydroxylation, these carboxylic acids were then oxidized to CO2 and H2O, achieving the complete mineralization of IBP.

  7. Composite polymer/oxide hollow fiber contactors: versatile and scalable flow reactors for heterogeneous catalytic reactions in organic synthesis.

    Science.gov (United States)

    Moschetta, Eric G; Negretti, Solymar; Chepiga, Kathryn M; Brunelli, Nicholas A; Labreche, Ying; Feng, Yan; Rezaei, Fateme; Lively, Ryan P; Koros, William J; Davies, Huw M L; Jones, Christopher W

    2015-05-26

    Flexible composite polymer/oxide hollow fibers are used as flow reactors for heterogeneously catalyzed reactions in organic synthesis. The fiber synthesis allows for a variety of supported catalysts to be embedded in the walls of the fibers, thus leading to a diverse set of reactions that can be catalyzed in flow. Additionally, the fiber synthesis is scalable (e.g. several reactor beds containing many fibers in a module may be used) and thus they could potentially be used for the large-scale production of organic compounds. Incorporating heterogeneous catalysts in the walls of the fibers presents an alternative to a traditional packed-bed reactor and avoids large pressure drops, which is a crucial challenge when employing microreactors.

  8. A New Domain of Reactivity for High-Valent Dinuclear [M(μ-O)2 M'] Complexes in Oxidation Reactions.

    Science.gov (United States)

    Engelmann, Xenia; Yao, Shenglai; Farquhar, Erik R; Szilvási, Tibor; Kuhlmann, Uwe; Hildebrandt, Peter; Driess, Matthias; Ray, Kallol

    2017-01-02

    The strikingly different reactivity of a series of homo- and heterodinuclear [(M(III) )(μ-O)2 (M(III) )'](2+) (M=Ni; M'=Fe, Co, Ni and M=M'=Co) complexes with β-diketiminate ligands in electrophilic and nucleophilic oxidation reactions is reported, and can be correlated to the spectroscopic features of the [(M(III) )(μ-O)2 (M(III) )'](2+) core. In particular, the unprecedented nucleophilic reactivity of the symmetric [Ni(III) (μ-O)2 Ni(III) ](2+) complex and the decay of the asymmetric [Ni(III) (μ-O)2 Co(III) ](2+) core through aromatic hydroxylation reactions represent a new domain for high-valent bis(μ-oxido)dimetal reactivity.

  9. Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

    DEFF Research Database (Denmark)

    Dale, A.W.; Regnier, P.; Knab, N.J.;

    2008-01-01

    A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction...... for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby...... methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ...

  10. Analysis of tissue reactions to methacrylate resin-based, epoxy resin-based, and zinc oxide-eugenol endodontic sealers.

    Science.gov (United States)

    Scarparo, Roberta Kochenborger; Grecca, Fabiana Soares; Fachin, Elaine Vianna Freitas

    2009-02-01

    The purpose of this study was to investigate the reaction of the subcutaneous connective tissue of rats to methacrylate resin-based sealer (EndoREZ), epoxy resin-based sealer (AH Plus), and zinc oxide-eugenol sealer (EndoFill). Polyethylene tubes containing the test materials were implanted in 18 rats. After 7, 30, and 60 days, tissues were collected for biopsy and fixed and processed for histologic evaluation. Observations were made of the cellular inflammatory component, the fibrous condensation, and the abscess formation. Comparisons between groups and times were made with the Friedman and Kruskall-Wallis tests. EndoREZ and EndoFill sealers showed a more intense and longer-lasting inflammation. With AH Plus, the inflammatory reaction showed a tendency to diminish over time. The only group to show a statistically significant reduction in inflammation during the 60-day period was the control group. None of the materials tested proved to have ideal characteristics for biocompatibility.

  11. Bimetallic PtAu superlattice arrays: Highly electroactive and durable catalyst for oxygen reduction and methanol oxidation reactions

    Science.gov (United States)

    Feng, Jiu-Ju; He, Li-Li; Fang, Rui; Wang, Qiao-Li; Yuan, Junhua; Wang, Ai-Jun

    2016-10-01

    Superlattice arrays, an important type of nanomaterials, have wide applications in catalysis, optic/electronics and energy storage for the synergetic effects determined by both individual metals and collective interactions. Herein, a simple one-pot solvothermal coreduction approach is developed for facile preparation of bimetallic PtAu alloyed superlattice arrays (PtAu SLAs) in oleylamine, with the assistance of urea via hydrogen bonding induced self-assembly. Urea is essential in morphology-controlled process and prevents PtAu nanoparticles from the disordered aggregation. The characterization and formation mechanism of PtAu SLAs are investigated in details. The as-synthesized hybrid nanocrystals exhibit enhanced electrocatalytic performances for oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in alkaline electrolyte in comparison with commercial Pt-C (50%, wt.%) and Pt black catalysts.

  12. In situ transmission electron microscopy of ionic conductivity and reaction mechanisms in ultrathin solid oxide fuel cells.

    Science.gov (United States)

    Tavabi, Amir H; Arai, Shigeo; Muto, Shunsuke; Tanji, Takayoshi; Dunin-Borkowski, Rafal E

    2014-12-01

    Solid oxide fuel cells (SOFCs) are promising candidates for use in alternative energy technologies. A full understanding of the reaction mechanisms in these dynamic material systems is required to optimize device performance and overcome present limitations. Here, we show that in situ transmission electron microscopy (TEM) can be used to study redox reactions and ionic conductivity in SOFCs in a gas environment at elevated temperature. We examine model ultrathin half and complete cells in two environmental TEMs using off-axis electron holography and electron energy-loss spectroscopy. Our results from the model cells provide insight into the essential phenomena that are important for the operation of commercial devices. Changes in the activities of dopant cations in the solid electrolyte are detected during oxygen anion conduction, demonstrating the key role of dopants in electrolyte architecture in SOFCs.

  13. Oxidation of Co(II) by ozone and reactions of Co(III) in solutions of sulfuric acid

    Science.gov (United States)

    Levanov, A. V.; Isaikina, O. Ya.; Lunin, V. V.

    2016-12-01

    Reactions of the oxidation of bivalent cobalt ions by ozone, of the spontaneous decomposition of trivalent cobalt, and of interactions between Co(III) and chloride ions in solutions of sulfuric acid are studied. The order and rate constant of the process of decomposition of Co(III) are determined. Information on the kinetics of the interaction between Co(III) and Cl- is obtained. Kinetic patterns of the accumulation of Co(III) during the ozonation of solutions of CoSO4 in sulfuric acid are explained. Molar absorption coefficients of Co(III) and Co2+ ions in the visible range of wavelengths are determined.

  14. C60的氧化反应研究%Studies on Oxidation Reaction of C60

    Institute of Scientific and Technical Information of China (English)

    李旭; 孔庆宇; 等

    2001-01-01

    Two oxidation products of the reaction of C60 with O3 in toluene or dichlorobenzene were obtained in dependence on the amount of ozone absorbed by the solution and the reaction time. The short time oxidized product is insoluble in common organic solvents and water, but the water-soluble derivatives were obtained after hydrolysis under a basic condition. It′s IR spectrum is similar with that of C60 polyhydric derivatives. The extensive oxidation product of C60 is water-soluble without any further dispose. The structures of the two oxidized products were characterized by variable-temperature FTIR, XPS, elementary analysis, TGA and TOF-MS, ESI-MS, FAB-MS technique. Both products are thermally unstable, H2O, CO and CO2 are eliminated during the increase of temperature.%在C60的甲苯或二氯苯溶液中通入O3,通过改变O3的吸收量及反应时间可得到两种氧化产物. 一种产物在有机溶剂及水中均不溶,但经碱性水解后得到水溶性产物,其红外光谱与C60羟基化合物相似;在长时间通O3条件下,得到水溶性的C60氧化产物. 用变温红外光谱、 XPS、元素分析、热谱和质谱研究了氧化产物的可能结构,发现生成的C60氧化产物对热不稳定,随着温度升高,有CO2, CO和H2O放出.

  15. Bioenergetic studies of coal sulfur oxidation by extremely thermophilic bacteria. Final report, September 15, 1992--August 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, R.M.; Han, C.J.

    1997-12-31

    Thermoacidophilic microorganisms have been considered for inorganic sulfur removal from coal because of expected improvements in rates of both biotic and abiotic sulfur oxidation reactions with increasing temperature. In this study, the bioenergetic response of the extremely thermoacidophilic archaeon, Metallosphaera sedula, to environmental changes have been examined in relation to its capacity to catalyze pyrite oxidation in coal. Given an appropriate bioenergetic challenge, the metabolic response was to utilize additional amounts of energy sources (i.e., pyrite) to survive. Of particular interest were the consequences of exposing the organism to various forms of stress (chemical, nutritional, thermal, pH) in the presence of coal pyrite. Several approaches to take advantage of stress response to accelerate pyrite oxidation by this organism were examined, including attempts to promote acquired thermal tolerance to extend its functional range, exposure to chemical uncouplers and decouplers, and manipulation of heterotrophic and chemolithotrophic tendencies to optimize biomass concentration and biocatalytic activity. Promising strategies were investigated in a continuous culture system. This study identified environmental conditions that promote better coupling of biotic and abiotic oxidation reactions to improve biosulfurization rates of thermoacidophilic microorganisms.

  16. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    Energy Technology Data Exchange (ETDEWEB)

    Nagaraju, D.H., E-mail: dhnagu@gmail.com [Department of Mechanical Engineering, 117 576 (Singapore); Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 (Saudi Arabia); Devaraj, S. [Department of Mechanical Engineering, 117 576 (Singapore); School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401 (India); Balaya, P., E-mail: mpepb@nus.edu.sg [Department of Mechanical Engineering, 117 576 (Singapore); Engineering Science Program, National University of Singapore, 117 576 (Singapore)

    2014-12-15

    Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

  17. Applied reaction dynamics: Efficient synthesis gas production via single collision partial oxidation of methane to CO on Rh(111)

    Science.gov (United States)

    Gibson, K. D.; Viste, M.; Sibener, S. J.

    2006-10-01

    Supersonic molecular beams have been used to determine the yield of CO from the partial oxidation of CH4 on a Rh(111) catalytic substrate, CH4+(1/2)O2→CO +2H2, as a function of beam kinetic energy. These experiments were done under ultrahigh vacuum conditions with concurrent molecular beams of O2 and CH4, ensuring that there was only a single collision for the CH4 to react with the surface. The fraction of CH4 converted is strongly dependent on the normal component of the incident beam's translational energy, and approaches unity for energies greater than ˜1.3eV. Comparison with a simplified model of the methane-Rh(111) reactive potential gives insight into the barrier for methane dissociation. These results demonstrate the efficient conversion of methane to synthesis gas, CO +2H2, are of interest in hydrogen generation, and have the optimal stoichiometry for subsequent utilization in synthetic fuel production (Fischer-Tropsch or methanol synthesis). Moreover, under the reaction conditions explored, no CO2 was detected, i.e., the reaction proceeded with the production of very little, if any, unwanted greenhouse gas by-products. These findings demonstrate the efficacy of overcoming the limitations of purely thermal reaction mechanisms by coupling nonthermal mechanistic steps, leading to efficient C-H bond activation with subsequent thermal heterogeneous reactions.

  18. Oxidative photoredox-catalytic activation of aliphatic nucleophiles for C(sp(3))-C(sp(2)) cross-coupling reactions.

    Science.gov (United States)

    Jahn, Emanuela; Jahn, Ullrich

    2014-12-01

    In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions.

  19. The Effect of Temperature and Ionic Strength on the Oxidation of Iodide by Iron(III) : A Clock Reaction Kinetic Study

    NARCIS (Netherlands)

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

    2012-01-01

    A laboratory exercise has recently been reported in which the students use the initial rates method based on the clock reaction approach to deduce the rate law and propose a reaction mechanism for the oxidation of iodide by iron(III) ions. The same approach is used in the exercise proposed herein; t

  20. Calculated ionisation potentials to determine the oxidation of vanillin precursors by lignin peroxidase.

    NARCIS (Netherlands)

    ten Have, R.; Rietjens, I.M.C.M.; Hartmans, S.; Swarts, H.J.; Field, J.A.

    1998-01-01

    In view of the biocatalytic production of vanillin, this research focused on the lignin peroxidase (LiP) catalysed oxidation of naturally occurring phenolic derivatives: O-methyl ethers, O-acetyl esters, and O-glucosyl ethers. The ionisation potential (IP) of a series of model compounds was calculat

  1. Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways.

    Science.gov (United States)

    Perez-Benito, Joaquin F

    2011-09-08

    The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.

  2. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions.

    Science.gov (United States)

    Kelly, Paul P; Eichler, Anja; Herter, Susanne; Kranz, David C; Turner, Nicholas J; Flitsch, Sabine L

    2015-01-01

    Cytochrome P450 monooxygenases are useful biocatalysts for C-H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations.

  3. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

    Directory of Open Access Journals (Sweden)

    Paul P. Kelly

    2015-09-01

    Full Text Available Cytochrome P450 monooxygenases are useful biocatalysts for C–H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations.

  4. Mechanochemical Reaction of Lanthanum Carbonate with Sodium Hydroxide and Preparation of Lanthanum Oxide Nanoparticle

    Institute of Scientific and Technical Information of China (English)

    李永绣; 周雪珍; 王志强

    2002-01-01

    The preparation of nano sized La2O3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X-ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi-phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La2(OH)2(CO3)2*H2O under a quasi-hydrothermal synthesis condition caused by the mechanical ball-milling. The synthesized La2O3 powder appears clearly separated spherical-like monodisperse nano-size particles in which particle size ranges from 30 to 50 nm.

  5. Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization–Carbonylation–Alkynylation

    Science.gov (United States)

    2016-01-01

    A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C–C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an additional CO insertion takes place to give spiro[4.4]nonenes with formation of overall five C–C bonds. PMID:27704805

  6. OH-initiated oxidation of monoterpenes: reaction of alpha-pinene.

    Science.gov (United States)

    Librando, Vito; Tomaselli, Gaetano; Tringali, Giuseppe

    2003-04-01

    The aim of this paper is to study the reaction products of alpha-pinene, beta-pinene, limonene, 3-carene and sabinene with OH radicals by FT-IR spectroscopy and by HPLC-MS-MS, to evaluate the secondary aerosol formation. All gas phase reaction products were quantified using reference compounds. As source of OH radicals were used H2O2 and CH3ONO. The experiments were performed at low terpene concentration (0.9-2.1 ppm) and at high terpene concentration (4.1-13.2 ppm), using H2O2 and CH3ONO as sources of OH radicals.

  7. Nitric Oxide Donors as Neuroprotective Agents after an Ischemic Stroke-Related Inflammatory Reaction

    Directory of Open Access Journals (Sweden)

    Marisol Godínez-Rubí

    2013-01-01

    Full Text Available Cerebral ischemia initiates a cascade of detrimental events including glutamate-associated excitotoxicity, intracellular calcium accumulation, formation of Reactive oxygen species (ROS, membrane lipid degradation, and DNA damage, which lead to the disruption of cellular homeostasis and structural damage of ischemic brain tissue. Cerebral ischemia also triggers acute inflammation, which exacerbates primary brain damage. Therefore, reducing oxidative stress (OS and downregulating the inflammatory response are options that merit consideration as potential therapeutic targets for ischemic stroke. Consequently, agents capable of modulating both elements will constitute promising therapeutic solutions because clinically effective neuroprotectants have not yet been discovered and no specific therapy for stroke is available to date. Because of their ability to modulate both oxidative stress and the inflammatory response, much attention has been focused on the role of nitric oxide donors (NOD as neuroprotective agents in the pathophysiology of cerebral ischemia-reperfusion injury. Given their short therapeutic window, NOD appears to be appropriate for use during neurosurgical procedures involving transient arterial occlusions, or in very early treatment of acute ischemic stroke, and also possibly as complementary treatment for neurodegenerative diseases such as Parkinson or Alzheimer, where oxidative stress is an important promoter of damage. In the present paper, we focus on the role of NOD as possible neuroprotective therapeutic agents for ischemia/reperfusion treatment.

  8. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl;

    2015-01-01

    are required in the reduction, and, nally, oxidation by NO + O2 or NO2 leads to the same state of the catalyst. These points are shown experimentally for a Cu-CHA catalyst, by combining in situ X-ray absorption spectrosocpy (XAS), electron paramagnetic resonance (EPR), and Fourier transform infrared...

  9. Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

    KAUST Repository

    Nagaraju, Doddahalli H.

    2014-12-01

    Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells. © 2014 Elsevier Ltd.

  10. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    KAUST Repository

    Yin, S. M.

    2017-01-18

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  11. Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

    Science.gov (United States)

    Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

    2011-08-01

    One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

  12. A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Lyubimov, Artem Y. [Department of Molecular, Cell and Developmental Biology, University of California, Santa Cruz, Sinsheimer Laboratories, 1156 High Street, Santa Cruz, CA 95064 (United States); Chen, Lin; Sampson, Nicole S. [Department of Chemistry, Stony Brook University, Stony Brook, NY 11794-3400 (United States); Vrielink, Alice, E-mail: alice.vrielink@uwa.edu.au [School of Biomedical, Biomolecular and Chemical Sciences, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009 (Australia); Department of Molecular, Cell and Developmental Biology, University of California, Santa Cruz, Sinsheimer Laboratories, 1156 High Street, Santa Cruz, CA 95064 (United States)

    2009-11-01

    The importance of active-site electrostatics for oxidative and reductive half-reactions in a redox flavoenzyme (cholesterol oxidase) have been investigated by a combination of biochemistry and atomic resolution crystallography. A detailed examination of active-site dynamics demonstrates that the oxidation of substrate and the re-oxidation of the flavin cofactor by molecular oxygen are linked by a single active-site asparagine. Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3β-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH⋯π interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k{sub cat}. Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0 Å resolution) reveals significant perturbations in the active site. As predicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH⋯π interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered.

  13. Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.

    Science.gov (United States)

    Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

    2016-05-25

    Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.

  14. Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

    Directory of Open Access Journals (Sweden)

    Kelly Pemartin-Biernath

    2016-06-01

    Full Text Available Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD, below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM. Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications.

  15. Investigation of lipid oxidation and non-enzymatic browning reactions in marine PL emulsions

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.;

    of amino acids (leucine, methionine and lysine) from 2 authentic standards (PC and PE) and 2 purified marine PL (LC and MPL) through sonication method. Emulsions were incubated at 60 ºC for 0, 2, 4 and 6 days. Non-enzymatic browning reactions were investigated through measurement of i) Strecker aldehydes...

  16. In situ Raman and pulse reaction study on the partial oxidation of methane to synthesis gas over a Pt/Al2O3 catalyst.

    Science.gov (United States)

    Wang, Mei-Liu; Zheng, Hao-Zhuan; Li, Jian-Mei; Weng, Wei-Zheng; Xia, Wen-Sheng; Huang, Chuan-Jing; Wan, Hui-Lin

    2011-02-01

    Catalytic partial oxidation of methane (POM) to synthesis gas (syngas) over Pt/Al(2)O(3) was investigated by in situ microprobe Raman and pulse reaction methods with attention focused on the mechanism of syngas formation in the oxidation zone (i.e., the catalyst zone in which O(2) was still available in the reaction feed). It was found that the amount of platinum oxide in the catalyst under POM conditions was below the detection level of Raman spectroscopy. Raman bands of carbon species that originated from methane dissociation were detected at the entrance of the catalyst bed under working conditions. The results of the pulse reaction study on POM as well as steam and CO(2) reforming of methane at 700 °C with a contact time of less than 1 ms over the catalyst suggest that pyrolysis of methane on reduced platinum sites followed by coupling of two surface hydrogen atoms to H(2) and partial oxidation of surface carbon species to CO are the major reactions responsible for syngas formation in the oxidation zone. Under the experimental conditions, steam and CO(2) reforming of methane play only a minor role in syngas formation in the same reaction zone. The contribution of the last two reactions increases with increasing contact time.

  17. Catalytic methanation reaction over alumina supported cobalt oxide doped noble metal oxides for the purification of simulated natural gas

    Institute of Scientific and Technical Information of China (English)

    Wan Azelee Wan Abu Bakar; Rusmidah Ali; Abdul Aziz Abdul Kadir; Salmiah Jamal Mat Rosid; Nurul Shafeeqa Mohammad

    2012-01-01

    A series of alumina supported cobalt oxide based catalysts doped with noble metals such as ruthenium and platinum were prepared by wet impregnation method.The variables studied were difference ratio and calcination temperatures.Pt/Co( 10∶90 )/Al2O3 catalyst calcined at 700 ℃ was found to be the best catalyst which able to convert 70.10% of CO2 into methane with 47% of CH4 formation at maximum temperature studied of 400 ℃.X-ray diffraction analysis showed that this catalyst possessed the active site Co3O4 in face-centered cubic and PtO2 in the orthorhombic phase with Al2O3 existed in the cubic phase.According to the FESEM micrographs,both fresh and spent Pt/Co( 10∶90)/Al2O3 catalysts displayed small particle size with undefined shape.Nitrogen Adsorption analysis showed that 5.50% reduction of the total surface area for the spent Pt/Co( 10∶90)/Al2O3 catalyst.Meanwhile,Energy Dispersive X-ray analysis (EDX) indicated that Co and Pt were reduced by 0.74% and 0.14% respectively on the spent Pt/Co( 10∶90)/Al2O3catalyst.Characterization using FT-IR and TGA-DTA analysis revealed the existence of residual nitrate and hydroxyl compounds on the Pt/Co( 10∶90)/Al2O3 catalyst.

  18. Synthesis of Pt and Pt-Fe nanoparticles supported on MWCNTs used as electrocatalysts in the methanol oxidation reaction

    Institute of Scientific and Technical Information of China (English)

    J.R.Rodriguez; R.M.F´elix; E.A.Reynoso; Y.Gochi-Ponce; Y.Verde Gómez; S.Fuentes Moyado; G.Alonso-N ´uñez

    2014-01-01

    This work reports a feasible synthesis of highly-dispersed Pt and Pt-Fe nanoparticles supported on multiwall carbon nanotubes (MWCNTs) without Fe and multiwall carbon nanotubes with iron (MWCNTs-Fe) which applied as electrocatalysts for methanol electrooxidation. A Pt coordination complex salt was synthesized in an aqueous solution and it was used as precursor to prepare Pt/MWCNTs, Pt/MWCNTs-Fe, and Pt-Fe/MWCNTs using FeCl2·4H2O as iron source which were named S1, S2 and S3, respectively. The coordination complex of platinum (TOA)2PtCl6 was obtained by the chemical reaction between (NH4)2PtCl6 with tetraoctylammonium bromide (TOAB) and it was characterized by FT-IR and TGA. The materials were characterized by Raman spectroscopy, SEM, EDS, XRD, TEM and TGA. The electrocatalytic activity of Pt-based supported on MWCNTs in the methanol oxidation was investigated by cyclic voltammetry (CV) and chronoamperometry (CA). Pt-Fe/MWCNTs electrocatalysts showed the highest electrocatalytic activity and stability among the tested electrocatalysts due to that the addition of”Fe”promotes the OH species adsorption on the electrocatalyst surface at low potentials, thus, enhancing the activity toward the methanol oxidation reaction (MOR).

  19. Nitrogen oxide formation from chemically-bound nitrogen during the combustion of fossil fuels. [Extended Zeldovich reactions

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, R.E.

    1976-06-01

    One of the many problems associated with the firing of fossil fuels is the impact on the ambient levels of nitrogen oxides. Since the use of coals, oils and coal-derived fuels is expected to triple by 1985, it is urgent that the formation of nitrogen oxides from molecular nitrogen and organo-nitrogen species be fully characterized so that emission abatement strategies can be formulated. The thermal fixation of atmospheric nitrogen and the free radical reactions of nitrogenous species are the sources of NO/sub x/. The fixation reactions can be described by the extended Zeldovich mechanism, and techniques such as staged combustion and flue gas recirculation have been employed to reduce combustion temperatures and, hence, thermally formed NO. These techniques have had little effect, however, on the conversion of chemically-bound nitrogen to NO/sub x/. The fate of chemically-bound nitrogen depends upon such factors as the nitrogen content of the fuel and the equivalence ratio and upon the physical processes governing combustion. Research is proposed to establish the kinetic processes involved in the conversion of fuel nitrogen to NO and N/sub 2/ in environments characteristic of fossil fuel combustion and to identify those conditions which favor the reduction of NO to N/sub 2/.

  20. Evaluation of revised polymerase chain reaction primers for more inclusive quantification of ammonia-oxidizing archaea and bacteria.

    Science.gov (United States)

    Meinhardt, Kelley A; Bertagnolli, Anthony; Pannu, Manmeet W; Strand, Stuart E; Brown, Sally L; Stahl, David A

    2015-04-01

    Ammonia-oxidizing archaea (AOA) and bacteria (AOB) fill key roles in the nitrogen cycle. Thus, well-vetted methods for characterizing their distribution are essential for framing studies of their significance in natural and managed systems. Quantification of the gene coding for one subunit of the ammonia monooxygenase (amoA) by polymerase chain reaction is frequently employed to enumerate the two groups. However, variable amplification of sequence variants comprising this conserved genetic marker for ammonia oxidizers potentially compromises within- and between-system comparisons. We compared the performance of newly designed non-degenerate quantitative polymerase chain reaction primer sets to existing primer sets commonly used to quantify the amoA of AOA and AOB using a collection of plasmids and soil DNA samples. The new AOA primer set provided improved quantification of model mixtures of different amoA sequence variants and increased detection of amoA in DNA recovered from soils. Although both primer sets for the AOB provided similar results for many comparisons, the new primers demonstrated increased detection in environmental application. Thus, the new primer sets should provide a useful complement to primers now commonly used to characterize the environmental distribution of AOA and AOB.

  1. Reaction kinetics and efficiencies for the hydroxyl and sulfate radical based oxidation of artificial sweeteners in water.

    Science.gov (United States)

    Toth, Janie E; Rickman, Kimberly A; Venter, Andre R; Kiddle, James J; Mezyk, Stephen P

    2012-10-11

    Over the past several decades, the increased use of artificial sweeteners as dietary supplements has resulted in rising concentrations of these contaminants being detected in influent waters entering treatment facilities. As conventional treatments may not quantitatively remove these sweeteners, radical-based advanced oxidation and reduction (AO/RP) treatments could be a viable alternative. In this study, we have established the reaction kinetics for both hydroxyl ((•)OH) and sulfate (SO(4)(•-)) radical reaction with five common artificial sweeteners, as well as their associated reaction efficiencies. Rate constants for acesulfame K, aspartame, rebaudioside A, saccharin, and sucralose were <2 × 10(7), (2.28 ± 0.02) × 10(9), (2.1 ± 0.1) × 10(8), <2 × 10(7), and (1.7 ± 0.1) × 10(8) M(-1) s(-1) for the sulfate radical, and (3.80 ± 0.27) × 10(9), (6.06 ± 0.05) × 10(9), (9.97 ± 0.12) × 10(9), (1.85 ± 0.01) × 10(9), and (1.50 ± 0.01) × 10(9) M(-1) s(-1) for the hydroxyl radical, respectively. These latter values have to be combined with their corresponding reaction efficiencies of 67.9 ± 0.9, 52.2 ± 0.7, 43.0 ± 2.5, 52.7 ± 2.9, and 98.3 ± 3.5% to give effective rate constants for the hydroxyl radical reaction that can be used in the modeling of the AOP based removal of these contaminants.

  2. DFT Study of Mechanism of Extraction Reaction Between Germylene Carbene (H2Ge=C:) and Its Derivatives and Ethylene Oxide

    Institute of Scientific and Technical Information of China (English)

    Xiu-hui Lu; Xin Che; Yong-qing Li; Zhi-na Wang

    2011-01-01

    The mechanism of the oxide extraction reaction between singlet germylene carbene and its derivatives X2Ge=C: (X=H, F, C1, CH3) and ethylene oxide has been investigated with B3LYP/6-311G(d,p) method. The results show that this kind of reaction has similar mechanism, the shift of 2p lone electron pair of O in ethylene oxide to the 2p unoccupied orbital of C in X2Ge=C: gives a p→p donor-acceptor bond, thereby leading to the formation of intermediate. As the p→p donor-acceptor bond continues to strengthen, that is the C-O bond continues to shorten, the intermediate generates product (P+C2H4) via transition state. It is the substituent electronegativity that mainly affect the extraction reactions. When the substituent electronegativity is greater, the energy barrier is lower, and the reaction rate is greater.

  3. Alcohol Selectivity in a Synthetic Thermophilic n-Butanol Pathway Is Driven by Biocatalytic and Thermostability Characteristics of Constituent Enzymes

    Science.gov (United States)

    Loder, Andrew J.; Zeldes, Benjamin M.; Garrison, G. Dale; Lipscomb, Gina L.; Adams, Michael W. W.

    2015-01-01

    n-Butanol is generated as a natural product of metabolism by several microorganisms, but almost all grow at mesophilic temperatures. A synthetic pathway for n-butanol production from acetyl coenzyme A (acetyl-CoA) that functioned at 70°C was assembled in vitro from enzymes recruited from thermophilic bacteria to inform efforts for engineering butanol production into thermophilic hosts. Recombinant versions of eight thermophilic enzymes (β-ketothiolase [Thl], 3-hydroxybutyryl-CoA dehydrogenase [Hbd], and 3-hydroxybutyryl-CoA dehydratase [Crt] from Caldanaerobacter subterraneus subsp. tengcongensis; trans-2-enoyl-CoA reductase [Ter] from Spirochaeta thermophila; bifunctional acetaldehyde dehydrogenase/alcohol dehydrogenase [AdhE] from Clostridium thermocellum; and AdhE, aldehyde dehydrogenase [Bad], and butanol dehydrogenase [Bdh] from Thermoanaerobacter sp. strain X514) were utilized to examine three possible pathways for n-butanol. These pathways differed in the two steps required to convert butyryl-CoA to n-butanol: Thl-Hbd-Crt-Ter-AdhE (C. thermocellum), Thl-Hbd-Crt-Ter-AdhE (Thermoanaerobacter X514), and Thl-Hbd-Crt-Ter-Bad-Bdh. n-Butanol was produced at 70°C, but with different amounts of ethanol as a coproduct, because of the broad substrate specificities of AdhE, Bad, and Bdh. A reaction kinetics model, validated via comparison to in vitro experiments, was used to determine relative enzyme ratios needed to maximize n-butanol production. By using large relative amounts of Thl and Hbd and small amounts of Bad and Bdh, >70% conversion to n-butanol was observed in vitro, but with a 60% decrease in the predicted pathway flux. With more-selective hypothetical versions of Bad and Bdh, >70% conversion to n-butanol is predicted, with a 19% increase in pathway flux. Thus, more-selective thermophilic versions of Bad, Bdh, and AdhE are needed to fully exploit biocatalytic n-butanol production at elevated temperatures. PMID:26253677

  4. Reduced graphene oxide as photocatalyst for CO2 reduction reaction(Conference Presentation)

    Science.gov (United States)

    Chang, Yu-Chung

    2016-10-01

    Photocatalytic conversion of carbon dioxide (CO2) to hydrocarbons such as methanol makes possible simultaneous solar energy harvesting and CO2 reduction. Our previous work is using graphene oxide (GO) as a promising photocatalyst for photocatalytic conversion of CO2 to methanol[1].When using graphene oxide as photocatalyst, the photocatalytic efficiency is 4-flod higher than TiO2 powder. GO has a lot of defects on the surface and those defects make sp2 carbon structure become sp3 carbon structure. The carbon structure change cause the GO has large energy gap about 2.7 eV to 3.2 eV. In order to remove the defect and reduce the energy gap of GO, Zhao et al. try to annealing GO powder in the nitrogen atmosphere at 900oC, the GO structure can be reduced to near graphene structure[2]. Zhu et al. do some low temperature annealing, it can control the structure and energy bandgap of GO by control annealing temperature. If the annealing temperature increase the bandgap of GO will be reduce[3]. So, we can using this annealing process to reduce the bandgap of the GO. In the varying temperature thermal reduction process, as the temperature increases from 130oC to 170oC, the functional groups of the graphene oxide will be reduced and band gap of graphene oxide will be narrowed at same time. The characteristic of thermal reduced graphene oxide were analyzed by SEM, XRD and Raman measurements. The band position was determined by UV/Vis. The reduction of functional groups correlates to red shift in light absorption and eventual quenching in the PL signal of RGOs. Combining hydrophobicity, light harvesting and PL quench, we get the highest yield of RGO150 (0.31 μmole g-1 -cat hr-1) is 1.7-fold higher than that of GO (0.18μmole g-1 -cat hr-1). This work investigates a modified method for using a thermal reduction process to reduce the energy gap of graphene oxide.

  5. Steam gasification of wood biomass in a fluidized biocatalytic system bed gasifier: A model development and validation using experiment and Boubaker Polynomials Expansion Scheme BPES

    Directory of Open Access Journals (Sweden)

    Luigi Vecchione

    2015-07-01

    Full Text Available One of the most important issues in biomass biocatalytic gasification is the correct prediction of gasification products, with particular attention to the Topping Atmosphere Residues (TARs. In this work, performedwithin the European 7FP UNIfHY project, we develops and validate experimentally a model which is able of predicting the outputs,including TARs, of a steam-fluidized bed biomass gasifier. Pine wood was chosen as biomass feedstock: the products obtained in pyrolysis tests are the relevant model input. Hydrodynamics and chemical properties of the reacting system are considered: the hydrodynamic approach is based on the two phase theory of fluidization, meanwhile the chemical model is based on the kinetic equations for the heterogeneous and homogenous reactions. The derived differentials equations for the gasifier at steady state were implemented MATLAB. Solution was consecutively carried out using the Boubaker Polynomials Expansion Scheme by varying steam/biomass ratio (0.5-1 and operating temperature (750-850°C.The comparison between models and experimental results showed that the model is able of predicting gas mole fractions and production rate including most of the representative TARs compounds

  6. Biocatalytic Behaviour of Immobilized Rhizopus oryzae Lipase in the 1,3-Selective Ethanolysis of Sunflower Oil to Obtain a Biofuel Similar to Biodiesel

    Directory of Open Access Journals (Sweden)

    Carlos Luna

    2014-08-01

    Full Text Available A new biofuel similar to biodiesel was obtained in the 1,3-selective transesterification reaction of sunflower oil with ethanol using as biocatalyst a Rhizopus oryzae lipase (ROL immobilized on Sepiolite, an inorganic support. The studied lipase was a low cost powdered enzyme preparation, Biolipase-R, from Biocon-Spain, a multipurpose additive used in food industry. In this respect, it is developed a study to optimize the immobilization procedure of these lipases on Sepiolite. Covalent immobilization was achieved by the development of an inorganic-organic hybrid linker formed by a functionalized hydrocarbon chain with a pendant benzaldehyde, bonded to the AlPO4 support surface. Thus, the covalent immobilization of lipases on amorphous AlPO4/sepiolite (20/80 wt % support was evaluated by using two different linkers (p-hydroxybenzaldehyde and benzylamine-terephthalic aldehyde, respectively. Besides, the catalytic behavior of lipases after physical adsorption on the demineralized sepiolite  was also evaluated. Obtained results indicated that covalent immobilization with the p-hydroxybenzaldehyde linker gave the best biocatalytic behavior. Thus, this covalently immobilized lipase showed a remarkable stability as well as an excellent capacity of reutilization (more than five successive reuses without a significant loss of its initial catalytic activity. This could allow a more efficient fabrication of biodiesel minimizing the glycerol waste production.

  7. Biocatalytic behaviour of immobilized Rhizopus oryzae lipase in the 1,3-selective ethanolysis of sunflower oil to obtain a biofuel similar to biodiesel.

    Science.gov (United States)

    Luna, Carlos; Verdugo, Cristóbal; Sancho, Enrique D; Luna, Diego; Calero, Juan; Posadillo, Alejandro; Bautista, Felipa M; Romero, Antonio A

    2014-08-04

    A new biofuel similar to biodiesel was obtained in the 1,3-selective transesterification reaction of sunflower oil with ethanol using as biocatalyst a Rhizopus oryzae lipase (ROL) immobilized on Sepiolite, an inorganic support. The studied lipase was a low cost powdered enzyme preparation, Biolipase-R, from Biocon-Spain, a multipurpose additive used in food industry. In this respect, it is developed a study to optimize the immobilization procedure of these lipases on Sepiolite. Covalent immobilization was achieved by the development of an inorganic-organic hybrid linker formed by a functionalized hydrocarbon chain with a pendant benzaldehyde, bonded to the AlPO4 support surface. Thus, the covalent immobilization of lipases on amorphous AlPO4/sepiolite (20/80 wt %) support was evaluated by using two different linkers (p-hydroxybenzaldehyde and benzylamine-terephthalic aldehyde, respectively). Besides, the catalytic behavior of lipases after physical adsorption on the demineralized sepiolite  was also evaluated. Obtained results indicated that covalent immobilization with the p-hydroxybenzaldehyde linker gave the best biocatalytic behavior. Thus, this covalently immobilized lipase showed a remarkable stability as well as an excellent capacity of reutilization (more than five successive reuses) without a significant loss of its initial catalytic activity. This could allow a more efficient fabrication of biodiesel minimizing the glycerol waste production.

  8. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    Energy Technology Data Exchange (ETDEWEB)

    Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

  9. Influence of O 2 and oxide on Cl/Si surface reactions

    Science.gov (United States)

    Aoto, Nahomi; Ikawa, Eiji; Kikkawa, Takamaro; Kurogi, Yukinori

    1991-05-01

    Variation of Si(111) and Si(100) surface conditions under sequential Cl 2 exposure, O 2 exposure, and other O-related treatments are examined by Auger electron spectroscopy (AES) and low-energy electron energy loss spectroscopy (LEELS). Cl-adsorbed Si surfaces, particularly Cl-adsorbed Si(111) surfaces, have a passivation effect under dry O 2 atmosphere, where O adsorption and oxidation are suppressed. On the other hand, Cl desorption and oxidation take place immediately on Cl-adsorbed surfaces when exposed to wet environments: humid clean-room air or de-ionized water. When O 2-treated Si surfaces are exposed to Cl 2 atmospheres, Cl adsorption occurs on SiO x but not on SiO 2.

  10. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  11. Degradation of cellulose at the wet-dry interface. II. Study of oxidation reactions and effect of antioxidants.

    Science.gov (United States)

    Jeong, Myung-Joon; Dupont, Anne-Laurence; de la Rie, E René

    2014-01-30

    To better understand the degradation of cellulose upon the formation of a tideline at the wet-dry interface when paper is suspended in water, the production of chemical species involved in oxidation reactions was studied. The quantitation of hydroperoxides and hydroxyl radicals was carried out in reverse phase chromatography using triphenylphosphine and terephthalic acid, respectively, as chemical probes. Both reactive oxygen species were found in the tideline immediately after its formation, in the range of micromoles and nanomoles per gram of paper, respectively. The results indicate that hydroxyl radicals form for the most part in paper before the tideline experiment, whereas hydroperoxides appear to be produced primarily during tideline formation. Iron sulfate impregnation of the paper raised the production of hydroperoxides. After hygrothermal aging in sealed vials the hydroxyl radical content in paper increased significantly. When aged together in the same vial, tideline samples strongly influenced the degradation of samples from other areas of the paper (multi-sample aging). Different types of antioxidants were added to the paper before the tideline experiment to investigate their effect on the oxidation reactions taking place. In samples treated with iron sulfate or artificially aged, the addition of Irgafos 168 (tris(2,4-ditert-butylphenyl) phosphate) and Tinuvin 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate) reduced the concentration of hydroperoxides and hydroxyl radicals, respectively. Tinuvin 292 was also found to considerably lower the rate of cellulose chain scission reactions during hygrothermal aging of the paper.

  12. IL-23 Promotes Myocardial I/R Injury by Increasing the Inflammatory Responses and Oxidative Stress Reactions

    Directory of Open Access Journals (Sweden)

    Xiaorong Hu

    2016-05-01

    Full Text Available Background/Aims: Inflammation and oxidative stress play an important role in myocardial ischemia and reperfusion (I/R injury. We hypothesized that IL-23, a pro-inflammatory cytokine, could promote myocardial I/R injury by increasing the inflammatory response and oxidative stress. Methods: Male Sprague-Dawley rats were randomly assigned into sham operated control (SO group, ischemia and reperfusion (I/R group, (IL-23 + I/R group and (anti-IL-23 + I/R group. At 4 h after reperfusion, the serum concentration of lactate dehydrogenase (LDH, creatine kinase (CK and the tissue MDA concentration and SOD activity were measured. The infarcte size was measured by TTC staining. Apoptosis in heart sections were measured by TUNEL staining. The expression of HMGB1 and IL-17A were detected by Western Blotting and the expression of TNF-α and IL-6 were detected by Elisa. Results: After 4 h reperfusion, compared with the I/R group, IL-23 significantly increased the infarct size, the apoptosis of cardiomyocytes and the levels of LDH and CK (all P 0.05. All these effects were abolished by anti-IL-23 administration. Conclusion: The present study suggested that IL-23 may promote myocardial I/R injury by increasing the inflammatory responses and oxidative stress reaction.

  13. Chemically directed assembly of photoactive metal oxide nanoparticle heterojunctions via the copper-catalyzed azide-alkyne cycloaddition "click" reaction.

    Science.gov (United States)

    Cardiel, Allison C; Benson, Michelle C; Bishop, Lee M; Louis, Kacie M; Yeager, Joseph C; Tan, Yizheng; Hamers, Robert J

    2012-01-24

    Metal oxides play a key role in many emerging applications in renewable energy, such as dye-sensitized solar cells and photocatalysts. Because the separation of charge can often be facilitated at junctions between different materials, there is great interest in the formation of heterojunctions between metal oxides. Here, we demonstrate use of the copper-catalyzed azide-alkyne cycloaddition reaction, widely referred to as "click" chemistry, to chemically assemble photoactive heterojunctions between metal oxide nanoparticles, using WO(3) and TiO(2) as a model system. X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy verify the nature and selectivity of the chemical linkages, while scanning electron microscopy reveals that the TiO(2) nanoparticles form a high-density, conformal coating on the larger WO(3) nanoparticles. Time-resolved surface photoresponse measurements show that the resulting dyadic structures support photoactivated charge transfer, while measurements of the photocatalytic degradation of methylene blue show that chemical grafting of TiO(2) nanoparticles to WO(3) increases the photocatalytic activity compared with the bare WO(3) film.

  14. Reaction and Transport Processes Controlling In Situ Chemical Oxidation of DNAPLs

    Science.gov (United States)

    2006-11-01

    culture used was Burkholderia cepacia G4 (G4), which was originally isolated from an industrial waste treatment facility in Pensacola, Florida (Nelson et...sealed serum bottles , containing a 1:12 electron equivalent PCE-methanol mixture (85mg/L PCE, 13.3 mg/L methanol), with the varied ground water types...introduction of chemical oxidants into the subsurface to destroy organic contaminants in soil and ground water , with the goal being to reduce the mass

  15. Histological evaluation of bone reactions to aluminium oxide dental implants in man: a case report.

    Science.gov (United States)

    Piattelli, A; Podda, G; Scarano, A

    1996-04-01

    Alumina implants have been shown to possess high biocompatibility. The authors present the case of an aluminium oxide ceramic implant removed because of fracture of the abutment after a 30-month loading period. It was possible to observe microscopically that the implant was covered by highly mineralized mature compact lamellar bone; no connective tissue or inflammatory cells were present at the interface. Osteocytes were observed very close to the bone-implant interface. These features indicate the good biocompatibility of the implant.

  16. Multi-resistive Reduced Graphene Oxide Diode with Reversible Surface Electrochemical Reaction induced Carrier Control

    OpenAIRE

    Hyungtak Seo; Seungbae Ahn; Jinseo Kim; Young-Ahn Lee; Koo-Hyun Chung; Ki-Joon Jeon

    2014-01-01

    The extended application of graphene-based electronic devices requires a bandgap opening in order to realize the targeted device functionality. Since the bandgap tuning of pristine graphene is limited to 360 meV, the chemical modification of graphene is considered essential to achieve a large bandgap opening at the expense of electrical properties degradation. Reduced graphene oxide (RGO) has attracted significant interest for fabricating graphene-based semiconductors since it has several adv...

  17. Anthocyanin Interactions with DNA: Intercalation, Topoisomerase I Inhibition and Oxidative Reactions.

    Science.gov (United States)

    Webb, Michael R; Min, Kyungmi; Ebeler, Susan E

    2008-09-23

    Anthocyanins and their aglycone anthocyanidins are pigmented flavonoids found in significant amounts in many commonly consumed foods. They exhibit a complex chemistry in aqueous solution, which makes it difficult to study their chemistry under physiological conditions. Here we used a gel electrophoresis assay employing supercoiled DNA plasmid to examine the ability of these compounds (1) to intercalate DNA, (2) to inhibit human topoisomerase I through both inhibition of plasmid relaxation activity (catalytic inhibition) and stabilization of the cleavable DNA-topoisomerase complex (poisoning), and (3) to inhibit or enhance oxidative single-strand DNA nicking. We found no evidence of DNA intercalation by anthocyan(id)ins in the physiological pH range for any of the compounds used in this study-cyanidin chloride, cyanidin 3-O-glucoside, cyanidin 3,5-O-diglucoside, malvidin 3-O-glucoside and luteolinidin chloride. The anthocyanins inhibited topoisomerase relaxation activity only at high concentrations (> 50 muM) and we could find no evidence of topoisomerase I cleavable complex stabilization by these compounds. However, we observed that all of the anthocyan(id)ins used in this study were capable of inducing significant oxidative DNA strand cleavage (nicking) in the presence of 1 mM DTT (dithiothreitol), while the free radical scavenger, DMSO, at concentrations typically used in similar studies, completely inhibited DNA nicking. Finally, we propose a mechanism to explain the anthocyan(id)in induced oxidative DNA cleavage observed under our experimental conditions.

  18. Iron(III) porphyrin-catalysed oxidation reactions by -chloroperbenzoic acid: Nature of reactive intermediates

    Indian Academy of Sciences (India)

    A Agarwala; V Bagchi; D Bandyopadhyay

    2005-03-01

    The reaction of -chloroperbenzoic (-CPBA) acid with meso-tetrakis (pentafluorophenyl) porphynatoiron(III) chloride (F20TPPFe(III)Cl) has been studied in dichloromethane and acetonitrile medium at 25 ± 1° C. The reactive intermediates formed in this reaction have been quantitatively trapped by 2,4,6-tri -butylphenol (TTBP) in both the solvents. It has been observed that the kinetic plots of the formation of TTBP$^{\\bullet}$ radical in dichloromethane are all multiexponential, supporting the formation of more than one reactive intermediate in this solvent. In acetonitrile solvent the formation of TTBP$^{\\bullet}$ radical was however observed to be distinctly single exponential. Different kinds of reactive intermediates are proposed in these two solvents.

  19. Carbon-supported palladium and ruthenium nanoparticles: application as catalysts in alcohol oxidation, cross-coupling and hydrogenation reactions.

    Science.gov (United States)

    García-Suárez, Eduardo J; Lara, Patricia; García, Ana B; Philippot, Karine

    2013-11-01

    In the last fifteen-years, the application of metal nanoparticles as catalysts in organic synthesis has received a renewed interest. Therefore, much attention is currently being paid to the synthesis of metal nanoparticles in order to achieve the control of their characteristics in terms of size, shape and surface chemistry. Besides this, the recyclability as well as the recovery from the reaction medium still remain the major drawbacks to widespread the use of nanoparticles in catalysis. To overcome these problems, the immobilization of metal nanoparticles on solid supports appears as a promising alternative. In that context, carbon materials offer several advantages as solid supports such as availability, relatively low cost, high mechanical strength, chemical stability, and a pore structure along with an attractive surface chemistry which allows easy modifications, such as its functionalization, to suit the nanoparticles immobilization needs. Among the transition metals Palladium and Ruthenium are widely employed as efficient catalysts in many reactions. Herein, the most recent advances, from recent papers and patents, in relation to the preparation of carbon-supported Pd or Ru nanoparticles systems as well as their application as catalysts in alcohol oxidation, cross-coupling or hydrogenation reactions, are reviewed.

  20. Preparation of Biocatalytic Microparticles by Interfacial Self-Assembly of Enzyme-Nanoparticle Conjugates Around a Cross-Linkable Core.

    Science.gov (United States)

    Andler, S M; Wang, L-S; Goddard, J M; Rotello, V M

    2016-01-01

    Rational design of hierarchical interfacial assembly of reusable biocatalytic microparticles is described in this chapter. Specifically, purified enzymes and functionalized nanoparticles are electrostatically assembled at the interface of cross-linked microparticles which are formed through ring opening metathesis polymerization. The diameters of microparticle assemblies average 10μm, and they show enhanced kinetic efficiency as well as improved stability against heat, pH, and solvent denaturation when compared to stabilities of the corresponding native enzymes.

  1. Efficiency Analysis and Mechanism Insight of that Whole-Cell Biocatalytic Production of Melibiose from Raffinose with Saccharomyces cerevisiae.

    Science.gov (United States)

    Zhou, Yingbiao; Zhu, Yueming; Dai, Longhai; Men, Yan; Wu, Jinhai; Zhang, Juankun; Sun, Yuanxia

    2017-01-01

    Melibiose is widely used as a functional carbohydrate. Whole-cell biocatalytic production of melibiose from raffinose could reduce its cost. However, characteristics of strains for whole-cell biocatalysis and mechanism of such process are unclear. We compared three different Saccharomyces cerevisiae strains (liquor, wine, and baker's yeasts) in terms of concentration variations of substrate (raffinose), target product (melibiose), and by-products (fructose and galactose) in whole-cell biocatalysis process. Distinct difference was observed in whole-cell catalytic efficiency among three strains. Furthermore, activities of key enzymes (invertase, α-galactosidase, and fructose transporter) involved in process and expression levels of their coding genes (suc2, mel1, and fsy1) were investigated. Conservation of key genes in S. cerevisiae strains was also evaluated. Results show that whole-cell catalytic efficiency of S. cerevisiae in the raffinose substrate was closely related to activity of key enzymes and expression of their coding genes. Finally, we summarized characteristics of producing strain that offered advantages, as well as contributions of key genes to excellent strains. Furthermore, we presented a dynamic mechanism model to achieve some mechanism insight for this whole-cell biocatalytic process. This pioneering study should contribute to improvement of whole-cell biocatalytic production of melibiose from raffinose.

  2. Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

    Science.gov (United States)

    Dale, A. W.; Regnier, P.; Knab, N. J.; Jørgensen, B. B.; Van Cappellen, P.

    2008-06-01

    A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction network for organic carbon degradation, which includes extracellular hydrolysis of macromolecular organic matter, fermentation, sulfate reduction, methanogenesis, AOM, acetogenesis and acetotrophy. Catabolic reaction rates are determined using a modified Monod rate expression that explicitly accounts for limitation by the in situ catabolic energy yields. The fraction of total sulfate reduction due to AOM in the sulfate-methane transition zone (SMTZ) at each site is calculated. The model provides an explanation for the methane tailing phenomenon which is observed here and in other marine sediments, whereby methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ at both sites because of high hydrogen concentrations (∼3-6 nM). The model results imply there is no straightforward relationship between pore water concentrations and the minimum catabolic energy needed to support life because of the highly coupled nature of the reaction network. Best model fits are obtained with a minimum energy for AOM of ∼11 kJ mol-1, which is within the range reported in the literature for anaerobic processes.

  3. NOVEL HYPERBRANCHED POLY(PHENYLENE OXIDE)S WITH PHENOLIC TERMINAL GROUPS: EFFECTS OF REACTION TIME AND CORE MOLECULES ON THE MOLECULAR WEIGHT AND POLYDISPERSITY

    Institute of Scientific and Technical Information of China (English)

    Ji-gui Zhang; Hai-qiao Wang; Xiao-yu Li

    2006-01-01

    A novel hyperbranched poly(phenylene oxide) (HPPO) with phenolic terminal groups was prepared from 4-bromo-4′,4″-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide (DMSO) via a modified Ullmann reaction.The molecular weight and polydispersity (PD) of the resulting polymers increased with increasing reaction time. In the presence of core molecules (bisphenol A and 1,3,5-trihydroxybenzene), which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by 1H-NMR, 13C-NMR, FT-IR, and GPC.

  4. The Synthesis, Characterization and Catalytic Reaction Studies of Monodisperse Platinum Nanoparticles in Mesoporous Oxide Materials

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, Robert M. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    A catalyst design program was implemented in which Pt nanoparticles, either of monodisperse size and/or shape were synthesized, characterized and studied in a number of hydrocarbon conversion reactions. The novel preparation of these materials enables exquisite control over their physical and chemical properties that could be controlled (and therefore rationally tuned) during synthesis. The ability to synthesize rather than prepare catalysts followed by thorough characterization enable accurate structure-function relationships to be elucidated. This thesis emphasizes all three aspects of catalyst design: synthesis, characterization and reactivity studies. The precise control of metal nanoparticle size, surface structure and composition may enable the development of highly active and selective heterogeneous catalysts.

  5. DFT studies on the SCR reaction mechanism of nitrogen monoxide with propylene catalyzed by copper oxide

    Institute of Scientific and Technical Information of China (English)

    TIAN Ying; XU Jing; ZHAO Jing-xiang

    2007-01-01

    The SCR reaction mechanism of NO with C3H6catalyzed by CuO was studied by the method of Density Functional Theory (DFT) at the B3LYP/LanL2DZ levels. The optimized geometries of the stationary points on the potential surface were obtained and the transition state was confirmed by IRC and vibration analysis. The activation energy was calculated being 34. 26 kJ/mol. It was shown that propylene reacted firstly with Cu forming intermediate, and then nitrogen monoxide immediately reacted with the intermediate to be reduced. It was proved to be a direct interaction mechanism.

  6. Cascade enzymatic reactions for efficient carbon sequestration.

    Science.gov (United States)

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

    2015-04-01

    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA.

  7. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Luma M. Ahmed

    2014-01-01

    Full Text Available Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100. The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD, atomic force microscopy (AFM, and UV-visible diffuse spectrophotometry (UV-Vis. XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

  8. [Photodynamic reaction and oxidative stress - influence of the photodynamic effect on the activity antioxidant enzymes].

    Science.gov (United States)

    Romiszewska, Anna; Nowak-Stępniowska, Agata

    2014-01-01

    The interaction of light with a photosensitizer, accumulated in a tissue in the presence of oxygen, leads to formation of reactive oxygen species, mainly of singlet oxygen and free radicals. These factors react with biomolecules producing their oxidized states. Reactive oxygen species, such as singlet oxygen and free radicals are able to damage membranes, DNA, enzymes, structural peptides and other cellular structures leading to cell death. An antioxidant protection of cell is formed by enzymes belonging to the family of oxidoreductases: superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) and glutathione reductase (GR). Photodynamic therapy leads to the increased production of oxidizing toxic forms. It is important to analyze impact of PDT on the activity of antioxidant enzymes, such as SOD, CAT, GPx. The activity of antioxidant enzymes during the photodynamic effect is influenced by both the light energy dose and the concentration of photosensitizer. The presence only of the photosensitizer or only the light energy may also result in changes in the activity of these enzymes. The differences in changes in the activity of these enzymes depend on the type of used photosensitizer. A phenomenon of selective accumulation of photosensitizer in tumor tissues is used in the photodynamic method of tumor diagnosis and treatment.

  9. Degradation of thiamethoxam by the synergetic effect between anodic oxidation and Fenton reactions.

    Science.gov (United States)

    Meijide, J; Gómez, J; Pazos, M; Sanromán, M A

    2016-12-05

    In this work, a comparative study using anodic oxidation, Fenton and electro-Fenton treatments was performed in order to determine the synergic effect for the removal of thiamethoxan. The results determined that electro-Fenton process showed high efficiency in comparison with Fenton or anodic oxidation. After that, this hybrid process was optimized and the influence of iron catalyst concentration and applied current intensity on the degradation and mineralization were evaluated. Degradation profiles were monitored by high performance liquid chromatography (HPLC) being satisfactorily described by pseudo-first order kinetic model. At the optimal experimental conditions (300mA and 0.2mM Fe(+2)), the complete degradation of thiamethoxam was achieved after 10min. On the other hand, mineralization of thiamethoxam was monitored by total organic carbon (TOC) decay reaching more than 92% of TOC removal after 8h. Furthermore, a plausible mineralization pathway for the thiamethoxam degradation was proposed based on the identification of by-products such as aromatic intermediates, carboxylic acids and inorganic ions released throughout electro-Fenton process.

  10. Insights into solar photo-Fenton reaction parameters in the oxidation of a sanitary landfill leachate at lab-scale.

    Science.gov (United States)

    Silva, Tânia F C V; Ferreira, Rui; Soares, Petrick A; Manenti, Diego R; Fonseca, Amélia; Saraiva, Isabel; Boaventura, Rui A R; Vilar, Vítor J P

    2015-12-01

    This work evaluates the effect of the main photo-Fenton (PF) reaction variables on the treatment of a sanitary landfill leachate collected at the outlet of a leachate treatment plant, which includes aerated lagooning followed by aerated activated sludge and a final coagulation-flocculation step. The PF experiments were performed in a lab-scale compound parabolic collector (CPC) photoreactor using artificial solar radiation. The photocatalytic reaction rate was determined while varying the total dissolved iron concentration (20-100 mg Fe(2+)/L), solution pH (2.0-3.6), operating temperature (10-50 °C), type of acid used for acidification (H2SO4, HCl and H2SO4 + HCl) and UV irradiance (22-68 W/m(2)). This work also tries to elucidate the role of ferric hydroxides, ferric sulphate and ferric chloride species, by taking advantage of ferric speciation diagrams, in the efficiency of the PF reaction when applied to leachate oxidation. The molar fraction of the most photoactive ferric species, FeOH(2+), was linearly correlated with the PF pseudo-first order kinetic constants obtained at different solution pH and temperature values. Ferric ion speciation diagrams also showed that the presence of high amounts of chloride ions negatively affected the PF reaction, due to the decrease of ferric ions solubility and scavenging of hydroxyl radicals for chlorine radical formation. The increment of the PF reaction rates with temperature was mainly associated with the increase of the molar fraction of FeOH(2+). The optimal parameters for the photo-Fenton reaction were: pH = 2.8 (acidification agent: H2SO4); T = 30 °C; [Fe(2+)] = 60 mg/L and UV irradiance = 44 WUV/m(2), achieving 72% mineralization after 25 kJUV/L of accumulated UV energy and 149 mM of H2O2 consumed.

  11. Thermochemical reaction mechanism of lead oxide with poly(vinyl chloride) in waste thermal treatment.

    Science.gov (United States)

    Wang, Si-Jia; Zhang, Hua; Shao, Li-Ming; Liu, Shu-Meng; He, Pin-Jing

    2014-12-01

    Poly(vinyl chloride) (PVC) as a widely used plastic that can promote the volatilization of heavy metals during the thermal treatment of solid waste, thus leading to environmental problems of heavy metal contamination. In this study, thermogravimetric analysis (TGA) coupled with differential scanning calorimeter, TGA coupled with Fourier transform infrared spectroscopy and lab-scale tube furnace experiments were carried out with standard PVC and PbO to explicate the thermochemical reaction mechanism of PVC with semi-volatile lead. The results showed that PVC lost weight from 225 to 230°C under both air and nitrogen with an endothermic peak, and HCl and benzene release were also detected. When PbO was present, HCl that decomposed from PVC instantly reacted with PbO via an exothermal gas-solid reaction. The product was solid-state PbCl2 at 501°C, PbCl2 melted, volatilized and transferred into flue gas or condensed into fly ash. Almost all PbCl2 volatilized above 900°C, while PbO just started to volatilize slowly at this temperature. Therefore, the chlorination effect of PVC on lead was apt to lower-temperature and rapid. Without oxygen, Pb2O was generated due to the deoxidizing by carbon, with oxygen, the amount of residual Pb in the bottom ash was significantly decreased.

  12. The oxidant and laser power-dependent plasmon-driven surface photocatalysis reaction of p-aminothiophenol dimerizing into p,p'-dimercaptoazobenzene on Au nanoparticles.

    Science.gov (United States)

    Tan, Enzhong; Yin, Penggang; Yu, Chunna; Yu, Ge; Zhao, Chang

    2016-09-05

    Recently, plasmon-driven surface photocatalysis (PDSPC) reactions have attracted more and more attention by means of surface-enhanced Raman scattering (SERS) because we can in situ monitor the reaction process and determine the final products and their quantities by the real-time SERS spectrum. In this work, self-assembly AuNPs with both high catalytic activity and strong SERS effect were used as a bifunctional platform for in situ monitoring of PDSPC reactions. p-Aminothiophenol (PATP), a famous model molecule, was selected as a probe molecule and FeCl3 and NaClO were selected as oxidants. In this way, oxidation reaction of PATP dimerizing into p,p'-dimercaptoazobenzene (DMAB) has been investigated by SERS, and the results show that oxidant and laser power can alter the conversion rate of the reaction. This work provides a novel approach for controlling PDSPC reaction rate, which may be useful for understanding the mechanism of PDSPC reactions.

  13. The oxidant and laser power-dependent plasmon-driven surface photocatalysis reaction of p-aminothiophenol dimerizing into p,p‧-dimercaptoazobenzene on Au nanoparticles

    Science.gov (United States)

    Tan, Enzhong; Yin, Penggang; Yu, Chunna; Yu, Ge; Zhao, Chang

    2016-09-01

    Recently, plasmon-driven surface photocatalysis (PDSPC) reactions have attracted more and more attention by means of surface-enhanced Raman scattering (SERS) because we can in situ monitor the reaction process and determine the final products and their quantities by the real-time SERS spectrum. In this work, self-assembly AuNPs with both high catalytic activity and strong SERS effect were used as a bifunctional platform for in situ monitoring of PDSPC reactions. p-Aminothiophenol (PATP), a famous model molecule, was selected as a probe molecule and FeCl3 and NaClO were selected as oxidants. In this way, oxidation reaction of PATP dimerizing into p,p‧-dimercaptoazobenzene (DMAB) has been investigated by SERS, and the results show that oxidant and laser power can alter the conversion rate of the reaction. This work provides a novel approach for controlling PDSPC reaction rate, which may be useful for understanding the mechanism of PDSPC reactions.

  14. Staining of wool using the reaction products of ABTS oxidation by laccase: synergetic effects of ultrasound and cyclic voltammetry.

    Science.gov (United States)

    Munteanu, Florentina-Daniela; Basto, Carlos; Gübitz, Georg M; Cavaco-Paulo, Artur

    2007-03-01

    The effects of ultrasound on 2,2'-Azinobis(3-ethylbenzothiazoline-6-sulfonate) enzymatic oxidation by laccase (Trametes villosa) has been studied by means of cyclic voltammetry. The reaction was allowed to proceed in the presence of a piece of wool and the coloration depth of the wool fabric was measured by means of K/S. It was observed that cyclic voltammetry is influenced the dyeing process and higher K/S values were obtained when the cyclic voltammetry was combined with the ultrasonic irradiation. Moreover, the K/S value is the sum of the values obtained when the wool staining is done in just the presence of cyclic voltammetry or in just the presence of ultrasound. The results obtained on the indigo carmine decolourization gives information on the importance of controlling the amount of ABTS(+) formed during the ultrasonication process.

  15. Structural and optical properties of zinc oxide doped by V2O5 synthesized by solid-state reaction

    Science.gov (United States)

    Abaira, R.; Dammak, T.; Matoussi, A.; Younes, A.

    2016-03-01

    Vanadium doped zinc oxide with different vanadium concentration were synthesized by conventional solid state reaction. The structural and optical properties of ZnO: V2O5 pellets were studied by using a panalytic diffraktometer (X'pert) with Cu-K radiation, the UV-visible spectrophotometer and photoluminescence (PL). X-ray diffraction (XRD) show that all the samples have a wurtzite structure and grow mainly in the (101) orientation, we show also the presence of dominated phase Zn3 (VO4)2, Optical studied indicate a decrease in optical band gap energy, and photoluminescence (PL) spectra showed a strong visible emission band, energy position and intensity of this emission depends on the temperature measurement. The activate energy Ea has been fitted and studied using Arunis equation.

  16. Modified Self-adaptive Immune Genetic Algorithm for Optimization of Combustion Side Reaction of p-Xylene Oxidation

    Institute of Scientific and Technical Information of China (English)

    陶莉莉; 孔祥东; 钟伟民; 钱锋

    2012-01-01

    In recent years, immune genetic algorithm (IGA) is gaining popularity for finding the optimal solution for non-linear optimization problems in many engineering applications. However, IGA with deterministic mutation factor suffers from the problem of premature convergence. In this study, a modified self-adaptive immune genetic algorithm (MSIGA) with two memory bases, in which immune concepts are applied to determine the mutation parameters, is proposed to improve the searching ability of the algorithm and maintain population diversity. Performance comparisons with other well-known population-based iterative algorithms show that the proposed method converges quickly to the global optimum and overcomes premature problem. This algorithm is applied to optimize a feed forward neural network to measure the content of products in the combustion side reaction of p-xylene oxidation, and satisfactory results are obtained.

  17. A promising green method in cyclization reaction.Oxidation of 3-methylcatechol in the presence of 1,10-phenanthroline

    Institute of Scientific and Technical Information of China (English)

    Davood Nematollahi; Bita Dadpou

    2011-01-01

    Electrochemical oxidation of 3-methylcatechol as a model compound has been studied in the presence of 1,10-phenanthroline as a bi-dentate nucleophile in water/acetonitrile (70/30, v/v) solution using cyclic voltammetry and controlled-potential coulometry. The results revealed that anodically generated 3-methylcyclohexa-3,5-diene-l,2-dione participates in inter and intramolecular Michael addition reactions with 1,10-phenanthroline and via an ECEC pathway converts to the corresponding heterocyclic compound. The present work has led to the development of a facile and one-pot method with high atom economy under ambient conditions and in an undivided cell using a carbon electrode.

  18. Photo-catalytic oxidation reaction of gaseous mercury over titanium dioxide nanoparticle surfaces

    Science.gov (United States)

    Snider, Graydon; Ariya, Parisa

    2010-05-01

    Hg 0(g) is known to undergo photo-catalytic oxidation by UVA-irradiated TiO 2 surfaces. One micrometre layers of TiO 2 on quartz glass were irradiated within the 240-800 nm range. Gaseous mercury was measured by mass spectrometry single ion monitoring. The surface configuration and elemental characterization of TiO 2 layer was evaluated using scanning electron microcopy with energy dispersive spectroscopy. The LH adsorption constant of was found to be KHg = (5.1 ± 2.4) × 10 -14 cm 3 and an apparent surface deposition rate of k = (7.4 ± 2.5) × 10 14 min -1 cm -2 under experimental conditions. Water did not affect the rate constant. We show TiO 2 could be employed to reduce mercury concentrations in gas streams, even at very high Hg 0 concentrations.

  19. Sulfur Poisoning of the Water Gas Shift Reaction on Anode Supported Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Hagen, Anke

    2013-01-01

    Investigation of fuels containing sulfur impurities is important regarding durability of solid oxide fuel cells (SOFC) because they are present in various potential fuels for SOFC applications. The effect of H2S in the ppm range on the performance of state-of-the-art anode supported SOFC at 850...... and 750°C is evaluated in either hydrogen/steam or hydrogen/steam/CO fuel. It was found that the poisoning effect is more severe in H2/H2O/CO vs. H2/H2O fuel. Only ∼8 ppm H2S can be allowed in the CO containing fuel without risking damage to the anode, whereas 90 ppm (or even more) is possible in H2/H2O...

  20. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane.

    Science.gov (United States)

    Rotavera, Brandon; Zádor, Judit; Welz, Oliver; Sheps, Leonid; Scheer, Adam M; Savee, John D; Akbar Ali, Mohamad; Lee, Taek Soon; Simmons, Blake A; Osborn, David L; Violi, Angela; Taatjes, Craig A

    2014-11-01

    Product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). Interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.